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NASSAU COMMUNITY
COLLEGE
CHE151 - GENERAL
CHEMISTRY I
Daniel Resch
Nassau Community College
OpenStax CNX
Chemistry (OpenStax)
Flowers, Theopold and Langley

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TABLE OF CONTENTS
Licensing
1: Essential Ideas of Chemistry

1.1: Chemistry in Context
1.2: Phases and Classification of Matter
1.3: Physical and Chemical Properties
1.4: Measurements
1.5: Measurement Uncertainty, Accuracy, and Precision
1.6: Mathematical Treatment of Measurement Results
1.E: Essential Ideas of Chemistry (Exercises)
2: Atoms, Molecules, and Ions

2.1: Prelude to Atoms
2.2: Early Ideas in Atomic Theory
2.3: Evolution of Atomic Theory
2.4: Atomic Structure and Symbolism
2.5: Chemical Formulas
2.6: The Periodic Table
2.7: Molecular and Ionic Compounds
2.8: Chemical Nomenclature
2.E: Atoms, Molecules, and Ions (Exercises)
3: Electronic Structure and Periodic Properties

3.1: Electromagnetic Energy
3.2: The Bohr Model
3.3: Development of Quantum Theory
3.4: Electronic Structure of Atoms (Electron Configurations)
3.5: Periodic Variations in Element Properties
3.E: Electronic Structure and Periodic Properties (Exercises)
4: Chemical Bonding and Molecular Geometry

4.1: Prelude to Chemical Bonding and Molecular Geometry
4.2: Ionic Bonding
4.3: Covalent Bonding
4.4: Lewis Symbols and Structures
4.5: Formal Charges and Resonance
4.6: Strengths of Ionic and Covalent Bonds
4.7: Molecular Structure and Polarity
4.E: Chemical Bonding and Molecular Geometry (Exercises)
5: Advanced Theories of Covalent Bonding

5.1: Prelude to Covalent Bonding
5.2: Valence Bond Theory
5.3: Hybrid Atomic Orbitals
5.4: Multiple Bonds
5.5: Molecular Orbital Theory
1 https://chem.libretexts.org/@go/page/210202
5.E: Advanced Theories of Covalent Bonding (Exercises)
6: Composition of Substances and Solutions

6.1: Formula Mass and the Mole Concept
6.2: Determining Empirical and Molecular Formulas
6.3: Molarity
6.4: Other Units for Solution Concentrations
6.E: Composition of Substances and Solutions (Exercises)
7: Stoichiometry of Chemical Reactions

7.1: Prelude to Stoichiometry
7.2: Writing and Balancing Chemical Equations
7.3: Classifying Chemical Reactions
7.4: Reaction Stoichiometry
7.5: Reaction Yields
7.6: Quantitative Chemical Analysis
7.E: Stoichiometry of Chemical Reactions (Exercises)
8: Gases
8.1: Gas Pressure
8.2: Relating Pressure, Volume, Amount, and Temperature- The Ideal Gas Law
8.3: Stoichiometry of Gaseous Substances, Mixtures, and Reactions
8.4: Effusion and Diffusion of Gases
8.5: The Kinetic-Molecular Theory
8.6: Non-Ideal Gas Behavior
8.E: Gases (Exercises)
9: Thermochemistry
9.1: Prelude to Thermochemistry
9.2: Energy Basics
9.3: Calorimetry
9.4: Enthalpy
9.E: Thermochemistry (Exercises)
10: Liquids and Solids

10.1: Prelude to Liquids and Solids
10.2: Intermolecular Forces
10.3: Properties of Liquids
10.4: Phase Transitions
10.5: Phase Diagrams
10.6: The Solid State of Matter
10.7: Lattice Structures in Crystalline Solids
10.E: Liquids and Solids (Exercises)
11: Solutions and Colloids

11.1: Prelude to Solutions and Colloids
11.2: The Dissolution Process
11.3: Electrolytes
11.4: Solubility
11.5: Colligative Properties
11.6: Colloids
11.E: Solutions and Colloids (Exercises)
12: Appendices
12.1: Composition of Commercial Acids and Bases
12.2: Essential Mathematics
12.3: Formation Constants for Complex Ions
12.4: Fundamental Physical Constants
12.5: Ionization Constants of Weak Acids
12.6: Ionization Constants of Weak Bases
12.7: Solubility Products
12.8: Standard Electrode (Half-Cell) Potentials
12.9: Standard Thermodynamic Properties for Selected Substances
12.11: Units and Conversion Factors
12.12: Water Properties
Index
Glossary
Detailed Licensing
Licensing
A detailed breakdown of this resource's licensing can be found in Back Matter/Detailed Licensing.
CHAPTER OVERVIEW
1: Essential Ideas of Chemistry
A general chemistry Libretexts Textbook remixed and remastered from

OpenStax's textbook:
General Chemistry
Most everything you do and encounter during your day involves chemistry. Making coffee, cooking eggs, and toasting bread
involve chemistry. The products you use—like soap and shampoo, the fabrics you wear, the electronics that keep you connected to
your world, the gasoline that propels your car—all of these and more involve chemical substances and processes. Whether you are
aware or not, chemistry is part of your everyday world. In this course, you will learn many of the essential principles underlying the
chemistry of modern-day life.
1.4: Measurements
Contributors
Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley
(Stephen F. Austin State University) with contributing authors. Textbook content produced by OpenStax College is licensed
under a Creative Commons Attribution License 4.0 license. Download for free at http://cnx.org/contents/85abf193-
[email protected]).
This page titled 1: Essential Ideas of Chemistry is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
1
 Learning Objectives
Outline the historical development of chemistry
Provide examples of the importance of chemistry in everyday life
Describe the scientific method and informs the scientific process
Differentiate among hypotheses, theories, and laws
Provide examples illustrating macroscopic, microscopic, and symbolic domains
Throughout human history, people have tried to convert matter into more useful forms. Our Stone Age ancestors chipped pieces of
flint into useful tools and carved wood into statues and toys. These endeavors involved changing the shape of a substance without
changing the substance itself. But as our knowledge increased, humans began to change the composition of the substances as well
—clay was converted into pottery, hides were cured to make garments, copper ores were transformed into copper tools and
weapons, and grain was made into bread.
Humans began to practice chemistry when they learned to control fire and use it to cook, make pottery, and smelt metals.
Subsequently, they began to separate and use specific components of matter. A variety of drugs such as aloe, myrrh, and opium
were isolated from plants. Dyes, such as indigo and Tyrian purple, were extracted from plant and animal matter. Metals were
combined to form alloys—for example, copper and tin were mixed together to make bronze—and more elaborate smelting
techniques produced iron. Alkalis were extracted from ashes, and soaps were prepared by combining these alkalis with fats.
Alcohol was produced by fermentation and purified by distillation.
Attempts to understand the behavior of matter extend back for more than 2500 years. As early as the sixth century BC, Greek
philosophers discussed a system in which water was the basis of all things. You may have heard of the Greek postulate that matter
consists of four elements: earth, air, fire, and water. Subsequently, an amalgamation of chemical technologies and philosophical
speculations were spread from Egypt, China, and the eastern Mediterranean by alchemists, who endeavored to transform “base
metals” such as lead into “noble metals” like gold, and to create elixirs to cure disease and extend life (Figure 1.1.1).
Figure 1.1.1 : This portrayal shows an alchemist’s workshop circa 1580. Although alchemy made some useful contributions to how
to manipulate matter, it was not scientific by modern standards. (credit: Chemical Heritage Foundation).
A sketch depicts 4 people stirring and handling chemicals. The chemicals are held in a variety of barrels and large cylinders.
Several of the containers are being heated over burning embers. A large stove in the laboratory is filled with burning embers. There
is also a large chest in the corner that is producing steam.
From alchemy came the historical progressions that led to modern chemistry: the isolation of drugs from natural sources,
metallurgy, and the dye industry. Today, chemistry continues to deepen our understanding and improve our ability to harness and
control the behavior of matter. This effort has been so successful that many people do not realize either the central position of
chemistry among the sciences or the importance and universality of chemistry in daily life.
Access for free at OpenStax 1.1.1 https://chem.libretexts.org/@go/page/207444

Chemistry: The Central Science
Chemistry is sometimes referred to as “the central science” due to its interconnectedness with a vast array of other STEM
disciplines (STEM stands for areas of study in the science, technology, engineering, and math fields). Chemistry and the language
of chemists play vital roles in biology, medicine, materials science, forensics, environmental science, and many other fields (Figure
1.1.2). The basic principles of physics are essential for understanding many aspects of chemistry, and there is extensive overlap
between many subdisciplines within the two fields, such as chemical physics and nuclear chemistry. Mathematics, computer
science, and information theory provide important tools that help us calculate, interpret, describe, and generally make sense of the
chemical world. Biology and chemistry converge in biochemistry, which is crucial to understanding the many complex factors and
processes that keep living organisms (such as us) alive. Chemical engineering, materials science, and nanotechnology combine
chemical principles and empirical findings to produce useful substances, ranging from gasoline to fabrics to electronics.
Agriculture, food science, veterinary science, and brewing and wine making help provide sustenance in the form of food and drink
to the world’s population. Medicine, pharmacology, biotechnology, and botany identify and produce substances that help keep us
healthy. Environmental science, geology, oceanography, and atmospheric science incorporate many chemical ideas to help us better
understand and protect our physical world. Chemical ideas are used to help understand the universe in astronomy and cosmology.
Figure 1.1.2 : Knowledge of chemistry is central to understanding a wide range of scientific disciplines. This diagram shows just
some of the interrelationships between chemistry and other fields.
A flowchart shows a box containing chemistry at its center. Chemistry is connected to geochemistry, nuclear chemistry, chemical
physics, nanoscience and nanotechnology, materials science, chemical engineering, biochemistry and molecular biology,
environmental science, agriculture, and mathematics. Each of these disciplines is further connected to other related fields including
medicine, biology, food science, geology earth sciences, toxicology, physics, and computer science.
What are some changes in matter that are essential to daily life? Digesting and assimilating food, synthesizing polymers that are
used to make clothing, containers, cookware, and credit cards, and refining crude oil into gasoline and other products are just a few
examples. As you proceed through this course, you will discover many different examples of changes in the composition and
structure of matter, how to classify these changes and how they occurred, their causes, the changes in energy that accompany them,
and the principles and laws involved. As you learn about these things, you will be learning chemistry, the study of the composition,
properties, and interactions of matter. The practice of chemistry is not limited to chemistry books or laboratories: It happens
whenever someone is involved in changes in matter or in conditions that may lead to such changes.
The Scientific Method

Chemistry is a science based on observation and experimentation. Doing chemistry involves attempting to answer questions and
explain observations in terms of the laws and theories of chemistry, using procedures that are accepted by the scientific community.
There is no single route to answering a question or explaining an observation, but there is an aspect common to every approach:
Each uses knowledge based on experiments that can be reproduced to verify the results. Some routes involve a hypothesis, a
tentative explanation of observations that acts as a guide for gathering and checking information. We test a hypothesis by
experimentation, calculation, and/or comparison with the experiments of others and then refine it as needed.
Some hypotheses are attempts to explain the behavior that is summarized in laws. The laws of science summarize a vast number of
experimental observations, and describe or predict some facet of the natural world. If such a hypothesis turns out to be capable of

explaining a large body of experimental data, it can reach the status of a theory. Scientific theories are well-substantiated,
comprehensive, testable explanations of particular aspects of nature. Theories are accepted because they provide satisfactory
explanations, but they can be modified if new data become available. The path of discovery that leads from question and
observation to law or hypothesis to theory, combined with experimental verification of the hypothesis and any necessary
modification of the theory, is called the scientific method (Figure 1.1.3).
In this flowchart, the observation and curiosity box has an arrow pointing to a box labeled form hypothesis; make prediction. A
curved arrow labeled next connects this box to a box labeled perform experiment; make more observations. Another arrow points
back to the box that says form hypothesis; make prediction. This arrow is labeled results not consistent with prediction. Another
arrow, labeled results are consistent with prediction points from the perform experiment box to a box labeled contributes to body of
knowledge. However, an arrow also points from contributes to body of knowledge back to the form hypothesis; make prediction
box. This arrow is labeled further testing does not support hypothesis. There are also two other arrows leading out from contributes
to body of knowledge. One arrow is labeled much additional testing yields constant observations. This leads to the observation
becomes law box. The other arrow is labeled much additional testing supports hypothesis. This arrow leads to the hypothesis
becomes theory box.
Figure 1.1.3 : The scientific method follows a process similar to the one shown in this diagram. All the key components are shown,
in roughly the right order. Scientific progress is seldom neat and clean: It requires open inquiry and the reworking of questions and
ideas in response to findings.
The Domains of Chemistry

Chemists study and describe the behavior of matter and energy in three different domains: macroscopic, microscopic, and
symbolic. These domains provide different ways of considering and describing chemical behavior.
Macro is a Greek word that means “large.” The macroscopic domain is familiar to us: It is the realm of everyday things that are
large enough to be sensed directly by human sight or touch. In daily life, this includes the food you eat and the breeze you feel on
your face. The macroscopic domain includes everyday and laboratory chemistry, where we observe and measure physical and
chemical properties, or changes such as density, solubility, and flammability.
The microscopic domain of chemistry is almost always visited in the imagination. Micro also comes from Greek and means
“small.” Some aspects of the microscopic domains are visible through a microscope, such as a magnified image of graphite or
bacteria. Viruses, for instance, are too small to be seen with the naked eye, but when we’re suffering from a cold, we’re reminded
of how real they are.
However, most of the subjects in the microscopic domain of chemistry—such as atoms and molecules—are too small to be seen
even with standard microscopes and often must be pictured in the mind. Other components of the microscopic domain include ions
and electrons, protons and neutrons, and chemical bonds, each of which is far too small to see. This domain includes the individual
metal atoms in a wire, the ions that compose a salt crystal, the changes in individual molecules that result in a color change, the
conversion of nutrient molecules into tissue and energy, and the evolution of heat as bonds that hold atoms together are created.
The symbolic domain contains the specialized language used to represent components of the macroscopic and microscopic
domains. Chemical symbols (such as those used in the periodic table), chemical formulas, and chemical equations are part of the
symbolic domain, as are graphs and drawings. We can also consider calculations as part of the symbolic domain. These symbols

play an important role in chemistry because they help interpret the behavior of the macroscopic domain in terms of the components
of the microscopic domain. One of the challenges for students learning chemistry is recognizing that the same symbols can
represent different things in the macroscopic and microscopic domains, and one of the features that makes chemistry fascinating is
the use of a domain that must be imagined to explain behavior in a domain that can be observed.
A helpful way to understand the three domains is via the essential and ubiquitous substance of water. That water is a liquid at
moderate temperatures, will freeze to form a solid at lower temperatures, and boil to form a gas at higher temperatures (Figure
1.1.4) are macroscopic observations. But some properties of water fall into the microscopic domain—what we cannot observe with
the naked eye. The description of water as comprised of two hydrogen atoms and one oxygen atom, and the explanation of freezing
and boiling in terms of attractions between these molecules, is within the microscopic arena. The formula H2O, which can describe
water at either the macroscopic or microscopic levels, is an example of the symbolic domain. The abbreviations (g) for gas, (s) for
solid, and (l) for liquid are also symbolic.
Figure 1.1.4 : (a) Moisture in the air, icebergs, and the ocean represent water in the macroscopic domain. (b) At the molecular level
(microscopic domain), gas molecules are far apart and disorganized, solid water molecules are close together and organized, and
liquid molecules are close together and disorganized. (c) The formula H2O symbolizes water, and (g), (s), and (l) symbolize its
phases. Note that clouds are actually comprised of either very small liquid water droplets or solid water crystals; gaseous water in
our atmosphere is not visible to the naked eye, although it may be sensed as humidity. (credit a: modification of work by
“Gorkaazk”/Wikimedia Commons).
Figure A shows a photo of an iceberg floating in a sea has three arrows. Each arrow points to figure B, which contains three
diagrams showing how the water molecules are organized in the air, ice, and sea. In the air, which contains the gaseous form of
water, H subscript 2 O gas, the water molecules are disconnected and widely spaced. In the ice, which is the solid form of water, H
subscript 2 O solid, the water molecules are bonded together into rings, with each ring containing six water molecules. Three of
these rings are connected to each other. In the sea, which is the liquid form of water, H subscript 2 O liquid, the water molecules are
very densely packed. The molecules are not bonded together.
Key Concepts and Summary

Chemistry deals with the composition, structure, and properties of matter, and the ways by which various forms of matter may be
interconverted. Thus, it occupies a central place in the study and practice of science and technology. Chemists use the scientific
method to perform experiments, pose hypotheses, and formulate laws and develop theories, so that they can better understand the
behavior of the natural world. To do so, they operate in the macroscopic, microscopic, and symbolic domains. Chemists measure,
analyze, purify, and synthesize a wide variety of substances that are important to our lives.
Glossary
chemistry
study of the composition, properties, and interactions of matter
hypothesis
tentative explanation of observations that acts as a guide for gathering and checking information
law
statement that summarizes a vast number of experimental observations, and describes or predicts some aspect of the natural
world

macroscopic domain
realm of everyday things that are large enough to sense directly by human sight and touch
microscopic domain
realm of things that are much too small to be sensed directly
scientific method
path of discovery that leads from question and observation to law or hypothesis to theory, combined with experimental
verification of the hypothesis and any necessary modification of the theory
symbolic domain
specialized language used to represent components of the macroscopic and microscopic domains, such as chemical symbols,
chemical formulas, chemical equations, graphs, drawings, and calculations
theory
well-substantiated, comprehensive, testable explanation of a particular aspect of nature
This page titled 1.1: Chemistry in Context is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
1.1: Chemistry in Context is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

Describe the basic properties of each physical state of matter: solid, liquid, and gas.
Define and give examples of atoms and molecules.
Classify matter as an element, compound, homogeneous mixture, or heterogeneous mixture with regard to its physical state
and composition.
Use symbolic, particulate, or macroscopic representations to describe or classify the different types of matter.
Distinguish between mass and weight.
Apply the law of conservation of matter.
Matter is defined as anything that occupies space and has mass, and it is all around us. Solids and liquids are more obviously
matter: We can see that they take up space, and their weight tells us that they have mass. Gases are also matter; if gases did not take
up space, a balloon would stay collapsed rather than inflate when filled with gas.
Solids, liquids, and gases are the three states of matter commonly found on earth (Figure 1.2.1). A solid is rigid and possesses a
definite shape. A liquid flows and takes the shape of a container, except that it forms a flat or slightly curved upper surface when
acted upon by gravity. (In zero gravity, liquids assume a spherical shape.) Both liquid and solid samples have volumes that are very
nearly independent of pressure. A gas takes both the shape and volume of its container.
Figure 1.2.1 : The three most common states or phases of matter are solid, liquid, and gas.
A beaker labeled solid contains a cube of red matter and says has fixed shape and volume. A beaker labeled liquid contains a
brownish-red colored liquid. This beaker says takes shape of container, forms horizontal surfaces, has fixed volume. The beaker
labeled gas is filled with a light brown gas. This beaker says expands to fill container.
A fourth state of matter, plasma, occurs naturally in the interiors of stars. A plasma is a gaseous state of matter that contains
appreciable numbers of electrically charged particles (Figure 1.2.2). The presence of these charged particles imparts unique
properties to plasmas that justify their classification as a state of matter distinct from gases. In addition to stars, plasmas are found
in some other high-temperature environments (both natural and man-made), such as lightning strikes, certain television screens,
and specialized analytical instruments used to detect trace amounts of metals.

Figure 1.2.2 : A plasma torch can be used to cut metal. (credit: “Hypertherm”/Wikimedia Commons)
A cutting torch is being used to cut a piece of metal. Bright, white colored plasma can be seen near the tip of the torch, where it is
contacting the metal.
What is Plasma?
Video 1.2.1 : In a tiny cell in a plasma television, the plasma emits ultraviolet light, which in turn causes the display at that
location to appear a specific color. The composite of these tiny dots of color makes up the image that you see. Watch this video to
learn more about plasma and the places you encounter it.
Some samples of matter appear to have properties of solids, liquids, and/or gases at the same time. This can occur when the sample
is composed of many small pieces. For example, we can pour sand as if it were a liquid because it is composed of many small
grains of solid sand. Matter can also have properties of more than one state when it is a mixture, such as with clouds. Clouds appear
to behave somewhat like gases, but they are actually mixtures of air (gas) and tiny particles of water (liquid or solid).
The mass of an object is a measure of the amount of matter in it. One way to measure an object’s mass is to measure the force it
takes to accelerate the object. It takes much more force to accelerate a car than a bicycle because the car has much more mass. A
more common way to determine the mass of an object is to use a balance to compare its mass with a standard mass.
Although weight is related to mass, it is not the same thing. Weight refers to the force that gravity exerts on an object. This force is
directly proportional to the mass of the object. The weight of an object changes as the force of gravity changes, but its mass does
not. An astronaut’s mass does not change just because she goes to the moon. But her weight on the moon is only one-sixth her
earth-bound weight because the moon’s gravity is only one-sixth that of the earth’s. She may feel “weightless” during her trip when
she experiences negligible external forces (gravitational or any other), although she is, of course, never “massless.”
The law of conservation of matter summarizes many scientific observations about matter: It states that there is no detectable
change in the total quantity of matter present when matter converts from one type to another (a chemical change) or changes
among solid, liquid, or gaseous states (a physical change). Brewing beer and the operation of batteries provide examples of the
conservation of matter (Figure 1.2.4). During the brewing of beer, the ingredients (water, yeast, grains, malt, hops, and sugar) are
converted into beer (water, alcohol, carbonation, and flavoring substances) with no actual loss of substance. This is most clearly
seen during the bottling process, when glucose turns into ethanol and carbon dioxide, and the total mass of the substances does not
change. This can also be seen in a lead-acid car battery: The original substances (lead, lead oxide, and sulfuric acid), which are

capable of producing electricity, are changed into other substances (lead sulfate and water) that do not produce electricity, with no
change in the actual amount of matter.
Figure 1.2.3 : (a) The mass of beer precursor materials is the same as the mass of beer produced: Sugar has become alcohol and
carbonation. (b) The mass of the lead, lead oxide plates, and sulfuric acid that goes into the production of electricity is exactly
equal to the mass of lead sulfate and water that is formed.
Diagram A shows a beer bottle containing pre-beer and sugar. An arrow points from this bottle to a second bottle. This second
bottle contains the same volume of liquid, however, the sugar has been converted into ethanol and carbonation as beer was made.
Diagram B shows a car battery that contains sheets of P B and P B O subscript 2 along with H subscript 2 S O subscript 4. After the
battery is used, it contains an equal mass of P B S O subscript 4 and H subscript 2 O.
Although this conservation law holds true for all conversions of matter, convincing examples are few and far between because,
outside of the controlled conditions in a laboratory, we seldom collect all of the material that is produced during a particular
conversion. For example, when you eat, digest, and assimilate food, all of the matter in the original food is preserved. But because
some of the matter is incorporated into your body, and much is excreted as various types of waste, it is challenging to verify by
measurement.
Atoms and Molecules

An atom is the smallest particle of an element that has the properties of that element and can enter into a chemical combination.
Consider the element gold, for example. Imagine cutting a gold nugget in half, then cutting one of the halves in half, and repeating
this process until a piece of gold remained that was so small that it could not be cut in half (regardless of how tiny your knife may
be). This minimally sized piece of gold is an atom (from the Greek atomos, meaning “indivisible”) (Figure 1.2.4). This atom would
no longer be gold if it were divided any further.
Figure 1.2.4 : (a) This photograph shows a gold nugget. (b) A scanning-tunneling microscope (STM) can generate views of the
surfaces of solids, such as this image of a gold crystal. Each sphere represents one gold atom. (credit a: modification of work by
United States Geological Survey; credit b: modification of work by “Erwinrossen”/Wikimedia Commons)
Figure A shows a gold nugget as it would appear to the naked eye. The gold nugget is very irregular, with many sharp edges. It
appears gold in color. The microscope image of a gold crystal shows many similarly sized gold stripes that are separated by dark
areas. Looking closely, one can see that the gold stripes are made of many, tiny, circular atoms.
The first suggestion that matter is composed of atoms is attributed to the Greek philosophers Leucippus and Democritus, who
developed their ideas in the 5th century BCE. However, it was not until the early nineteenth century that John Dalton (1766–1844),
a British schoolteacher with a keen interest in science, supported this hypothesis with quantitative measurements. Since that time,
repeated experiments have confirmed many aspects of this hypothesis, and it has become one of the central theories of chemistry.

Other aspects of Dalton’s atomic theory are still used but with minor revisions (details of Dalton’s theory are provided in the
chapter on atoms and molecules).
An atom is so small that its size is difficult to imagine. One of the smallest things we can see with our unaided eye is a single thread
of a spider web: These strands are about 1/10,000 of a centimeter (0.0001 cm) in diameter. Although the cross-section of one strand
is almost impossible to see without a microscope, it is huge on an atomic scale. A single carbon atom in the web has a diameter of
about 0.000000015 centimeter, and it would take about 7000 carbon atoms to span the diameter of the strand. To put this in
perspective, if a carbon atom were the size of a dime, the cross-section of one strand would be larger than a football field, which
would require about 150 million carbon atom “dimes” to cover it. (Figure 1.2.5) shows increasingly close microscopic and atomic-
level views of ordinary cotton.
Figure 1.2.5 : These images provide an increasingly closer view: (a) a cotton boll, (b) a single cotton fiber viewed under an optical
microscope (magnified 40 times), (c) an image of a cotton fiber obtained with an electron microscope (much higher magnification
than with the optical microscope); and (d and e) atomic-level models of the fiber (spheres of different colors represent atoms of
different elements). (credit c: modification of work by “Featheredtar”/Wikimedia Commons)
Figure A shows a puffy white cotton boll growing on a brown twig. Figure B shows a magnified cotton strand. The strand appears
transparent but contains dark areas within its interior. Figure C shows the surface of several crisscrossing and overlapping cotton
fibers. Its surface is rough along the edges but smooth near the center of each strand. Figure D shows three strands of molecules
connected into three vertical chains. Each strand contains about five molecules. Figure E shows that the cotton molecule contains
about a dozen atoms. The black carbon atoms form rings that are connected by red oxygen atoms. Many of the carbon atoms are
also bonded to hydrogen atoms, shown as white balls, or other oxygen atoms.
An atom is so light that its mass is also difficult to imagine. A billion lead atoms (1,000,000,000 atoms) weigh about 3 × 10 −13
grams, a mass that is far too light to be weighed on even the world’s most sensitive balances. It would require over
300,000,000,000,000 lead atoms (300 trillion, or 3 × 1014) to be weighed, and they would weigh only 0.0000001 gram.
It is rare to find collections of individual atoms. Only a few elements, such as the gases helium, neon, and argon, consist of a
collection of individual atoms that move about independently of one another. Other elements, such as the gases hydrogen, nitrogen,
oxygen, and chlorine, are composed of units that consist of pairs of atoms (Figure 1.2.6). One form of the element phosphorus
consists of units composed of four phosphorus atoms. The element sulfur exists in various forms, one of which consists of units
composed of eight sulfur atoms. These units are called molecules. A molecule consists of two or more atoms joined by strong
forces called chemical bonds. The atoms in a molecule move around as a unit, much like the cans of soda in a six-pack or a bunch
of keys joined together on a single key ring. A molecule may consist of two or more identical atoms, as in the molecules found in
the elements hydrogen, oxygen, and sulfur, or it may consist of two or more different atoms, as in the molecules found in water.
Each water molecule is a unit that contains two hydrogen atoms and one oxygen atom. Each glucose molecule is a unit that
contains 6 carbon atoms, 12 hydrogen atoms, and 6 oxygen atoms. Like atoms, molecules are incredibly small and light. If an
ordinary glass of water were enlarged to the size of the earth, the water molecules inside it would be about the size of golf balls.

Figure 1.2.6 : The elements hydrogen, oxygen, phosphorus, and sulfur form molecules consisting of two or more atoms of the same
element. The compounds water, carbon dioxide, and glucose consist of combinations of atoms of different elements.
The hydrogen molecule, H subscript 2, is shown as two small, white balls bonded together. The oxygen molecule O subscript 2, is
shown as two red balls bonded together. The phosphorous molecule, P subscript 4, is shown as four orange balls bonded tightly
together. The sulfur molecule, S subscript 8, is shown as 8 yellow balls linked together. Water molecules, H subscript 2 O, consist
of one red oxygen atom bonded to two smaller white hydrogen atoms. The hydrogen atoms are at an angle on the oxygen molecule.
Carbon dioxide, C O subscript 2, consists of one carbon atom and two oxygen atoms. One oxygen atom is bonded to the carbon’s
right side and the other oxygen is bonded to the carbon’s left side. Glucose, C subscript 6 H subscript 12 O subscript 6, contains a
chain of carbon atoms that have attached oxygen or hydrogen atoms.
Classifying Matter
We can classify matter into several categories. Two broad categories are mixtures and pure substances. A pure substance has a
constant composition. All specimens of a pure substance have exactly the same makeup and properties. Any sample of sucrose
(table sugar) consists of 42.1% carbon, 6.5% hydrogen, and 51.4% oxygen by mass. Any sample of sucrose also has the same
physical properties, such as melting point, color, and sweetness, regardless of the source from which it is isolated.
We can divide pure substances into two classes: elements and compounds. Pure substances that cannot be broken down into simpler
substances by chemical changes are called elements. Iron, silver, gold, aluminum, sulfur, oxygen, and copper are familiar examples
of the more than 100 known elements, of which about 90 occur naturally on the earth, and two dozen or so have been created in
laboratories.
Pure substances that can be broken down by chemical changes are called compounds. This breakdown may produce either elements
or other compounds, or both. Mercury(II) oxide, an orange, crystalline solid, can be broken down by heat into the elements
mercury and oxygen (Figure 1.2.7). When heated in the absence of air, the compound sucrose is broken down into the element
carbon and the compound water. (The initial stage of this process, when the sugar is turning brown, is known as caramelization—
this is what imparts the characteristic sweet and nutty flavor to caramel apples, caramelized onions, and caramel). Silver(I) chloride
is a white solid that can be broken down into its elements, silver and chlorine, by absorption of light. This property is the basis for
the use of this compound in photographic films and photochromic eyeglasses (those with lenses that darken when exposed to light).
Figure 1.2.7 : (a)The compound mercury(II) oxide, (b)when heated, (c) decomposes into silvery droplets of liquid mercury and
invisible oxygen gas. (credit: modification of work by Paul Flowers)
This figure shows a series of three photos labeled a, b, and c. Photo a shows the bottom of a test tube that is filled with an orange-
red substance. A slight amount of a silver substance is also visible. Photo b shows the substance in the test tube being heated over a
flame. Photo c shows a test tube that is not longer being heated. The orange-red substance is almost completely gone, and small,
silver droplets of a substance are left.
The properties of combined elements are different from those in the free, or uncombined, state. For example, white crystalline
sugar (sucrose) is a compound resulting from the chemical combination of the element carbon, which is a black solid in one of its
uncombined forms, and the two elements hydrogen and oxygen, which are colorless gases when uncombined. Free sodium, an
element that is a soft, shiny, metallic solid, and free chlorine, an element that is a yellow-green gas, combine to form sodium
chloride (table salt), a compound that is a white, crystalline solid.

A mixture is composed of two or more types of matter that can be present in varying amounts and can be separated by physical
changes, such as evaporation (you will learn more about this later). A mixture with a composition that varies from point to point is
called a heterogeneous mixture. Italian dressing is an example of a heterogeneous mixture (Figure 1.2.1a). Its composition can
vary because we can make it from varying amounts of oil, vinegar, and herbs. It is not the same from point to point throughout the
mixture—one drop may be mostly vinegar, whereas a different drop may be mostly oil or herbs because the oil and vinegar
separate and the herbs settle. Other examples of heterogeneous mixtures are chocolate chip cookies (we can see the separate bits of
chocolate, nuts, and cookie dough) and granite (we can see the quartz, mica, feldspar, and more).
A homogeneous mixture, also called a solution, exhibits a uniform composition and appears visually the same throughout. An
example of a solution is a sports drink, consisting of water, sugar, coloring, flavoring, and electrolytes mixed together uniformly
(Figure 1.2.1b). Each drop of a sports drink tastes the same because each drop contains the same amounts of water, sugar, and other
components. Note that the composition of a sports drink can vary—it could be made with somewhat more or less sugar, flavoring,
or other components, and still be a sports drink. Other examples of homogeneous mixtures include air, maple syrup, gasoline, and a
solution of salt in water.
Figure 1.2.7 : (a) Oil and vinegar salad dressing is a heterogeneous mixture because its composition is not uniform throughout. (b)
A commercial sports drink is a homogeneous mixture because its composition is uniform throughout. (credit a “left”: modification
of work by John Mayer; credit a “right”: modification of work by Umberto Salvagnin; credit b “left: modification of work by Jeff
Bedford)
Diagram A shows a glass containing a red liquid with a layer of yellow oil floating on the surface of the red liquid. A zoom in box
is magnifying a portion of the red liquid that contains some of the yellow oil. The zoomed in image shows that oil is forming round
droplets within the red liquid. Diagram B shows a photo of Gatorade G 2. A zoom in box is magnifying a portion of the Gatorade,
which is uniformly red.
Although there are just over 100 elements, tens of millions of chemical compounds result from different combinations of these
elements. Each compound has a specific composition and possesses definite chemical and physical properties by which we can
distinguish it from all other compounds. And, of course, there are innumerable ways to combine elements and compounds to form
different mixtures. A summary of how to distinguish between the various major classifications of matter is shown in (Figure 1.2.8).
Figure 1.2.8 : Depending on its properties, a given substance can be classified as a homogeneous mixture, a heterogeneous mixture,
a compound, or an element.
This flow chart begins with matter at the top and the question: does the matter have constant properties and composition? If no,
then it is a mixture. This leads to the next question: is it uniform throughout? If no, it is heterogeneous. If yes, it is homogenous. If
the matter does have constant properties and composition, it is a pure substance. This leads to the next question: can it be simplified
chemically? If no, it is an element. If yes, then it is a compound.
Eleven elements make up about 99% of the earth’s crust and atmosphere (Table 1.2.1). Oxygen constitutes nearly one-half and
silicon about one-quarter of the total quantity of these elements. A majority of elements on earth are found in chemical
combinations with other elements; about one-quarter of the elements are also found in the free state.
Table 1.2.1 : Elemental Composition of Earth
Element Symbol Percent Mass Element Symbol Percent Mass

Element Symbol Percent Mass Element Symbol Percent Mass
oxygen O 49.20 chlorine Cl 0.19
silicon Si 25.67 phosphorus P 0.11
aluminum Al 7.50 manganese Mn 0.09
iron Fe 4.71 carbon C 0.08
calcium Ca 3.39 sulfur S 0.06
sodium Na 2.63 barium Ba 0.04
potassium K 2.40 nitrogen N 0.03
magnesium Mg 1.93 fluorine F 0.03
hydrogen H 0.87 strontium Sr 0.02
titanium Ti 0.58 all others - 0.47
Decomposition of Water / Production of Hydrogen

Water consists of the elements hydrogen and oxygen combined in a 2 to 1 ratio. Water can be broken down into hydrogen and
oxygen gases by the addition of energy. One way to do this is with a battery or power supply, as shown in (Figure 1.2.9).
Figure 1.2.9 : The decomposition of water is shown at the macroscopic, microscopic, and symbolic levels. The battery provides an
electric current (microscopic) that decomposes water. At the macroscopic level, the liquid separates into the gases hydrogen (on the
left) and oxygen (on the right). Symbolically, this change is presented by showing how liquid H2O separates into H2 and O2 gases.
A rectangular battery is immersed in a beaker filled with liquid. Each of the battery terminals are covered by an overturned test
tube. The test tubes each contain a bubbling liquid. Zoom in areas indicate that the liquid in the beaker is water, 2 H subscript 2 O
liquid. The bubbles in the test tube over the negative terminal are hydrogen gas, 2 H subscript 2 gas. The bubbles in the test tube
over the positive terminal are oxygen gas, O subscript 2 gas.
The breakdown of water involves a rearrangement of the atoms in water molecules into different molecules, each composed of two
hydrogen atoms and two oxygen atoms, respectively. Two water molecules form one oxygen molecule and two hydrogen
molecules. The representation for what occurs, 2 H O(l) → 2 H (g) + O (g) , will be explored in more depth in later chapters.
2 2 2
The two gases produced have distinctly different properties. Oxygen is not flammable but is required for combustion of a fuel, and
hydrogen is highly flammable and a potent energy source. How might this knowledge be applied in our world? One application
involves research into more fuel-efficient transportation. Fuel-cell vehicles (FCV) run on hydrogen instead of gasoline (Figure
1.2.10). They are more efficient than vehicles with internal combustion engines, are nonpolluting, and reduce greenhouse gas
emissions, making us less dependent on fossil fuels. FCVs are not yet economically viable, however, and current hydrogen
production depends on natural gas. If we can develop a process to economically decompose water, or produce hydrogen in another
environmentally sound way, FCVs may be the way of the future.

Figure 1.2.10 : A fuel cell generates electrical energy from hydrogen and oxygen via an electrochemical process and produces only
water as the waste product.
The fuel cell consists of a proton exchange membrane sandwiched between an anode and a cathode. Hydrogen gas enters the
battery near the anode. Oxygen gas enters the battery near the cathode. The entering hydrogen gas is broken up into single white
spheres that each have a positive charge. These are protons. The protons repel negatively-charged electrons within the anode. These
electrons travel through a circuit, providing electricity to anything attached to the battery. The protons continue through the proton
exchange membrane and through the cathode to reach the oxygen gas molecules at the opposite end of the battery. There, the
oxygen atoms split up into single red spheres. Each oxygen atom takes on two of the incoming protons to form a water molecule.
Chemistry of Cell Phones

Imagine how different your life would be without cell phones (Figure 1.2.11) and other smart devices. Cell phones are made from
numerous chemical substances, which are extracted, refined, purified, and assembled using an extensive and in-depth
understanding of chemical principles. About 30% of the elements that are found in nature are found within a typical smart phone.
The case/body/frame consists of a combination of sturdy, durable polymers comprised primarily of carbon, hydrogen, oxygen, and
nitrogen [acrylonitrile butadiene styrene (ABS) and polycarbonate thermoplastics], and light, strong, structural metals, such as
aluminum, magnesium, and iron. The display screen is made from a specially toughened glass (silica glass strengthened by the
addition of aluminum, sodium, and potassium) and coated with a material to make it conductive (such as indium tin oxide). The
circuit board uses a semiconductor material (usually silicon); commonly used metals like copper, tin, silver, and gold; and more
unfamiliar elements such as yttrium, praseodymium, and gadolinium. The battery relies upon lithium ions and a variety of other
materials, including iron, cobalt, copper, polyethylene oxide, and polyacrylonitrile.
Figure 1.2.11 : Almost one-third of naturally occurring elements are used to make a modern cell phone. (credit: modification of
work by John Taylor)
A cell phone is labeled to show what its components are made of. The case components are made of polymers such as A B S and or
metals such as aluminum, iron, and magnesium. The processor components are made of silicon, common metals such as copper, tin
and gold, and uncommon elements such as yttrium and gadolinium. The screen components are made of silicon oxide, also known
as glass. The glass is strengthened by the addition of aluminum, sodium, and potassium. The battery components contain lithium
combined with other metals such as cobalt, iron, and copper.

Summary
Matter is anything that occupies space and has mass. The basic building block of matter is the atom, the smallest unit of an element
that can enter into combinations with atoms of the same or other elements. In many substances, atoms are combined into
molecules. On earth, matter commonly exists in three states: solids, of fixed shape and volume; liquids, of variable shape but fixed
volume; and gases, of variable shape and volume. Under high-temperature conditions, matter also can exist as a plasma. Most
matter is a mixture: It is composed of two or more types of matter that can be present in varying amounts and can be separated by
physical means. Heterogeneous mixtures vary in composition from point to point; homogeneous mixtures have the same
composition from point to point. Pure substances consist of only one type of matter. A pure substance can be an element, which
consists of only one type of atom and cannot be broken down by a chemical change, or a compound, which consists of two or more
types of atoms.
Glossary
atom
smallest particle of an element that can enter into a chemical combination
compound
pure substance that can be decomposed into two or more elements
element
substance that is composed of a single type of atom; a substance that cannot be decomposed by a chemical change
gas
state in which matter has neither definite volume nor shape
heterogeneous mixture
combination of substances with a composition that varies from point to point
homogeneous mixture
(also, solution) combination of substances with a composition that is uniform throughout
liquid
state of matter that has a definite volume but indefinite shape
law of conservation of matter

when matter converts from one type to another or changes form, there is no detectable change in the total amount of matter
present
mass
fundamental property indicating amount of matter
matter
anything that occupies space and has mass
mixture
matter that can be separated into its components by physical means
molecule
bonded collection of two or more atoms of the same or different elements
plasma
gaseous state of matter containing a large number of electrically charged atoms and/or molecules
pure substance
homogeneous substance that has a constant composition

solid
state of matter that is rigid, has a definite shape, and has a fairly constant volume
weight
force that gravity exerts on an object
This page titled 1.2: Phases and Classification of Matter is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
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Describe the difference between physical and chemical properties or changed.
Identify a property or transformation as either physical or chemical using symbolic, particulate, or macroscopic
representations.
Identify the properties of matter as extensive or intensive.
Recognize and describe the parts of the NFPA hazard diamond.
The characteristics that enable us to distinguish one substance from another are called properties. A physical property is a
characteristic of matter that is not associated with a change in its chemical composition. Familiar examples of physical properties
include density, color, hardness, melting and boiling points, and electrical conductivity. We can observe some physical properties,
such as density and color, without changing the physical state of the matter observed. Other physical properties, such as the melting
temperature of iron or the freezing temperature of water, can only be observed as matter undergoes a physical change. A physical
change is a change in the state or properties of matter without any accompanying change in its chemical composition (the identities
of the substances contained in the matter). We observe a physical change when wax melts, when sugar dissolves in coffee, and
when steam condenses into liquid water (Figure 1.3.1). Other examples of physical changes include magnetizing and
demagnetizing metals (as is done with common antitheft security tags) and grinding solids into powders (which can sometimes
yield noticeable changes in color). In each of these examples, there is a change in the physical state, form, or properties of the
substance, but no change in its chemical composition.
Figure 1.3.1 : (a) Wax undergoes a physical change when solid wax is heated and forms liquid wax. (b) Steam condensing inside a
cooking pot is a physical change, as water vapor is changed into liquid water. (credit a: modification of work by
“95jb14”/Wikimedia Commons; credit b: modification of work by “mjneuby”/Flickr).
The change of one type of matter into another type (or the inability to change) is a chemical property. Examples of chemical
properties include flammability, toxicity, acidity, reactivity (many types), and heat of combustion. Iron, for example, combines with
oxygen in the presence of water to form rust; chromium does not oxidize (Figure 1.3.2). Nitroglycerin is very dangerous because it
explodes easily; neon poses almost no hazard because it is very unreactive.
Figure 1.3.2 : (a) One of the chemical properties of iron is that it rusts; (b) one of the chemical properties of chromium is that it
does not. (credit a: modification of work by Tony Hisgett; credit b: modification of work by “Atoma”/Wikimedia Commons)
Comparison of two metal equipments. The first image shows a rusted brown appearance and the following image shows a shiny
metallic appearance.

To identify a chemical property, we look for a chemical change. A chemical change always produces one or more types of matter
that differ from the matter present before the change. The formation of rust is a chemical change because rust is a different kind of
matter than the iron, oxygen, and water present before the rust formed. The explosion of nitroglycerin is a chemical change because
the gases produced are very different kinds of matter from the original substance. Other examples of chemical changes include
reactions that are performed in a lab (such as copper reacting with nitric acid), all forms of combustion (burning), and food being
cooked, digested, or rotting (Figure 1.3.3).
Figure 1.3.3 : (a) Copper and nitric acid undergo a chemical change to form copper nitrate and brown, gaseous nitrogen dioxide. (b)
During the combustion of a match, cellulose in the match and oxygen from the air undergo a chemical change to form carbon
dioxide and water vapor. (c) Cooking red meat causes a number of chemical changes, including the oxidation of iron in myoglobin
that results in the familiar red-to-brown color change. (d) A banana turning brown is a chemical change as new, darker (and less
tasty) substances form. (credit b: modification of work by Jeff Turner; credit c: modification of work by Gloria Cabada-Leman;
credit d: modification of work by Roberto Verzo)
Four pictures. A. a flask with copper wires placed in a blue solution and also the presence of a gas. B. A lighted match. C. meat
cubes being cooked on a pan. D. Bananas forming black spots on its peel.
Properties of matter fall into one of two categories. If the property depends on the amount of matter present, it is an extensive
property. The mass and volume of a substance are examples of extensive properties; for instance, a gallon of milk has a larger mass
and volume than a cup of milk. The value of an extensive property is directly proportional to the amount of matter in question. If
the property of a sample of matter does not depend on the amount of matter present, it is an intensive property. Temperature is an
example of an intensive property. If the gallon and cup of milk are each at 20 °C (room temperature), when they are combined, the
temperature remains at 20 °C. As another example, consider the distinct but related properties of heat and temperature. A drop of
hot cooking oil spattered on your arm causes brief, minor discomfort, whereas a pot of hot oil yields severe burns. Both the drop
and the pot of oil are at the same temperature (an intensive property), but the pot clearly contains much more heat (extensive
property).
Hazard Diamond
You may have seen the symbol shown in Figure 1.3.4 on containers of chemicals in a laboratory or workplace. Sometimes called a
“fire diamond” or “hazard diamond,” this chemical hazard diamond provides valuable information that briefly summarizes the
various dangers of which to be aware when working with a particular substance.

Figure 1.3.4 : The National Fire Protection Agency (NFPA) hazard diamond summarizes the major hazards of a chemical
substance.
The National Fire Protection Agency (NFPA) 704 Hazard Identification System was developed by NFPA to provide safety
information about certain substances. The system details flammability, reactivity, health, and other hazards. Within the overall
diamond symbol, the top (red) diamond specifies the level of fire hazard (temperature range for flash point). The blue (left)
diamond indicates the level of health hazard. The yellow (right) diamond describes reactivity hazards, such as how readily the
substance will undergo detonation or a violent chemical change. The white (bottom) diamond points out special hazards, such as if
it is an oxidizer (which allows the substance to burn in the absence of air/oxygen), undergoes an unusual or dangerous reaction with
water, is corrosive, acidic, alkaline, a biological hazard, radioactive, and so on. Each hazard is rated on a scale from 0 to 4, with 0
being no hazard and 4 being extremely hazardous.
While many elements differ dramatically in their chemical and physical properties, some elements have similar properties. We can
identify sets of elements that exhibit common behaviors. For example, many elements conduct heat and electricity well, whereas
others are poor conductors. These properties can be used to sort the elements into three classes: metals (elements that conduct
well), nonmetals (elements that conduct poorly), and metalloids (elements that have properties of both metals and nonmetals).
The periodic table is a table of elements that places elements with similar properties close together (Figure 1.3.5 ). You will learn
more about the periodic table as you continue your study of chemistry.

Figure 1.3.5 : The periodic table shows how elements may be grouped according to certain similar properties. Note the background
color denotes whether an element is a metal, metalloid, or nonmetal, whereas the element symbol color indicates whether it is a
solid, liquid, or gas.
Summary
All substances have distinct physical and chemical properties, and may undergo physical or chemical changes. Physical properties,
such as hardness and boiling point, and physical changes, such as melting or freezing, do not involve a change in the composition
of matter. Chemical properties, such flammability and acidity, and chemical changes, such as rusting, involve production of matter
that differs from that present beforehand.
Measurable properties fall into one of two categories. Extensive properties depend on the amount of matter present, for example,
the mass of gold. Intensive properties do not depend on the amount of matter present, for example, the density of gold. Heat is an
example of an extensive property, and temperature is an example of an intensive property.
Glossary
chemical change
change producing a different kind of matter from the original kind of matter
chemical property
behavior that is related to the change of one kind of matter into another kind of matter
extensive property
property of a substance that depends on the amount of the substance
intensive property
property of a substance that is independent of the amount of the substance
physical change
change in the state or properties of matter that does not involve a change in its chemical composition
physical property

characteristic of matter that is not associated with any change in its chemical composition
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1.4: Measurements
Explain the process of measurement and describe the three basic parts of a quantity.
Describe the properties and units of length, mass, volume, density, temperature, and time.
Recognize the common unit prefixes and use them to describe the magnitude of a measurement.
Describe and calculate the density of a substance.
Perform basic unit calculations and conversions in the metric and other unit systems.
Measurements provide the macroscopic information that is the basis of most of the hypotheses, theories, and laws that describe the
behavior of matter and energy in both the macroscopic and microscopic domains of chemistry. Every measurement provides three
kinds of information: the size or magnitude of the measurement (a number); a standard of comparison for the measurement (a unit);
and an indication of the uncertainty of the measurement. While the number and unit are explicitly represented when a quantity is
written, the uncertainty is an aspect of the measurement result that is more implicitly represented and will be discussed later.
The number in the measurement can be represented in different ways, including decimal form and scientific notation. For example,
the maximum takeoff weight of a Boeing 777-200ER airliner is 298,000 kilograms, which can also be written as 2.98 × 105 kg.
The mass of the average mosquito is about 0.0000025 kilograms, which can be written as 2.5 × 10−6 kg.
Units, such as liters, pounds, and centimeters, are standards of comparison for measurements. When we buy a 2-liter bottle of a soft
drink, we expect that the volume of the drink was measured, so it is two times larger than the volume that everyone agrees to be 1
liter. The meat used to prepare a 0.25-pound hamburger is measured so it weighs one-fourth as much as 1 pound. Without units, a
number can be meaningless, confusing, or possibly life threatening. Suppose a doctor prescribes phenobarbital to control a patient’s
seizures and states a dosage of “100” without specifying units. Not only will this be confusing to the medical professional giving
the dose, but the consequences can be dire: 100 mg given three times per day can be effective as an anticonvulsant, but a single
dose of 100 g is more than 10 times the lethal amount.
We usually report the results of scientific measurements in SI units, an updated version of the metric system, using the units listed
in Table 1.4.1. Other units can be derived from these base units. The standards for these units are fixed by international agreement,
and they are called the International System of Units or SI Units (from the French, Le Système International d’Unités). SI units
have been used by the United States National Institute of Standards and Technology (NIST) since 1964.
Table 1.4.1 : Base Units of the SI System
Property Measured Name of Unit Symbol of Unit
length meter m
mass kilogram kg
time second s
temperature kelvin K
electric current ampere A
amount of substance mole mol
luminous intensity candela cd
Sometimes we use units that are fractions or multiples of a base unit. Ice cream is sold in quarts (a familiar, non-SI base unit), pints
(0.5 quart), or gallons (4 quarts). We also use fractions or multiples of units in the SI system, but these fractions or multiples are
always powers of 10. Fractional or multiple SI units are named using a prefix and the name of the base unit. For example, a length
of 1000 meters is also called a kilometer because the prefix kilo means “one thousand,” which in scientific notation is 103 (1
kilometer = 1000 m = 103 m). The prefixes used and the powers to which 10 are raised are listed in Table 1.4.2.
NG, equals 4 times ten to the negative 9, or 0.000000004 g. The prefix micro has the greek letter mu as its symbol and a factor of
10 to the negative sixth power. Therefore, 1 microliter, or mu L, is equal to one times ten to the negative 6 or 0.000001 L. The
prefix milli has a lowercase M as its symbol and a factor of 10 to the negative third power. Therefore, 2 millimoles, or M mol, are
equal to two times ten to the negative 3 or 0.002 mol. The prefix centi has a lowercase C as its symbol and a factor of 10 to the

negative second power. Therefore, 7 centimeters, or C M, are equal to seven times ten to the negative 2 meters or 0.07 M O L. The
prefix deci has a lowercase D as its symbol and a factor of 10 to the negative first power. Therefore, 1 deciliter, or lowercase D
uppercase L, are equal to one times ten to the negative 1 meters or 0.1 L. The prefix kilo has a lowercase K as its symbol and a
factor of 10 to the third power. Therefore, 1 kilometer, or K M, is equal to one times ten to the third meters or 1000 M. The prefix
mega has an uppercase M as its symbol and a factor of 10 to the sixth power. Therefore, 3 megahertz, or M H Z, are equal to three
times 10 to the sixth hertz, or 3000000 H Z. The prefix giga has an uppercase G as its symbol and a factor of 10 to the ninth power.
Therefore, 8 gigayears, or G Y R, are equal to eight times 10 to the ninth years, or 800000000 G Y R. The prefix tera has an
uppercase T as its symbol and a factor of 10 to the twelfth power. Therefore, 5 terawatts, or T W, are equal to five times 10 to the
twelfth watts, or 5000000000000 W." data-quail-id="64" data-mt-width="1076">
Table 1.4.2 : Common Unit Prefixes
Prefix Symbol Factor Example
1 femtosecond (fs) = 1 × 10−15 s

femto f 10−15
(0.000000000000001 s)
1 picometer (pm) = 1 × 10−12 m
pico p 10−12
(0.000000000001 m)
4 nanograms (ng) = 4 × 10−9 g
nano n 10−9
(0.000000004 g)
1 microliter (μL) = 1 × 10−6 L
micro µ 10−6
(0.000001 L)
2 millimoles (mmol) = 2 × 10−3
milli m 10−3
mol (0.002 mol)
7 centimeters (cm) = 7 × 10−2 m
centi c 10−2
(0.07 m)
1 deciliter (dL) = 1 × 10−1 L (0.1
deci d 10−1
L)
1 kilometer (km) = 1 × 103 m
kilo k 103
(1000 m)
3 megahertz (MHz) = 3 × 106 Hz
mega M 106
(3,000,000 Hz)
8 gigayears (Gyr) = 8 × 109 yr
giga G 109
(8,000,000,000 Gyr)
5 terawatts (TW) = 5 × 1012 W
tera T 1012
(5,000,000,000,000 W)
SI Base Units
The initial units of the metric system, which eventually evolved into the SI system, were established in France during the French
Revolution. The original standards for the meter and the kilogram were adopted there in 1799 and eventually by other countries.
This section introduces four of the SI base units commonly used in chemistry. Other SI units will be introduced in subsequent
chapters.
Length
The standard unit of length in both the SI and original metric systems is the meter (m). A meter was originally specified as
1/10,000,000 of the distance from the North Pole to the equator. It is now defined as the distance light in a vacuum travels in
1/299,792,458 of a second. A meter is about 3 inches longer than a yard (Figure 1.4.1); one meter is about 39.37 inches or 1.094
yards. Longer distances are often reported in kilometers (1 km = 1000 m = 103 m), whereas shorter distances can be reported in
centimeters (1 cm = 0.01 m = 10−2 m) or millimeters (1 mm = 0.001 m = 10−3 m).

Figure 1.4.1 : The relative lengths of 1 m, 1 yd, 1 cm, and 1 in. are shown (not actual size), as well as comparisons of 2.54 cm and 1
in., and of 1 m and 1.094 yd.
A ruler is shown with various lengths of black line shown above it to compare the relative lengths of 1 inch, meter, centimeter, and
yard.
Mass
The standard unit of mass in the SI system is the kilogram (kg). A kilogram was originally defined as the mass of a liter of water (a
cube of water with an edge length of exactly 0.1 meter). It is now defined by a certain cylinder of platinum-iridium alloy, which is
kept in France (Figure 1.4.2). Any object with the same mass as this cylinder is said to have a mass of 1 kilogram. One kilogram is
about 2.2 pounds. The gram (g) is exactly equal to 1/1000 of the mass of the kilogram (10−3 kg).
Figure 1.4.2 : This replica prototype kilogram is housed at the National Institute of Standards and Technology (NIST) in Maryland.
(credit: National Institutes of Standards and Technology).
Temperature
Temperature is an intensive property. The SI unit of temperature is the kelvin (K). The IUPAC convention is to use kelvin (all
lowercase) for the word, K (uppercase) for the unit symbol, and neither the word “degree” nor the degree symbol (°). The degree
Celsius (°C) is also allowed in the SI system, with both the word “degree” and the degree symbol used for Celsius measurements.
Celsius degrees are the same magnitude as those of kelvin, but the two scales place their zeros in different places. Water freezes at
273.15 K (0 °C) and boils at 373.15 K (100 °C) by definition, and normal human body temperature is approximately 310 K (37
°C). The conversion between these two units and the Fahrenheit scale will be discussed later in this chapter.
Time
The SI base unit of time is the second (s). Small and large time intervals can be expressed with the appropriate prefixes; for
example, 3 microseconds = 0.000003 s = 3 × 10−6 and 5 megaseconds = 5,000,000 s = 5 × 106 s. Alternatively, hours, days, and
years can be used.
Derived SI Units
We can derive many units from the seven SI base units. For example, we can use the base unit of length to define a unit of volume,
and the base units of mass and length to define a unit of density.

Volume
Volume is the measure of the amount of space occupied by an object. The standard SI unit of volume is defined by the base unit of
length (Figure 1.4.3). The standard volume is a cubic meter (m3), a cube with an edge length of exactly one meter. To dispense a
cubic meter of water, we could build a cubic box with edge lengths of exactly one meter. This box would hold a cubic meter of
water or any other substance.
Figure 1.4.3 : (a) The relative volumes are shown for cubes of 1 m3, 1 dm3 (1 L), and 1 cm3 (1 mL) (not to scale). (b) The diameter
of a dime is compared relative to the edge length of a 1-cm3 (1-mL) cube.
A more commonly used unit of volume is derived from the decimeter (0.1 m, or 10 cm). A cube with edge lengths of exactly one
decimeter contains a volume of one cubic decimeter (dm3). A liter (L) is the more common name for the cubic decimeter. One liter
is about 1.06 quarts. A cubic centimeter (cm3) is the volume of a cube with an edge length of exactly one centimeter. The
abbreviation cc (for cubic centimeter) is often used by health professionals. A cubic centimeter is also called a milliliter (mL) and is
1/1000 of a liter.
Density
We use the mass and volume of a substance to determine its density. Thus, the units of density are defined by the base units of mass
and length.
The density of a substance is the ratio of the mass of a sample of the substance to its volume. The SI unit for density is the kilogram
per cubic meter (kg/m3). For many situations, however, this as an inconvenient unit, and we often use grams per cubic centimeter
(g/cm3) for the densities of solids and liquids, and grams per liter (g/L) for gases. Although there are exceptions, most liquids and
solids have densities that range from about 0.7 g/cm3 (the density of gasoline) to 19 g/cm3 (the density of gold). The density of air
is about 1.2 g/L. Table 1.4.3 shows the densities of some common substances.
Table 1.4.3 : Densities of Common Substances
Solids Liquids Gases (at 25 °C and 1 atm)
ice (at 0 °C) 0.92 g/cm3 water 1.0 g/cm3 dry air 1.20 g/L
oak (wood) 0.60–0.90 g/cm3 ethanol 0.79 g/cm3 oxygen 1.31 g/L
iron 7.9 g/cm3 acetone 0.79 g/cm3 nitrogen 1.14 g/L
copper 9.0 g/cm3 glycerin 1.26 g/cm3 carbon dioxide 1.80 g/L
lead 11.3 g/cm3 olive oil 0.92 g/cm3 helium 0.16 g/L
silver 10.5 g/cm3 gasoline 0.70–0.77 g/cm3 neon 0.83 g/L
gold 19.3 g/cm3 mercury 13.6 g/cm3 radon 9.1 g/L
While there are many ways to determine the density of an object, perhaps the most straightforward method involves separately
finding the mass and volume of the object, and then dividing the mass of the sample by its volume. In the following example, the
mass is found directly by weighing, but the volume is found indirectly through length measurements.
mass
density =
volume

 Example 1.4.1
Calculation of Density Gold—in bricks, bars, and coins—has been a form of currency for centuries. In order to swindle people
into paying for a brick of gold without actually investing in a brick of gold, people have considered filling the centers of
hollow gold bricks with lead to fool buyers into thinking that the entire brick is gold. It does not work: Lead is a dense
substance, but its density is not as great as that of gold, 19.3 g/cm3. What is the density of lead if a cube of lead has an edge
length of 2.00 cm and a mass of 90.7 g?
Solution
The density of a substance can be calculated by dividing its mass by its volume. The volume of a cube is calculated by cubing
the edge length.
3
volume of lead cube = 2.00 cm × 2.00 cm × 2.00 cm = 8.00 cm
mass 90.7 g 11.3 g 3

density = = = = 11.3 g/cm
3
volume 8.00 cm 1.00 cm3
(We will discuss the reason for rounding to the first decimal place in the next section.)
 Exercise 1.4.1
a. To three decimal places, what is the volume of a cube (cm3) with an edge length of 0.843 cm?
b. If the cube in part (a) is copper and has a mass of 5.34 g, what is the density of copper to two decimal places?
Answer a
0.599 cm3;
Answer b
8.91 g/cm3
 Example 1.4.2: Using Displacement of Water to Determine Density
This PhET simulation illustrates another way to determine density, using displacement of water. Determine the density of the
red and yellow blocks.
Solution
When you open the density simulation and select Same Mass, you can choose from several 5.00-kg colored blocks that you can
drop into a tank containing 100.00 L water. The yellow block floats (it is less dense than water), and the water level rises to
105.00 L. While floating, the yellow block displaces 5.00 L water, an amount equal to the weight of the block. The red block
sinks (it is more dense than water, which has density = 1.00 kg/L), and the water level rises to 101.25 L.
The red block therefore displaces 1.25 L water, an amount equal to the volume of the block. The density of the red block is:
mass 5.00 kg
density = = = 4.00 kg/L
volume 1.25 L
Note that since the yellow block is not completely submerged, you cannot determine its density from this information. But if
you hold the yellow block on the bottom of the tank, the water level rises to 110.00 L, which means that it now displaces 10.00
L water, and its density can be found:
mass 5.00 kg
density = = = 0.500 kg/L
volume 10.00 L

 Exercise 1.4.1
Remove all of the blocks from the water and add the green block to the tank of water, placing it approximately in the middle of
the tank. Determine the density of the green block.
Answer
2.00 kg/L
Summary
Measurements provide quantitative information that is critical in studying and practicing chemistry. Each measurement has an
amount, a unit for comparison, and an uncertainty. Measurements can be represented in either decimal or scientific notation.
Scientists primarily use the SI (International System) or metric systems. We use base SI units such as meters, seconds, and
kilograms, as well as derived units, such as liters (for volume) and g/cm3 (for density). In many cases, we find it convenient to use
unit prefixes that yield fractional and multiple units, such as microseconds (10−6 seconds) and megahertz (106 hertz), respectively.
Key Equations
mass
density =
volume
Glossary
Celsius (°C)
unit of temperature; water freezes at 0 °C and boils at 100 °C on this scale
cubic centimeter (cm3 or cc)

volume of a cube with an edge length of exactly 1 cm
cubic meter (m3)

SI unit of volume
density
ratio of mass to volume for a substance or object
kelvin (K)
SI unit of temperature; 273.15 K = 0 ºC
kilogram (kg)
standard SI unit of mass; 1 kg = approximately 2.2 pounds
length
measure of one dimension of an object
liter (L)
(also, cubic decimeter) unit of volume; 1 L = 1,000 cm3
meter (m)
standard metric and SI unit of length; 1 m = approximately 1.094 yards
milliliter (mL)
1/1,000 of a liter; equal to 1 cm3
second (s)
SI unit of time
SI units (International System of Units)

standards fixed by international agreement in the International System of Units (Le Système International d’Unités)
unit
standard of comparison for measurements
volume
amount of space occupied by an object
This page titled 1.4: Measurements is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
1.4: Measurements is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

Compare and contrast exact and uncertain numbers.
Correctly represent uncertainty in quantities using significant figures.
Identify the number of significant figures in value.
Solve problems that involve various calculations and report the results with the appropriate number of significant figures.
Apply proper rounding rules to computed quantities
Define accuracy and precision, and use accuracy and precision to describe data sets.
Counting is the only type of measurement that is free from uncertainty, provided the number of objects being counted does not
change while the counting process is underway. The result of such a counting measurement is an example of an exact number. If
we count eggs in a carton, we know exactly how many eggs the carton contains. The numbers of defined quantities are also exact.
By definition, 1 foot is exactly 12 inches, 1 inch is exactly 2.54 centimeters, and 1 gram is exactly 0.001 kilogram. Quantities
derived from measurements other than counting, however, are uncertain to varying extents due to practical limitations of the
measurement process used.
Significant Figures in Measurement

The numbers of measured quantities, unlike defined or directly counted quantities, are not exact. To measure the volume of liquid
in a graduated cylinder, you should make a reading at the bottom of the meniscus, the lowest point on the curved surface of the
liquid.
Figure 1.5.1 : To measure the volume of liquid in this graduated cylinder, you must mentally subdivide the distance between the 21
and 22 mL marks into tenths of a milliliter, and then make a reading (estimate) at the bottom of the meniscus.
A 25 millilter graduated cylinder filled with liquid. The markings on the cylinders is zoomed in to show the bottom of the meniscus
between 21 and 22 milliliters.
Refer to the illustration in Figure 1.5.1. The bottom of the meniscus in this case clearly lies between the 21 and 22 markings,
meaning the liquid volume is certainly greater than 21 mL but less than 22 mL. The meniscus appears to be a bit closer to the 22-
mL mark than to the 21-mL mark, and so a reasonable estimate of the liquid’s volume would be 21.6 mL. In the number 21.6, then,
the digits 2 and 1 are certain, but the 6 is an estimate. Some people might estimate the meniscus position to be equally distant from
each of the markings and estimate the tenth-place digit as 5, while others may think it to be even closer to the 22-mL mark and
estimate this digit to be 7. Note that it would be pointless to attempt to estimate a digit for the hundredths place, given that the
tenths-place digit is uncertain. In general, numerical scales such as the one on this graduated cylinder will permit measurements to
one-tenth of the smallest scale division. The scale in this case has 1-mL divisions, and so volumes may be measured to the nearest
0.1 mL.

This concept holds true for all measurements, even if you do not actively make an estimate. If you place a quarter on a standard
electronic balance, you may obtain a reading of 6.72 g. The digits 6 and 7 are certain, and the 2 indicates that the mass of the
quarter is likely between 6.71 and 6.73 grams. The quarter weighs about 6.72 grams, with a nominal uncertainty in the
measurement of ± 0.01 gram. If we weigh the quarter on a more sensitive balance, we may find that its mass is 6.723 g. This means
its mass lies between 6.722 and 6.724 grams, an uncertainty of 0.001 gram. Every measurement has some uncertainty, which
depends on the device used (and the user’s ability). All of the digits in a measurement, including the uncertain last digit, are called
significant figures or significant digits. Note that zero may be a measured value; for example, if you stand on a scale that shows
weight to the nearest pound and it shows “120,” then the 1 (hundreds), 2 (tens) and 0 (ones) are all significant (measured) values.
Whenever you make a measurement properly, all the digits in the result are significant. But what if you were analyzing a reported
value and trying to determine what is significant and what is not? Well, for starters, all nonzero digits are significant, and it is only
zeros that require some thought. We will use the terms “leading,” “trailing,” and “captive” for the zeros and will consider how to
deal with them.
The left diagram uses the example of 3090. The zero in the hundreds place is labeled “captive” and the zero in the ones place is
labeled trailing. The right diagram uses the example 0.008020. The three zeros in the ones, tenths, and hundredths places are
labeled “leading.” The zero in the ten-thousandths place is labeled “captive” and the zero in the millionths place is labeled
“trailing.”
Starting with the first nonzero digit on the left, count this digit and all remaining digits to the right. This is the number of
significant figures in the measurement unless the last digit is a trailing zero lying to the left of the decimal point.
The left diagram uses the example of 1267 meters. The number 1 is the first nonzero figure on the left. 1267 has 4 significant
figures in total. The right diagram uses the example of 55.0 grams. The number 5 in the tens place is the first nonzero figure on the
left. 55.0 has 3 significant figures. Note that the 0 is to the right of the decimal point and therefore is a significant figure.
Captive zeros result from measurement and are therefore always significant. Leading zeros, however, are never significant—they
merely tell us where the decimal point is located.
The left diagram uses the example of 70.607 milliliters. The number 7 is the first nonzero figure on the left. 70.607 has 5
significant figures in total, as all figures are measured including the 2 zeros. The right diagram uses the example of 0.00832407 M
L. The number 8 is the first nonzero figure on the left. 0.00832407 has 6 significant figures.
The leading zeros in this example are not significant. We could use exponential notation (as described in Appendix B) and express
the number as 8.32407 × 10−3; then the number 8.32407 contains all of the significant figures, and 10−3 locates the decimal point.
The number of significant figures is uncertain in a number that ends with a zero to the left of the decimal point location. The zeros
in the measurement 1,300 grams could be significant or they could simply indicate where the decimal point is located. The
ambiguity can be resolved with the use of exponential notation: 1.3 × 103 (two significant figures), 1.30 × 103 (three significant
figures, if the tens place was measured), or 1.300 × 103 (four significant figures, if the ones place was also measured). In cases
where only the decimal-formatted number is available, it is prudent to assume that all trailing zeros are not significant.

This figure uses the example of 1300 grams. The one and the 3 are significant figures as they are clearly the result of measurement.
The 2 zeros could be significant if they were measured or they could be placeholders.
When determining significant figures, be sure to pay attention to reported values and think about the measurement and significant
figures in terms of what is reasonable or likely—that is, whether the value makes sense. For example, the official January 2014
census reported the resident population of the US as 317,297,725. Do you think the US population was correctly determined to the
reported nine significant figures, that is, to the exact number of people? People are constantly being born, dying, or moving into or
out of the country, and assumptions are made to account for the large number of people who are not actually counted. Because of
these uncertainties, it might be more reasonable to expect that we know the population to within perhaps a million or so, in which
case the population should be reported as 317 million, or 3.17 × 10 people.
8
Significant Figures in Calculations

A second important principle of uncertainty is that results calculated from a measurement are at least as uncertain as the
measurement itself. We must take the uncertainty in our measurements into account to avoid misrepresenting the uncertainty in
calculated results. One way to do this is to report the result of a calculation with the correct number of significant figures, which is
determined by the following three rules for rounding numbers:
1. When we add or subtract numbers, we should round the result to the same number of decimal places as the number with the
least number of decimal places (the least precise value in terms of addition and subtraction).
2. When we multiply or divide numbers, we should round the result to the same number of digits as the number with the least
number of significant figures (the least precise value in terms of multiplication and division).
3. If the digit to be dropped (the one immediately to the right of the digit to be retained) is less than 5, we “round down” and leave
the retained digit unchanged; if it is more than 5, we “round up” and increase the retained digit by 1; if the dropped digit is 5,
we round up or down, whichever yields an even value for the retained digit. (The last part of this rule may strike you as a bit
odd, but it’s based on reliable statistics and is aimed at avoiding any bias when dropping the digit “5,” since it is equally close to
both possible values of the retained digit.)
The following examples illustrate the application of this rule in rounding a few different numbers to three significant figures:
0.028675 rounds “up” to 0.0287 (the dropped digit, 7, is greater than 5)
18.3384 rounds “down” to 18.3 (the dropped digit, 3, is less than 5)
6.8752 rounds “up” to 6.88 (the dropped digit is 5, and the retained digit is even)
92.85 rounds “down” to 92.8 (the dropped digit is 5, and the retained digit is even)
Let’s work through these rules with a few examples.
 Example 1.5.1: Rounding Numbers
Round the following to the indicated number of significant figures:

a. 31.57 (to two significant figures)
b. 8.1649 (to three significant figures)
c. 0.051065 (to four significant figures)
d. 0.90275 (to four significant figures)
Solution
a. 31.57 rounds “up” to 32 (the dropped digit is 5, and the retained digit is even)
b. 8.1649 rounds “down” to 8.16 (the dropped digit, 4, is less than 5)
c. 0.051065 rounds “down” to 0.05106 (the dropped digit is 5, and the retained digit is even)
d. 0.90275 rounds “up” to 0.9028 (the dropped digit is 5, and the retained digit is even)

 Exercise 1.5.1
Round the following to the indicated number of significant figures:
a. 0.424 (to two significant figures)
b. 0.0038661 (to three significant figures)
c. 421.25 (to four significant figures)
d. 28,683.5 (to five significant figures)
Answer a
0.42
Answer b
0.00387
Answer c
421.2
Answer d
28,684
 Example 1.5.2: Addition and Subtraction with Significant Figures Rule:
When we add or subtract numbers, we should round the result to the same number of decimal places as the number with the
least number of decimal places (i.e., the least precise value in terms of addition and subtraction).
a. Add 1.0023 g and 4.383 g.
b. Subtract 421.23 g from 486 g.
Solution
(a)
1.0023 g
+ 4.383 g
––––––––
5.3853 g
Answer is 5.385 g (round to the thousandths place; three decimal places)

(b)
486 g
− 421.23 g
––––––––
64.77 g
Answer is 65 g (round to the ones place; no decimal places)

 Exercise 1.5.2
a. Add 2.334 mL and 0.31 mL.
b. Subtract 55.8752 m from 56.533 m.
Answer a
2.64 mL
Answer b
0.658 m
 Example 1.5.3: Multiplication and Division with Significant Figures
Rule: When we multiply or divide numbers, we should round the result to the same number of digits as the number with the
least number of significant figures (the least precise value in terms of multiplication and division).
a. Multiply 0.6238 cm by 6.6 cm.
b. Divide 421.23 g by 486 mL.
Solution
(a)
2 2
0.6238 cm × 6.6 cm = 4.11708 cm → result is 4.1 cm (round to two significant figures)
four significant figures × two significant figures → two significant figures answer
(b)
421.23 g
= 0.86728... g/mL → result is 0.867 g/mL (round to three significant figures)
486 mL
f ive signif icant f igures

→ three signif icant f igures answer
three signif icant f igures
 Exercise 1.5.3
a. Multiply 2.334 cm and 0.320 cm.
b. Divide 55.8752 m by 56.53 s.
Answer a
0.747 cm2
Answer b
0.9884 m/s
In the midst of all these technicalities, it is important to keep in mind the reason why we use significant figures and rounding rules
—to correctly represent the certainty of the values we report and to ensure that a calculated result is not represented as being more
certain than the least certain value used in the calculation.
 Example 1.5.4: Calculation with Significant Figures
One common bathtub is 13.44 dm long, 5.920 dm wide, and 2.54 dm deep. Assume that the tub is rectangular and calculate its
approximate volume in liters.

Solution
V = l×w ×d
= 13.44 dm × 5.920 dm × 2.54 dm

3
= 202.09459...dm (value from calculator)
3
= 202 dm , or 202 L (answer rounded to three significant figures)
 Exercise 1.5.4: Determination of Density Using Water Displacement
What is the density of a liquid with a mass of 31.1415 g and a volume of 30.13 cm3?
Answer
1.034 g/mL
 Example 1.5.4
A piece of rebar is weighed and then submerged in a graduated cylinder partially filled with water, with results as shown.
A graduated cylinder filled with liquid is shown. One shows the level before the rebar is added and the other shows the level
with the rebar submerged in the liquid. Rebar mass is 69.658 grams, final volume is 22.4 milliliters, and initial volume is 13.5
milliliters.
a. Use these values to determine the density of this piece of rebar.
b. Rebar is mostly iron. Does your result in (a) support this statement? How?
Solution
The volume of the piece of rebar is equal to the volume of the water displaced:
3
volume = 22.4 mL − 13.5 mL = 8.9 mL = 8.9 cm
(rounded to the nearest 0.1 mL, per the rule for addition and subtraction)
The density is the mass-to-volume ratio:
mass 69.658 g
3
density = = = 7.8 g/cm
3
volume 8.9 cm
(rounded to two significant figures, per the rule for multiplication and division)
The density of iron is 7.9 g/cm3, very close to that of rebar, which lends some support to the fact that rebar is mostly iron.

 Exercise 1.5.4
An irregularly shaped piece of a shiny yellowish material is weighed and then submerged in a graduated cylinder, with results
as shown.
A graduated cylinder filled with liquid is shown. One shows the level before the material is added and the other shows the level
with the material submerged in the liquid. Mass is 51.842 grams, final volume is 19.8 milliliters, and initial volume is 17.1
milliliters.
a. Use these values to determine the density of this material.
b. Do you have any reasonable guesses as to the identity of this material? Explain your reasoning.
Answer a
19 g/cm3
Answer b
It is likely gold; it has the right appearance for gold and very close to the density given for gold.
Accuracy and Precision

Scientists typically make repeated measurements of a quantity to ensure the quality of their findings and to know both the precision
and the accuracy of their results. Measurements are said to be precise if they yield very similar results when repeated in the same
manner. A measurement is considered accurate if it yields a result that is very close to the true or accepted value. Precise values
agree with each other; accurate values agree with a true value. These characterizations can be extended to other contexts, such as
the results of an archery competition (Figure 1.5.2).
Figure 1.5.2 : (a) These arrows are close to both the bull’s eye and one another, so they are both accurate and precise. (b) These
arrows are close to one another but not on target, so they are precise but not accurate. (c) These arrows are neither on target nor
close to one another, so they are neither accurate nor precise.
Suppose a quality control chemist at a pharmaceutical company is tasked with checking the accuracy and precision of three
different machines that are meant to dispense 10 ounces (296 mL) of cough syrup into storage bottles. She proceeds to use each

machine to fill five bottles and then carefully determines the actual volume dispensed, obtaining the results tabulated in Table
1.5.2.
Table 1.5.2 : Volume (mL) of Cough Medicine Delivered by 10-oz (296 mL) Dispensers
Dispenser #1 Dispenser #2 Dispenser #3
283.3 298.3 296.1
284.1 294.2 295.9
283.9 296.0 296.1
284.0 297.8 296.0
284.1 293.9 296.1
Considering these results, she will report that dispenser #1 is precise (values all close to one another, within a few tenths of a
milliliter) but not accurate (none of the values are close to the target value of 296 mL, each being more than 10 mL too low).
Results for dispenser #2 represent improved accuracy (each volume is less than 3 mL away from 296 mL) but worse precision
(volumes vary by more than 4 mL). Finally, she can report that dispenser #3 is working well, dispensing cough syrup both
accurately (all volumes within 0.1 mL of the target volume) and precisely (volumes differing from each other by no more than 0.2
mL).
Summary
Quantities can be exact or measured. Measured quantities have an associated uncertainty that is represented by the number of
significant figures in the measurement. The uncertainty of a calculated value depends on the uncertainties in the values used in the
calculation and is reflected in how the value is rounded. Measured values can be accurate (close to the true value) and/or precise
(showing little variation when measured repeatedly).
Glossary
uncertainty
estimate of amount by which measurement differs from true value
significant figures
(also, significant digits) all of the measured digits in a determination, including the uncertain last digit
rounding
procedure used to ensure that calculated results properly reflect the uncertainty in the measurements used in the calculation
precision
how closely a measurement matches the same measurement when repeated
exact number
number derived by counting or by definition
accuracy
how closely a measurement aligns with a correct value
This page titled 1.5: Measurement Uncertainty, Accuracy, and Precision is shared under a CC BY license and was authored, remixed, and/or
curated by OpenStax.
1.5: Measurement Uncertainty, Accuracy, and Precision is licensed CC BY 4.0. Original source:
https://openstax.org/details/books/chemistry-2e.

Explain the dimensional analysis (factor label) approach to mathematical calculations involving quantities.
Describe how to use dimensional analysis to carry out unit conversions for a given property and computations involving two or more properties.
Convert between the three main temperature units: Fahrenheit, Celsius, and Kelvin.
It is often the case that a quantity of interest may not be easy (or even possible) to measure directly but instead must be calculated from other directly measured properties and appropriate
mathematical relationships. For example, consider measuring the average speed of an athlete running sprints. This is typically accomplished by measuring the time required for the athlete to run from
the starting line to the finish line, and the distance between these two lines, and then computing speed from the equation that relates these three properties:
distance
speed =
time
An Olympic-quality sprinter can run 100 m in approximately 10 s, corresponding to an average speed of

100 m
= 10 m/s
10 s
Note that this simple arithmetic involves dividing the numbers of each measured quantity to yield the number of the computed quantity (100/10 = 10) and likewise dividing the units of each measured
quantity to yield the unit of the computed quantity (m/s = m/s). Now, consider using this same relation to predict the time required for a person running at this speed to travel a distance of 25 m. The
same relation between the three properties is used, but in this case, the two quantities provided are a speed (10 m/s) and a distance (25 m). To yield the sought property, time, the equation must be
rearranged appropriately:
distance
time =
speed
The time can then be computed as:

25 m
= 2.5 s
10 m/s
Again, arithmetic on the numbers (25/10 = 2.5) was accompanied by the same arithmetic on the units (m/m/s = s) to yield the number and unit of the result, 2.5 s. Note that, just as for numbers, when
a unit is divided by an identical unit (in this case, m/m), the result is “1”—or, as commonly phrased, the units “cancel.”
These calculations are examples of a versatile mathematical approach known as dimensional analysis (or the factor-label method). Dimensional analysis is based on this premise: the units of quantities
must be subjected to the same mathematical operations as their associated numbers. This method can be applied to computations ranging from simple unit conversions to more complex, multi-step
calculations involving several different quantities.
Conversion Factors and Dimensional Analysis

A ratio of two equivalent quantities expressed with different measurement units can be used as a unit conversion factor. For example, the lengths of 2.54 cm and 1 in. are equivalent (by definition),
and so a unit conversion factor may be derived from the ratio,
2.54 cm cm
(2.54 cm = 1 in. ) or 2.54
1 in. in.
Several other commonly used conversion factors are given in Table 1.6.1.
Table 1.6.1 : Common Conversion Factors
Length Volume Mass
1 m = 1.0936 yd 1 L = 1.0567 qt 1 kg = 2.2046 lb
1 in. = 2.54 cm (exact) 1 qt = 0.94635 L 1 lb = 453.59 g
1 km = 0.62137 mi 1 ft3 = 28.317 L 1 (avoirdupois) oz = 28.349 g
1 mi = 1609.3 m 1 tbsp = 14.787 mL 1 (troy) oz = 31.103 g
When we multiply a quantity (such as distance given in inches) by an appropriate unit conversion factor, we convert the quantity to an equivalent value with different units (such as distance in
centimeters). For example, a basketball player’s vertical jump of 34 inches can be converted to centimeters by:
2.54 cm
34 in. × = 86 cm
1 in.
Since this simple arithmetic involves quantities, the premise of dimensional analysis requires that we multiply both numbers and units. The numbers of these two quantities are multiplied to yield the
number of the product quantity, 86, whereas the units are multiplied to yield
in. ×cm
.
in.
Just as for numbers, a ratio of identical units is also numerically equal to one,
in.
=1
in.
and the unit product thus simplifies to cm. (When identical units divide to yield a factor of 1, they are said to “cancel.”) Using dimensional analysis, we can determine that a unit conversion factor has
been set up correctly by checking to confirm that the original unit will cancel, and the result will contain the sought (converted) unit.
 Example 1.6.1: Using a Unit Conversion Factor
The mass of a competition Frisbee is 125 g. Convert its mass to ounces using the unit conversion factor derived from the relationship 1 oz = 28.349 g (Table 1.6.1).
Solution
If we have the conversion factor, we can determine the mass in kilograms using an equation similar the one used for converting length from inches to centimeters.
x oz = 125 g × unit conversion f actor
We write the unit conversion factor in its two forms:

1 oz 28.349 g
and
28.349 g 1 oz
The correct unit conversion factor is the ratio that cancels the units of grams and leaves ounces.
1 oz
x oz = 125 g ×
28.349 g
125
=( ) oz
28.349
= 4.41 oz (three signif icant f igures)
 Exercise 1.6.1
Convert a volume of 9.345 qt to liters.
Answer
8.844 L
Beyond simple unit conversions, the factor-label method can be used to solve more complex problems involving computations. Regardless of the details, the basic approach is the same—all the
factors involved in the calculation must be appropriately oriented to insure that their labels (units) will appropriately cancel and/or combine to yield the desired unit in the result. This is why it is
referred to as the factor-label method. As your study of chemistry continues, you will encounter many opportunities to apply this approach.
 Example 1.6.2: Computing Quantities from Measurement Results
What is the density of common antifreeze in units of g/mL? A 4.00-qt sample of the antifreeze weighs 9.26 lb.
Solution
mass
Since density = , we need to divide the mass in grams by the volume in milliliters. In general: the number of units of B = the number of units of A × unit conversion factor. The
volume
necessary conversion factors are given in Table 1.7.1: 1 lb = 453.59 g; 1 L = 1.0567 qt; 1 L = 1,000 mL. We can convert mass from pounds to grams in one step:
453.59 g
3
9.26 lb × = 4.20 × 10 g
1 lb
We need to use two steps to convert volume from quarts to milliliters.

1. Convert quarts to liters.
1 L
4.00 qt × = 3.78 L
1.0567 qt
2. Convert liters to milliliters.

1000 mL 3
3.78 L × = 3.78 × 10 mL
1 L
Then,
3
4.20 × 10 g
density = = 1.11 g/mL
3
3.78 × 10 mL
Alternatively, the calculation could be set up in a way that uses three unit conversion factors sequentially as follows:
9.26 lb 1.0567 qt 1 L
453.59 g
× × × = 1.11 g/mL
4.00 qt 1 L 1000 mL
1 lb
 Exercise 1.6.2
What is the volume in liters of 1.000 oz, given that 1 L = 1.0567 qt and 1 qt = 32 oz (exactly)?
Answer
−2
2.956 × 10 L
 Example 1.6.3: Computing Quantities from Measurement Results
While being driven from Philadelphia to Atlanta, a distance of about 1250 km, a 2014 Lamborghini Aventador Roadster uses 213 L gasoline.
a. What (average) fuel economy, in miles per gallon, did the Roadster get during this trip?
b. If gasoline costs $3.80 per gallon, what was the fuel cost for this trip?
Solution
(a) We first convert distance from kilometers to miles:
0.62137 mi
1250 km × = 777 mi
1 km
and then convert volume from liters to gallons:
1.0567 qt
1 gal
213 L × × = 56.3 gal
1 L 4 qt
Then,

777 mi
(average) mileage = = 13.8 miles/gallon = 13.8 mpg
56.3 gal
Alternatively, the calculation could be set up in a way that uses all the conversion factors sequentially, as follows:
1250 km 0.62137 mi 1 L 4 qt
× × × = 13.8 mpg
213 L 1 km 1.0567 qt 1 gal
(b) Using the previously calculated volume in gallons, we find:

$3.80
56.3 gal × = $214
1 gal
 Exercise 1.6.3
A Toyota Prius Hybrid uses 59.7 L gasoline to drive from San Francisco to Seattle, a distance of 1300 km (two significant digits).
a. What (average) fuel economy, in miles per gallon, did the Prius get during this trip?
b. If gasoline costs $3.90 per gallon, what was the fuel cost for this trip?
Answer a
51 mpg
Answer b
$62
Conversion of Temperature Units

We use the word temperature to refer to the hotness or coldness of a substance. One way we measure a change in temperature is to use the fact that most substances expand when their temperature
increases and contract when their temperature decreases. The mercury or alcohol in a common glass thermometer changes its volume as the temperature changes. Because the volume of the liquid
changes more than the volume of the glass, we can see the liquid expand when it gets warmer and contract when it gets cooler.
To mark a scale on a thermometer, we need a set of reference values: Two of the most commonly used are the freezing and boiling temperatures of water at a specified atmospheric pressure. On the
Celsius scale, 0 °C is defined as the freezing temperature of water and 100 °C as the boiling temperature of water. The space between the two temperatures is divided into 100 equal intervals, which
we call degrees. On the Fahrenheit scale, the freezing point of water is defined as 32 °F and the boiling temperature as 212 °F. The space between these two points on a Fahrenheit thermometer is
divided into 180 equal parts (degrees).
Defining the Celsius and Fahrenheit temperature scales as described in the previous paragraph results in a slightly more complex relationship between temperature values on these two scales than for
different units of measure for other properties. Most measurement units for a given property are directly proportional to one another (y = mx). Using familiar length units as one example:
1 ft
length in f eet = ( ) × length in inches
12 in.
where
y = length in feet,
x = length in inches, and
the proportionality constant, m, is the conversion factor.
The Celsius and Fahrenheit temperature scales, however, do not share a common zero point, and so the relationship between these two scales is a linear one rather than a proportional one (
y = mx + b ). Consequently, converting a temperature from one of these scales into the other requires more than simple multiplication by a conversion factor, m, it also must take into account
differences in the scales’ zero points (b ).

The linear equation relating Celsius and Fahrenheit temperatures is easily derived from the two temperatures used to define each scale. Representing the Celsius temperature as x and the Fahrenheit
temperature as y , the slope, m, is computed to be:
Δy
m =
Δx
∘ ∘
212 F − 32 F
=
∘ ∘
100 C −0 C
∘
180 F
=
∘
100 C
∘
9 F
=
∘
5 C
The y-intercept of the equation, b, is then calculated using either of the equivalent temperature pairs, (100 °C, 212 °F) or (0 °C, 32 °F), as:
b = y − mx
∘
∘
9 F ∘
= 32 F− ×0 C
∘
5 C
∘
= 32 F
The equation relating the temperature scales is then:

∘
9 F
∘
T∘ F = ( × T∘ C ) + 32 C
∘
5 C
An abbreviated form of this equation that omits the measurement units is:
9
T∘ F = × T∘ C + 32
5
Rearrangement of this equation yields the form useful for converting from Fahrenheit to Celsius:
5
T∘ C = (T∘ F + 32)
9
As mentioned earlier in this chapter, the SI unit of temperature is the kelvin (K). Unlike the Celsius and Fahrenheit scales, the kelvin scale is an absolute temperature scale in which 0 (zero) K
corresponds to the lowest temperature that can theoretically be achieved. The early 19th-century discovery of the relationship between a gas's volume and temperature suggested that the volume of a

gas would be zero at −273.15 °C. In 1848, British physicist William Thompson, who later adopted the title of Lord Kelvin, proposed an absolute temperature scale based on this concept (further
treatment of this topic is provided in this text’s chapter on gases).
The freezing temperature of water on this scale is 273.15 K and its boiling temperature 373.15 K. Notice the numerical difference in these two reference temperatures is 100, the same as for the
K
Celsius scale, and so the linear relation between these two temperature scales will exhibit a slope of 1 ∘
. Following the same approach, the equations for converting between the kelvin and Celsius
C
temperature scales are derived to be:
TK = T∘ C + 273.15
T∘ C = TK − 273.15
The 273.15 in these equations has been determined experimentally, so it is not exact. Figure 1.6.1 shows the relationship among the three temperature scales. Recall that we do not use the degree sign
with temperatures on the kelvin scale.
Figure 1.6.1 : The Fahrenheit, Celsius, and kelvin temperature scales are compared.
Although the kelvin (absolute) temperature scale is the official SI temperature scale, Celsius is commonly used in many scientific contexts and is the scale of choice for nonscience contexts in almost
all areas of the world. Very few countries (the U.S. and its territories, the Bahamas, Belize, Cayman Islands, and Palau) still use Fahrenheit for weather, medicine, and cooking.
 Example 1.6.4: Conversion from Celsius
Normal body temperature has been commonly accepted as 37.0 °C (although it varies depending on time of day and method of measurement, as well as among individuals). What is this
temperature on the kelvin scale and on the Fahrenheit scale?
Solution
∘
K= C + 273.15 = 37.0 + 273.2 = 310.2 K
9 9
∘ ∘ ∘
F = C + 32.0 = ( × 37.0) + 32.0 = 66.6 + 32.0 = 98.6 F
5 5
 Exercise 1.6.4
Convert 80.92 °C to K and °F.
Answer
354.07 K, 177.7 °F
 Example 1.6.5: Conversion from Fahrenheit
Baking a ready-made pizza calls for an oven temperature of 450 °F. If you are in Europe, and your oven thermometer uses the Celsius scale, what is the setting? What is the kelvin temperature?
Solution
5 5 5
∘ ∘ ∘ ∘
C = ( F − 32) = (450 − 32) = × 418 = 232 C → set oven to 230 C (two significant figures)
9 9 9
∘ 2
K= C + 273.15 = 230 + 273 = 503 K → 5.0 × 10 K (two signif icant f igures)
 Exercise 1.6.5
Convert 50 °F to °C and K.
Answer
10 °C, 280 K
Summary
Measurements are made using a variety of units. It is often useful or necessary to convert a measured quantity from one unit into another. These conversions are accomplished using unit conversion
factors, which are derived by simple applications of a mathematical approach called the factor-label method or dimensional analysis. This strategy is also employed to calculate sought quantities using
measured quantities and appropriate mathematical relations.

Key Equations
5
T∘ C = × T∘ F − 32
9
9
T∘ F = × T∘ C + 32
5
∘
TK = C + 273.15
T∘ C = K − 273.15
Glossary
dimensional analysis
(also, factor-label method) versatile mathematical approach that can be applied to computations ranging from simple unit conversions to more complex, multi-step calculations involving several
different quantities
Fahrenheit
unit of temperature; water freezes at 32 °F and boils at 212 °F on this scale
unit conversion factor

ratio of equivalent quantities expressed with different units; used to convert from one unit to a different unit
This page titled 1.6: Mathematical Treatment of Measurement Results is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
1.6: Mathematical Treatment of Measurement Results is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

Q1.1.1
Explain how you could experimentally determine whether the outside temperature is higher or lower than 0 °C (32 °F) without
using a thermometer.
S1.1.1
Place a glass of water outside. It will freeze if the temperature is below 0 °C.
Q1.1.2
Identify each of the following statements as being most similar to a hypothesis, a law, or a theory. Explain your reasoning.
a. Falling barometric pressure precedes the onset of bad weather.
b. All life on earth has evolved from a common, primitive organism through the process of natural selection.
c. My truck’s gas mileage has dropped significantly, probably because it’s due for a tune-up.
Q1.1.3
Identify each of the following statements as being most similar to a hypothesis, a law, or a theory. Explain your reasoning.
a. The pressure of a sample of gas is directly proportional to the temperature of the gas.
b. Matter consists of tiny particles that can combine in specific ratios to form substances with specific properties.
c. At a higher temperature, solids (such as salt or sugar) will dissolve better in water.
S1.1.3
(a) law (states a consistently observed phenomenon, can be used for prediction); (b) theory (a widely accepted explanation of the
behavior of matter); (c) hypothesis (a tentative explanation, can be investigated by experimentation)
Identify each of the underlined items as a part of either the macroscopic domain, the microscopic domain, or the symbolic domain
of chemistry. For any in the symbolic domain, indicate whether they are symbols for a macroscopic or a microscopic feature.
a. (a) The mass of a lead pipe is 14 lb.
b. (b) The mass of a certain chlorine atom is 35 amu.
c. (c) A bottle with a label that reads Al contains aluminum metal.
d. (d) Al is the symbol for an aluminum atom.
Identify each of the underlined items as a part of either the macroscopic domain, the microscopic domain, or the symbolic domain
of chemistry. For those in the symbolic domain, indicate whether they are symbols for a macroscopic or a microscopic feature.
a. (a) A certain molecule contains one H atom and one Cl atom.
b. (b) Copper wire has a density of about 8 g/cm3.
c. (c) The bottle contains 15 grams of Ni powder.
d. (d) A sulfur molecule is composed of eight sulfur atoms.
(a) symbolic, microscopic; (b) macroscopic; (c) symbolic, macroscopic; (d) microscopic
According to one theory, the pressure of a gas increases as its volume decreases because the molecules in the gas have to move a
shorter distance to hit the walls of the container. Does this theory follow a macroscopic or microscopic description of chemical
behavior? Explain your answer.
The amount of heat required to melt 2 lbs of ice is twice the amount of heat required to melt 1 lb of ice. Is this observation a
macroscopic or microscopic description of chemical behavior? Explain your answer.
Macroscopic. The heat required is determined from macroscopic properties.
Access for free at OpenStax 1.E.1 https://chem.libretexts.org/@go/page/207450

Questions
1. Why do we use an object's mass, rather than its weight, to indicate the amount of matter it contains?
2. What properties distinguish solids from liquids? Liquids from gases? Solids from gases?
3. How does a heterogeneous mixture differ from a homogeneous mixture? How are they similar?
4. How does a homogeneous mixture differ from a pure substance? How are they similar?
5. How does an element differ from a compound? How are they similar?
6. How do molecules of elements and molecules of compounds differ? In what ways are they similar?
7. How does an atom differ from a molecule? In what ways are they similar?
8. Many of the items you purchase are mixtures of pure compounds. Select three of these commercial products and prepare a list
of the ingredients that are pure compounds.
9. Classify each of the following as an element, a compound, or a mixture:
a. copper
b. water
c. nitrogen
d. sulfur
e. air
f. sucrose
g. a substance composed of molecules each of which contains two iodine atoms
h. gasoline
10. Classify each of the following as an element, a compound, or a mixture:
a. iron
b. oxygen
c. mercury oxide
d. pancake syrup
e. carbon dioxide
f. a substance composed of molecules each of which contains one hydrogen atom and one chlorine atom
g. baking soda
h. baking powder
11. A sulfur atom and a sulfur molecule are not identical. What is the difference?
12. How are the molecules in oxygen gas, the molecules in hydrogen gas, and water molecules similar? How do they differ?
13. We refer to astronauts in space as weightless, but not without mass. Why?
14. As we drive an automobile, we don't think about the chemicals consumed and produced. Prepare a list of the principal
chemicals consumed and produced during the operation of an automobile.
15. Matter is everywhere around us. Make a list by name of fifteen different kinds of matter that you encounter every day. Your list
should include (and label at least one example of each) the following: a solid, a liquid, a gas, an element, a compound, a
homogenous mixture, a heterogeneous mixture, and a pure substance.
16. When elemental iron corrodes it combines with oxygen in the air to ultimately form red brown iron(III) oxide which we call
rust. (a) If a shiny iron nail with an initial mass of 23.2 g is weighed after being coated in a layer of rust, would you expect the
mass to have increased, decreased, or remained the same? Explain. (b) If the mass of the iron nail increases to 24.1 g, what
mass of oxygen combined with the iron?
17. As stated in the text, convincing examples that demonstrate the law of conservation of matter outside of the laboratory are few
and far between. Indicate whether the mass would increase, decrease, or stay the same for the following scenarios where
chemical reactions take place:
a. Exactly one pound of bread dough is placed in a baking tin. The dough is cooked in an oven at 350 °F releasing a wonderful
aroma of freshly baked bread during the cooking process. Is the mass of the baked loaf less than, greater than, or the same as
the one pound of original dough? Explain.
b. When magnesium burns in air a white flaky ash of magnesium oxide is produced. Is the mass of magnesium oxide less than,
greater than, or the same as the original piece of magnesium? Explain.
c. Antoine Lavoisier, the French scientist credited with first stating the law of conservation of matter, heated a mixture of tin
and air in a sealed flask to produce tin oxide. Did the mass of the sealed flask and contents decrease, increase, or remain the
same after the heating?

18. Yeast converts glucose to ethanol and carbon dioxide during anaerobic fermentation as depicted in the simple chemical equation
here:
glucose → ethanol + carbon dioxide (1.E.1)
a. If 200.0 g of glucose is fully converted, what will be the total mass of ethanol and carbon dioxide produced?
b. If the fermentation is carried out in an open container, would you expect the mass of the container and contents after
fermentation to be less than, greater than, or the same as the mass of the container and contents before fermentation?
Explain.
c. If 97.7 g of carbon dioxide is produced, what mass of ethanol is produced?
Solutions
2 Liquids can change their shape (flow); solids can’t. Gases can undergo large volume changes as pressure changes; liquids do not.
Gases flow and change volume; solids do not.
4.The mixture can have a variety of compositions; a pure substance has a definite composition. Both have the same composition
from point to point.
6 Molecules of elements contain only one type of atom; molecules of compounds contain two or more types of atoms. They are
similar in that both are comprised of two or more atoms chemically bonded together.
8. Answers will vary. Sample answer: Gatorade contains water, sugar, dextrose, citric acid, salt, sodium chloride, monopotassium
phosphate, and sucrose acetate isobutyrate.
11. (a) element; (b) element; (c) compound; (d) mixture, (e) compound; (f) compound; (g) compound; (h) mixture
12. In each case, a molecule consists of two or more combined atoms. They differ in that the types of atoms change from one
substance to the next.
14. Gasoline (a mixture of compounds), oxygen, and to a lesser extent, nitrogen are consumed. Carbon dioxide and water are the
principal products. Carbon monoxide and nitrogen oxides are produced in lesser amounts.
16. (a) Increased as it would have combined with oxygen in the air thus increasing the amount of matter and therefore the mass. (b)
0.9 g
18. (a) 200.0 g; (b) The mass of the container and contents would decrease as carbon dioxide is a gaseous product and would leave
the container. (c) 102.3 g

Classify the six underlined properties in the following paragraph as chemical or physical:
Fluorine is a pale yellow gas that reacts with most substances. The free element melts at −220 °C and boils at −188 °C. Finely
divided metals burn in fluorine with a bright flame. Nineteen grams of fluorine will react with 1.0 gram of hydrogen.
Classify each of the following changes as physical or chemical:
a. condensation of steam
b. burning of gasoline
c. souring of milk
d. dissolving of sugar in water
e. melting of gold
(a) physical; (b) chemical; (c) chemical; (d) physical; (e) physical
Classify each of the following changes as physical or chemical:
a. coal burning
b. ice melting
c. mixing chocolate syrup with milk
d. explosion of a firecracker
e. magnetizing of a screwdriver

The volume of a sample of oxygen gas changed from 10 mL to 11 mL as the temperature changed. Is this a chemical or physical
change?
physical
A 2.0-liter volume of hydrogen gas combined with 1.0 liter of oxygen gas to produce 2.0 liters of water vapor. Does oxygen
undergo a chemical or physical change?
Explain the difference between extensive properties and intensive properties.
The value of an extensive property depends upon the amount of matter being considered, whereas the value of an intensive
property is the same regardless of the amount of matter being considered.
Identify the following properties as either extensive or intensive.
a. volume
b. temperature
c. humidity
d. heat
e. boiling point
The density (d) of a substance is an intensive property that is defined as the ratio of its mass (m) to its volume (V).
mass m
density = d=
volume V
Considering that mass and volume are both extensive properties, explain why their ratio, density, is intensive.
Being extensive properties, both mass and volume are directly proportional to the amount of substance under study. Dividing one
extensive property by another will in effect “cancel” this dependence on amount, yielding a ratio that is independent of amount (an
intensive property).
1.4: Measurements
Is one liter about an ounce, a pint, a quart, or a gallon?
Is a meter about an inch, a foot, a yard, or a mile?
about a yard
Indicate the SI base units or derived units that are appropriate for the following measurements:
1. (a) the length of a marathon race (26 miles 385 yards)
2. (b) the mass of an automobile
3. (c) the volume of a swimming pool
4. (d) the speed of an airplane
5. (e) the density of gold
6. (f) the area of a football field
7. (g) the maximum temperature at the South Pole on April 1, 1913
Indicate the SI base units or derived units that are appropriate for the following measurements:
1. (a) the mass of the moon
2. (b) the distance from Dallas to Oklahoma City
3. (c) the speed of sound
4. (d) the density of air
5. (e) the temperature at which alcohol boils
6. (f) the area of the state of Delaware
7. (g) the volume of a flu shot or a measles vaccination
(a) kilograms; (b) meters; (c) kilometers/second; (d) kilograms/cubic meter; (e) kelvin; (f) square meters; (g) cubic meters
Give the name and symbol of the prefixes used with SI units to indicate multiplication by the following exact quantities.
1. (a) 103
2. (b) 10−2

3. (c) 0.1
4. (d) 10−3
5. (e) 1,000,000
6. (f) 0.000001
Give the name of the prefix and the quantity indicated by the following symbols that are used with SI base units.
1. (a) c
2. (b) d
3. (c) G
4. (d) k
5. (e) m
6. (f) n
7. (g) p
8. (h) T
(a) centi-, × 10−2; (b) deci-, × 10−1; (c) Giga-, × 109; (d) kilo-, × 103; (e) milli-, × 10−3; (f) nano-, × 10−9; (g) pico-, × 10−12; (h)
tera-, × 1012
A large piece of jewelry has a mass of 132.6 g. A graduated cylinder initially contains 48.6 mL water. When the jewelry is
submerged in the graduated cylinder, the total volume increases to 61.2 mL.
1. (a) Determine the density of this piece of jewelry.
2. (b) Assuming that the jewelry is made from only one substance, what substance is it likely to be? Explain.
Visit this PhET density simulation and select the Same Volume Blocks.
1. (a) What are the mass, volume, and density of the yellow block?
2. (b) What are the mass, volume and density of the red block?
3. (c) List the block colors in order from smallest to largest mass.
4. (d) List the block colors in order from lowest to highest density.
5. (e) How are mass and density related for blocks of the same volume?
(a) 8.00 kg, 5.00 L, 1.60 kg/L; (b) 2.00 kg, 5.00 L, 0.400 kg/L; (c) red < green < blue < yellow; (d) If the volumes are the same,
then the density is directly proportional to the mass.
Visit this PhET density simulation and select Custom Blocks and then My Block.
1. (a) Enter mass and volume values for the block such that the mass in kg is less than the volume in L. What does the block do?
Why? Is this always the case when mass < volume?
2. (b) Enter mass and volume values for the block such that the mass in kg is more than the volume in L. What does the block do?
Why? Is this always the case when mass > volume?
3. (c) How would (a) and (b) be different if the liquid in the tank were ethanol instead of water?
4. (d) How would (a) and (b) be different if the liquid in the tank were mercury instead of water?
Visit this PhET density simulation and select Mystery Blocks.
1. (a) Pick one of the Mystery Blocks and determine its mass, volume, density, and its likely identity.
2. (b) Pick a different Mystery Block and determine its mass, volume, density, and its likely identity.
3. (c) Order the Mystery Blocks from least dense to most dense. Explain.
(a) (b) Answer is one of the following. A/yellow: mass = 65.14 kg, volume = 3.38 L, density = 19.3 kg/L, likely identity = gold.
B/blue: mass = 0.64 kg, volume = 1.00 L, density = 0.64 kg/L, likely identity = apple. C/green: mass = 4.08 kg, volume = 5.83 L,
density = 0.700 kg/L, likely identity = gasoline. D/red: mass = 3.10 kg, volume = 3.38 L, density = 0.920 kg/L, likely identity =
ice; and E/purple: mass = 3.53 kg, volume = 1.00 L, density = 3.53 kg/L, likely identity = diamond. (c) B/blue/apple (0.64 kg/L) <
C/green/gasoline (0.700 kg/L) < D/red/ice (0.920 kg/L) < E/purple/diamond (3.53 kg/L) < A/yellow/gold (19.3 kg/L)

Express each of the following numbers in scientific notation with correct significant figures:
1. (a) 711.0

2. (b) 0.239
3. (c) 90743
4. (d) 134.2
5. (e) 0.05499
6. (f) 10000.0
7. (g) 0.000000738592
Express each of the following numbers in exponential notation with correct significant figures:
1. (a) 704
2. (b) 0.03344
3. (c) 547.9
4. (d) 22086
5. (e) 1000.00
6. (f) 0.0000000651
7. (g) 0.007157
(a) 7.04 × 102; (b) 3.344 × 10−2; (c) 5.479 × 102; (d) 2.2086 × 104; (e) 1.00000 × 103; (f) 6.51 × 10−8; (g) 7.157 × 10−3
Indicate whether each of the following can be determined exactly or must be measured with some degree of uncertainty:
1. (a) the number of eggs in a basket
2. (b) the mass of a dozen eggs
3. (c) the number of gallons of gasoline necessary to fill an automobile gas tank
4. (d) the number of cm in 2 m
5. (e) the mass of a textbook
6. (f) the time required to drive from San Francisco to Kansas City at an average speed of 53 mi/h
Indicate whether each of the following can be determined exactly or must be measured with some degree of uncertainty:
1. (a) the number of seconds in an hour
2. (b) the number of pages in this book
3. (c) the number of grams in your weight
4. (d) the number of grams in 3 kilograms
5. (e) the volume of water you drink in one day
6. (f) the distance from San Francisco to Kansas City
(a) exact; (b) exact; (c) uncertain; (d) exact; (e) uncertain; (f) uncertain
How many significant figures are contained in each of the following measurements?
1. (a) 38.7 g
2. (b) 2 × 1018 m
3. (c) 3,486,002 kg
4. (d) 9.74150 × 10−4 J
5. (e) 0.0613 cm3
6. (f) 17.0 kg
7. (g) 0.01400 g/mL
How many significant figures are contained in each of the following measurements?
1. (a) 53 cm
2. (b) 2.05 × 108 m
3. (c) 86,002 J
4. (d) 9.740 × 104 m/s
5. (e) 10.0613 m3
6. (f) 0.17 g/mL
7. (g) 0.88400 s
(a) two; (b) three; (c) five; (d) four; (e) six; (f) two; (g) five

The following quantities were reported on the labels of commercial products. Determine the number of significant figures in each.
1. (a) 0.0055 g active ingredients
2. (b) 12 tablets
3. (c) 3% hydrogen peroxide
4. (d) 5.5 ounces
5. (e) 473 mL
6. (f) 1.75% bismuth
7. (g) 0.001% phosphoric acid
8. (h) 99.80% inert ingredients
Round off each of the following numbers to two significant figures:
1. (a) 0.436
2. (b) 9.000
3. (c) 27.2
4. (d) 135
5. (e) 1.497 × 10−3
6. (f) 0.445
(a) 0.44; (b) 9.0; (c) 27; (d) 140; (e) 1.5 × 10−3; (f) 0.44
Round off each of the following numbers to two significant figures:
1. (a) 517
2. (b) 86.3
3. (c) 6.382 × 103
4. (d) 5.0008
5. (e) 22.497
6. (f) 0.885
Perform the following calculations and report each answer with the correct number of significant figures.
1. (a) 628 × 342
2. (b) (5.63 × 102) × (7.4 × 103)
3. (c)
28.0
4.
13.483
5. (d) 8119 × 0.000023
6. (e) 14.98 + 27,340 + 84.7593
7. (f) 42.7 + 0.259
(a) 2.15 × 105; (b) 4.2 × 106; (c) 2.08; (d) 0.19; (e) 27,440; (f) 43.0
Perform the following calculations and report each answer with the correct number of significant figures.
1. (a) 62.8 × 34
2. (b) 0.147 + 0.0066 + 0.012
3. (c) 38 × 95 × 1.792
4. (d) 15 – 0.15 – 0.6155
0.0500
5. (e) 8.78 × ( )
0.478
6. (f) 140 + 7.68 + 0.014

7. (g) 28.7 – 0.0483
(88.5 − 87.57)
8. (h)
45.13
Consider the results of the archery contest shown in this figure.

1. (a) Which archer is most precise?
2. (b) Which archer is most accurate?

3. (c) Who is both least precise and least accurate?
4 targets are shown each with 4 holes indicating where the arrows hit the targets. Archer W put all 4 arrows closely around the center of the target. Archer X put all 4 arrows in a tight cluster but far to the lower right
of the target. Archer Y put all 4 arrows at different corners of the target. All 4 arrows are very far from the center of the target. Archer Z put 2 arrows close to the target and 2 other arrows far outside of the target.
(a) Archer X; (b) Archer W; (c) Archer Y

Classify the following sets of measurements as accurate, precise, both, or neither.
1. (a) Checking for consistency in the weight of chocolate chip cookies: 17.27 g, 13.05 g, 19.46 g, 16.92 g
2. (b) Testing the volume of a batch of 25-mL pipettes: 27.02 mL, 26.99 mL, 26.97 mL, 27.01 mL
3. (c) Determining the purity of gold: 99.9999%, 99.9998%, 99.9998%, 99.9999%

Write conversion factors (as ratios) for the number of:
a. yards in 1 meter
b. liters in 1 liquid quart
c. pounds in 1 kilogram
1.0936 yd 0.94635 L 2.2046 lb
(a) ; (b) ; (c)
1 m 1 qt 1 kg
Write conversion factors (as ratios) for the number of:

1. (a) kilometers in 1 mile
2. (b) liters in 1 cubic foot
3. (c) grams in 1 ounce
The label on a soft drink bottle gives the volume in two units: 2.0 L and 67.6 fl oz. Use this information to derive a conversion
factor between the English and metric units. How many significant figures can you justify in your conversion factor?
2.0 L 0.030 L
=
67.6 f l oz 1 f l oz
Only two significant figures are justified.

The label on a box of cereal gives the mass of cereal in two units: 978 grams and 34.5 oz. Use this information to find a conversion
factor between the English and metric units. How many significant figures can you justify in your conversion factor?
Soccer is played with a round ball having a circumference between 27 and 28 in. and a weight between 14 and 16 oz. What are
these specifications in units of centimeters and grams?
68–71 cm; 400–450 g
A woman's basketball has a circumference between 28.5 and 29.0 inches and a maximum weight of 20 ounces (two significant
figures). What are these specifications in units of centimeters and grams?
How many milliliters of a soft drink are contained in a 12.0-oz can?
355 mL
A barrel of oil is exactly 42 gal. How many liters of oil are in a barrel?
The diameter of a red blood cell is about 3 × 10−4 in. What is its diameter in centimeters?
8 × 10−4 cm
The distance between the centers of the two oxygen atoms in an oxygen molecule is 1.21 × 10−8 cm. What is this distance in
inches?
Is a 197-lb weight lifter light enough to compete in a class limited to those weighing 90 kg or less?
yes; weight = 89.4 kg
A very good 197-lb weight lifter lifted 192 kg in a move called the clean and jerk. What was the mass of the weight lifted in
pounds?
Many medical laboratory tests are run using 5.0 μL blood serum. What is this volume in milliliters?

5.0 × 10−3 mL
If an aspirin tablet contains 325 mg aspirin, how many grams of aspirin does it contain?
Use scientific (exponential) notation to express the following quantities in terms of the SI base units in [link]:
1. (a) 0.13 g
2. (b) 232 Gg
3. (c) 5.23 pm
4. (d) 86.3 mg
5. (e) 37.6 cm
6. (f) 54 μm
7. (g) 1 Ts
8. (h) 27 ps
9. (i) 0.15 mK
(a) 1.3 × 10−4 kg; (b) 2.32 × 108 kg; (c) 5.23 × 10−12 m; (d) 8.63 × 10−5 kg; (e) 3.76 × 10−1 m; (f) 5.4 × 10−5 m; (g) 1 × 1012 s;
(h) 2.7 × 10−11 s; (i) 1.5 × 10−4 K
Complete the following conversions between SI units.
1. (a) 612 g = ________ mg
2. (b) 8.160 m = ________ cm
3. (c) 3779 μg = ________ g
4. (d) 781 mL = ________ L
5. (e) 4.18 kg = ________ g
6. (f) 27.8 m = ________ km
7. (g) 0.13 mL = ________ L
8. (h) 1738 km = ________ m
9. (i) 1.9 Gg = ________ g
Gasoline is sold by the liter in many countries. How many liters are required to fill a 12.0-gal gas tank?
45.4 L
Milk is sold by the liter in many countries. What is the volume of exactly 1/2 gal of milk in liters?
A long ton is defined as exactly 2240 lb. What is this mass in kilograms?
1.0160 × 103 kg
Make the conversion indicated in each of the following:
1. (a) the men’s world record long jump, 29 ft 4¼ in., to meters
2. (b) the greatest depth of the ocean, about 6.5 mi, to kilometers
3. (c) the area of the state of Oregon, 96,981 mi2, to square kilometers
4. (d) the volume of 1 gill (exactly 4 oz) to milliliters
5. (e) the estimated volume of the oceans, 330,000,000 mi3, to cubic kilometers.
6. (f) the mass of a 3525-lb car to kilograms
7. (g) the mass of a 2.3-oz egg to grams
Make the conversion indicated in each of the following:
1. (a) the length of a soccer field, 120 m (three significant figures), to feet
2. (b) the height of Mt. Kilimanjaro, at 19,565 ft the highest mountain in Africa, to kilometers
3. (c) the area of an 8.5 t 11-inch sheet of paper in cm2
4. (d) the displacement volume of an automobile engine, 161 in.3, to liters
5. (e) the estimated mass of the atmosphere, 5.6 t 1015 tons, to kilograms
6. (f) the mass of a bushel of rye, 32.0 lb, to kilograms
7. (g) the mass of a 5.00-grain aspirin tablet to milligrams (1 grain = 0.00229 oz)
1. (a) 394 ft

2.
3. (b) 5.9634 km
4.
5. (c) 6.0 × 102
6.
7. (d) 2.64 L
8.
9. (e) 5.1 × 1018 kg
10.
11. (f) 14.5 kg
12.
13. (g) 324 mg
Many chemistry conferences have held a 50-Trillion Angstrom Run (two significant figures). How long is this run in kilometers
and in miles? (1 Å = 1 × 10−10 m)
A chemist’s 50-Trillion Angstrom Run (see Exercise) would be an archeologist’s 10,900 cubit run. How long is one cubit in meters
and in feet? (1 Å = 1 × 10−8 cm)
0.46 m; 1.5 ft/cubit
The gas tank of a certain luxury automobile holds 22.3 gallons according to the owner’s manual. If the density of gasoline is 0.8206
g/mL, determine the mass in kilograms and pounds of the fuel in a full tank.
As an instructor is preparing for an experiment, he requires 225 g phosphoric acid. The only container readily available is a 150-
mL Erlenmeyer flask. Is it large enough to contain the acid, whose density is 1.83 g/mL?
Yes, the acid's volume is 123 mL.
To prepare for a laboratory period, a student lab assistant needs 125 g of a compound. A bottle containing 1/4 lb is available. Did
the student have enough of the compound?
A chemistry student is 159 cm tall and weighs 45.8 kg. What is her height in inches and weight in pounds?
62.6 in (about 5 ft 3 in.) and 101 lb
In a recent Grand Prix, the winner completed the race with an average speed of 229.8 km/h. What was his speed in miles per hour,
meters per second, and feet per second?
Solve these problems about lumber dimensions.
(a) To describe to a European how houses are constructed in the US, the dimensions of “two-by-four” lumber must be converted
into metric units. The thickness × width × length dimensions are 1.50 in. × 3.50 in. × 8.00 ft in the US. What are the dimensions
in cm × cm × m?
(b) This lumber can be used as vertical studs, which are typically placed 16.0 in. apart. What is that distance in centimeters?
(a) 3.81 cm × 8.89 cm × 2.44 m; (b) 40.6 cm
The mercury content of a stream was believed to be above the minimum considered safe—1 part per billion (ppb) by weight. An
analysis indicated that the concentration was 0.68 parts per billion. What quantity of mercury in grams was present in 15.0 L of the
1 ng Hg
water, the density of which is 0.998 g/ml? (1 ppb Hg = )
1 g water
Calculate the density of aluminum if 27.6 cm3 has a mass of 74.6 g.

2.70 g/cm3
Osmium is one of the densest elements known. What is its density if 2.72 g has a volume of 0.121 cm3?
Calculate these masses.
(a) What is the mass of 6.00 cm3 of mercury, density = 13.5939 g/cm3?
(b) What is the mass of 25.0 mL octane, density = 0.702 g/cm3?

(a) 81.6 g; (b) 17.6 g
Calculate these masses.
1. (a) What is the mass of 4.00 cm3 of sodium, density = 0.97 g/cm?
2. (b) What is the mass of 125 mL gaseous chlorine, density = 3.16 g/L?
Calculate these volumes.
1. (a) What is the volume of 25 g iodine, density = 4.93 g/cm3?
2. (b) What is the volume of 3.28 g gaseous hydrogen, density = 0.089 g/L?
(a) 5.1 mL; (b) 37 L
Calculate these volumes.
1. (a) What is the volume of 11.3 g graphite, density = 2.25 g/cm3?
2. (b) What is the volume of 39.657 g bromine, density = 2.928 g/cm3?
Convert the boiling temperature of gold, 2966 °C, into degrees Fahrenheit and kelvin.
5371 °F, 3239 K
Convert the temperature of scalding water, 54 °C, into degrees Fahrenheit and kelvin.
Convert the temperature of the coldest area in a freezer, −10 °F, to degrees Celsius and kelvin.
−23 °C, 250 K
Convert the temperature of dry ice, −77 °C, into degrees Fahrenheit and kelvin.
Convert the boiling temperature of liquid ammonia, −28.1 °F, into degrees Celsius and kelvin.
−33.4 °C, 239.8 K
The label on a pressurized can of spray disinfectant warns against heating the can above 130 °F. What are the corresponding
temperatures on the Celsius and kelvin temperature scales?
The weather in Europe was unusually warm during the summer of 1995. The TV news reported temperatures as high as 45 °C.
What was the temperature on the Fahrenheit scale?
113 °F
Contributors and Attributions

[email protected]).
This page titled 1.E: Essential Ideas of Chemistry (Exercises) is shared under a CC BY license and was authored, remixed, and/or curated by
OpenStax.

CHAPTER OVERVIEW
2: Atoms, Molecules, and Ions

General Chemistry
This chapter will describe some of the fundamental chemical principles related to the composition of matter, including those central
to the concept of molecular identity.
Contributors
[email protected]).
Thumbnail: Spinning Buckminsterfullerene (C ). Image used with permission (CC BY-SA 3.0; unported; Sponk).
60
This page titled 2: Atoms, Molecules, and Ions is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
1
Your overall health and susceptibility to disease depends upon the complex interaction between your genetic makeup and
environmental exposure, with the outcome difficult to predict. Early detection of biomarkers, substances that indicate an organism’s
disease or physiological state, could allow diagnosis and treatment before a condition becomes serious or irreversible. Recent
studies have shown that your exhaled breath can contain molecules that may be biomarkers for recent exposure to environmental
contaminants or for pathological conditions ranging from asthma to lung cancer.
Figure 2.1.1 : Analysis of molecules in an exhaled breath can provide valuable information, leading to early diagnosis of diseases or
detection of environmental exposure to harmful substances. (credit: modification of work by Paul Flowers)
A person is shown blowing into a tube connected to a plastic bag. There is a computer screen displaying data that reads “Mass
Spectral Breath Analysis.” An arrow from the plastic bag points to an illustration of different molecular compounds contained in
the person’s exhalation
Scientists are working to develop biomarker “fingerprints” that could be used to diagnose a specific disease based on the amounts
and identities of certain molecules in a patient’s exhaled breath. An essential concept underlying this goal is that of a molecule’s
identity, which is determined by the numbers and types of atoms it contains, and how they are bonded together. This chapter will
describe some of the fundamental chemical principles related to the composition of matter, including those central to the concept of
molecular identity.
This page titled 2.1: Prelude to Atoms is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
2.0: Prelude to Atoms is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

By the end of this section, you will be able to:

State the postulates of Dalton’s atomic theory
Use postulates of Dalton’s atomic theory to explain the laws of definite and multiple proportions
The language used in chemistry is seen and heard in many disciplines, ranging from medicine to engineering to forensics to art.
The language of chemistry includes its own vocabulary as well as its own form of shorthand. Chemical symbols are used to
represent atoms and elements. Chemical formulas depict molecules as well as the composition of compounds. Chemical equations
provide information about the quality and quantity of the changes associated with chemical reactions.
This chapter will lay the foundation for our study of the language of chemistry. The concepts of this foundation include the atomic
theory, the composition and mass of an atom, the variability of the composition of isotopes, ion formation, chemical bonds in ionic
and covalent compounds, the types of chemical reactions, and the naming of compounds. We will also introduce one of the most
powerful tools for organizing chemical knowledge: the periodic table.
Atomic Theory through the Nineteenth Century

The earliest recorded discussion of the basic structure of matter comes from ancient Greek philosophers, the scientists of their day.
In the fifth century BC, Leucippus and Democritus argued that all matter was composed of small, finite particles that they called
atomos, a term derived from the Greek word for “indivisible.” They thought of atoms as moving particles that differed in shape and
size, and which could join together. Later, Aristotle and others came to the conclusion that matter consisted of various
combinations of the four “elements”—fire, earth, air, and water—and could be infinitely divided. Interestingly, these philosophers
thought about atoms and “elements” as philosophical concepts, but apparently never considered performing experiments to test
their ideas.
The Aristotelian view of the composition of matter held sway for over two thousand years, until English schoolteacher John Dalton
helped to revolutionize chemistry with his hypothesis that the behavior of matter could be explained using an atomic theory. First
published in 1807, many of Dalton’s hypotheses about the microscopic features of matter are still valid in modern atomic theory.
Here are the postulates of Dalton’s atomic theory.
1. Matter is composed of exceedingly small particles called atoms. An atom is the smallest unit of an element that can participate
in a chemical change.
2. An element consists of only one type of atom, which has a mass that is characteristic of the element and is the same for all
atoms of that element (Figure 2.2.1). A macroscopic sample of an element contains an incredibly large number of atoms, all of
which have identical chemical properties.
Figure 2.2.1 : A pre-1982 copper penny (left) contains approximately 3 × 1022 copper atoms (several dozen are represented as
brown spheres at the right), each of which has the same chemical properties. (credit: modification of work by “slgckgc”/Flickr)
The left image shows a photograph of a stack of pennies. The right image calls out an area of one of the pennies, which is made up
of many sphere-shaped copper atoms. The atoms are densely organized.
3. Atoms of one element differ in properties from atoms of all other elements.
4. A compound consists of atoms of two or more elements combined in a small, whole-number ratio. In a given compound, the
numbers of atoms of each of its elements are always present in the same ratio (Figure 2.2.2).

Figure 2.2.2 : Copper(II) oxide, a powdery, black compound, results from the combination of two types of atoms—copper (brown
spheres) and oxygen (red spheres)—in a 1:1 ratio. (credit: modification of work by “Chemicalinterest”/Wikimedia Commons)
The left image shows a container with a black, powdery compound. The right image calls out the molecular structure of the powder
which contains copper atoms that are clustered together with an equal number of oxygen atoms.
5. Atoms are neither created nor destroyed during a chemical change, but are instead rearranged to yield substances that are
different from those present before the change (Figure 2.2.3).
Figure 2.2.3 : When the elements copper (a shiny, red-brown solid, shown here as brown spheres) and oxygen (a clear and colorless
gas, shown here as red spheres) react, their atoms rearrange to form a compound containing copper and oxygen (a powdery, black
solid). (credit copper: modification of work by Copper [images-of-elements.com]).
The left stoppered bottle contains copper and oxygen. There is a callout which shows that copper is made up of many sphere-
shaped atoms. The atoms are densely organized. The open space of the bottle contains oxygen gas, which is made up of bonded
pairs of oxygen atoms that are evenly spaced. The right stoppered bottle shows the compound copper two oxide. A callout from the
powder shows a molecule of copper two oxide, which contains copper atoms that are clustered together with an equal number of
oxygen atoms.
Dalton’s atomic theory provides a microscopic explanation of the many macroscopic properties of matter that you’ve learned about.
For example, if an element such as copper consists of only one kind of atom, then it cannot be broken down into simpler
substances, that is, into substances composed of fewer types of atoms. And if atoms are neither created nor destroyed during a
chemical change, then the total mass of matter present when matter changes from one type to another will remain constant (the law
of conservation of matter).
 Example 2.2.1: Testing Dalton’s Atomic Theory
In the following drawing, the green spheres represent atoms of a certain element. The purple spheres represent atoms of
another element. If the spheres touch, they are part of a single unit of a compound. Does the following chemical change
represented by these symbols violate any of the ideas of Dalton’s atomic theory? If so, which one?

This equation shows that the starting materials of the reaction are two bonded, green spheres, which are being combined with
two smaller, bonded purple spheres. The product of the change is one purple sphere that is bonded to one green sphere.
Solution
The starting materials consist of two green spheres and two purple spheres. The products consist of only one green sphere and
one purple sphere. This violates Dalton’s postulate that atoms are neither created nor destroyed during a chemical change, but
are merely redistributed. (In this case, atoms appear to have been destroyed.)
 Exercise 2.2.1
In the following drawing, the green spheres represent atoms of a certain element. The purple spheres represent atoms of
another element. If the spheres touch, they are part of a single unit of a compound. Does the following chemical change
represented by these symbols violate any of the ideas of Dalton’s atomic theory? If so, which one
This equation shows that the starting materials of the reaction are two sets of bonded, green spheres which are each being
combined with two smaller, bonded purple spheres. The products of the change are two molecules that each contain one purple
sphere bonded between two green spheres.
Answer
The starting materials consist of four green spheres and two purple spheres. The products consist of four green spheres and
two purple spheres. This does not violate any of Dalton’s postulates: Atoms are neither created nor destroyed, but are
redistributed in small, whole-number ratios.
Dalton knew of the experiments of French chemist Joseph Proust, who demonstrated that all samples of a pure compound contain
the same elements in the same proportion by mass. This statement is known as the law of definite proportions or the law of constant
composition. The suggestion that the numbers of atoms of the elements in a given compound always exist in the same ratio is
consistent with these observations. For example, when different samples of isooctane (a component of gasoline and one of the
standards used in the octane rating system) are analyzed, they are found to have a carbon-to-hydrogen mass ratio of 5.33:1, as
shown in Table 2.2.1.
Table 2.2.1 : Constant Composition of Isooctane
Sample Carbon Hydrogen Mass Ratio
14.82 g carbon 5.33 g carbon
A 14.82 g 2.78 g =
2.78 g hydrogen 1.00 g hydrogen

B 22.33 g 4.19 g =

C 19.40 g 3.64 g =
It is worth noting that although all samples of a particular compound have the same mass ratio, the converse is not true in general.
That is, samples that have the same mass ratio are not necessarily the same substance. For example, there are many compounds
other than isooctane that also have a carbon-to-hydrogen mass ratio of 5.33:1.00.
Dalton also used data from Proust, as well as results from his own experiments, to formulate another interesting law. The law of
multiple proportions states that when two elements react to form more than one compound, a fixed mass of one element will react

with masses of the other element in a ratio of small, whole numbers. For example, copper and chlorine can form a green, crystalline
solid with a mass ratio of 0.558 g chlorine to 1 g copper, as well as a brown crystalline solid with a mass ratio of 1.116 g chlorine to
1 g copper. These ratios by themselves may not seem particularly interesting or informative; however, if we take a ratio of these
ratios, we obtain a useful and possibly surprising result: a small, whole-number ratio.
1.116 g Cl
1 g Cu 2
=
0.558 g Cl 1
1 g Cu
This 2-to-1 ratio means that the brown compound has twice the amount of chlorine per amount of copper as the green compound.
This can be explained by atomic theory if the copper-to-chlorine ratio in the brown compound is 1 copper atom to 2 chlorine atoms,
and the ratio in the green compound is 1 copper atom to 1 chlorine atom. The ratio of chlorine atoms (and thus the ratio of their
masses) is therefore 2 to 1 (Figure 2.2.4).
Figure 2.2.4 : Compared to the copper chlorine compound in (a), where copper is represented by brown spheres and chlorine by
green spheres, the copper chlorine compound in (b) has twice as many chlorine atoms per copper atom. (credit a: modification of
work by “Benjah-bmm27”/Wikimedia Commons; credit b: modification of work by “Walkerma”/Wikimedia Commons)
Figure A shows a pile of green powder. A callout shows that the green powder is made up of a lattice of copper atoms interspersed
with chlorine atoms. The atoms are color coded brown for copper and green for chlorine. The number of copper atoms is equal to
the number of chlorine atoms in the molecule. Figure B shows a pile of brown powder. A callout shows that the brown powder is
also made up of copper and chlorine atoms similar to the molecule shown in figure A.
 Example 2.2.2: Laws of Definite and Multiple Proportions
A sample of compound A (a clear, colorless gas) is analyzed and found to contain 4.27 g carbon and 5.69 g oxygen. A sample
of compound B (also a clear, colorless gas) is analyzed and found to contain 5.19 g carbon and 13.84 g oxygen. Are these data
an example of the law of definite proportions, the law of multiple proportions, or neither? What do these data tell you about
substances A and B?
Solution
In compound A, the mass ratio of carbon to oxygen is:
1.33 g O
1 g C
In compound B, the mass ratio of carbon to oxygen is:

2.67 g O
1 g C
The ratio of these ratios is:

1.33 g O
1 g C 1
=
2.67 g O 2
1 g C
This supports the law of multiple proportions. This means that A and B are different compounds, with A having one-half as
much carbon per amount of oxygen (or twice as much oxygen per amount of carbon) as B. A possible pair of compounds that
would fit this relationship would be A = CO2 and B = CO.
 Exercise 2.2.1
A sample of compound X (a clear, colorless, combustible liquid with a noticeable odor) is analyzed and found to contain 14.13
g carbon and 2.96 g hydrogen. A sample of compound Y (a clear, colorless, combustible liquid with a noticeable odor that is
slightly different from X’s odor) is analyzed and found to contain 19.91 g carbon and 3.34 g hydrogen. Are these data an
example of the law of definite proportions, the law of multiple proportions, or neither? What do these data tell you about
substances X and Y?
Answer
14.13 g C
In compound X, the mass ratio of carbon to hydrogen is .
2.96 g H
19.91 g C
In compound Y, the mass ratio of carbon to oxygen is .
3.34 g H
The ratio of these ratios is

14.13 g C
2.96 g H 4.77 g C/g H 4

= = 0.800 = .
19.91 g C 5.96 g C/g H 5
3.34 g H
This small, whole-number ratio supports the law of multiple proportions. This means that X and Y are different
compounds.
Summary
The ancient Greeks proposed that matter consists of extremely small particles called atoms. Dalton postulated that each element has
a characteristic type of atom that differs in properties from atoms of all other elements, and that atoms of different elements can
combine in fixed, small, whole-number ratios to form compounds. Samples of a particular compound all have the same elemental
proportions by mass. When two elements form different compounds, a given mass of one element will combine with masses of the
other element in a small, whole-number ratio. During any chemical change, atoms are neither created nor destroyed.
Glossary
Dalton’s atomic theory
set of postulates that established the fundamental properties of atoms
law of constant composition

(also, law of definite proportions) all samples of a pure compound contain the same elements in the same proportions by mass
law of multiple proportions

when two elements react to form more than one compound, a fixed mass of one element will react with masses of the other
element in a ratio of small whole numbers
law of definite proportions

(also, law of constant composition) all samples of a pure compound contain the same elements in the same proportions by mass
[email protected]).
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Outline milestones in the development of modern atomic theory
Summarize and interpret the results of the experiments of Thomson, Millikan, and Rutherford
Describe the three subatomic particles that compose atoms
Introduce the term isotopes
In the two centuries since Dalton developed his ideas, scientists have made significant progress in furthering our understanding of
atomic theory. Much of this came from the results of several seminal experiments that revealed the details of the internal structure
of atoms. Here, we will discuss some of those key developments, with an emphasis on application of the scientific method, as well
as understanding how the experimental evidence was analyzed. While the historical persons and dates behind these experiments
can be quite interesting, it is most important to understand the concepts resulting from their work.
Atomic Theory after the Nineteenth Century

If matter were composed of atoms, what were atoms composed of? Were they the smallest particles, or was there something
smaller? In the late 1800s, a number of scientists interested in questions like these investigated the electrical discharges that could
be produced in low-pressure gases, with the most significant discovery made by English physicist J. J. Thomson using a cathode
ray tube. This apparatus consisted of a sealed glass tube from which almost all the air had been removed; the tube contained two
metal electrodes. When high voltage was applied across the electrodes, a visible beam called a cathode ray appeared between them.
This beam was deflected toward the positive charge and away from the negative charge, and was produced in the same way with
identical properties when different metals were used for the electrodes. In similar experiments, the ray was simultaneously
deflected by an applied magnetic field, and measurements of the extent of deflection and the magnetic field strength allowed
Thomson to calculate the charge-to-mass ratio of the cathode ray particles. The results of these measurements indicated that these
particles were much lighter than atoms (Figure 2.3.1).
Figure 2.3.1 : (a) J. J. Thomson produced a visible beam in a cathode ray tube. (b) This is an early cathode ray tube, invented in
1897 by Ferdinand Braun. (c) In the cathode ray, the beam (shown in yellow) comes from the cathode and is accelerated past the
anode toward a fluorescent scale at the end of the tube. Simultaneous deflections by applied electric and magnetic fields permitted
Thomson to calculate the mass-to-charge ratio of the particles composing the cathode ray. (credit a: modification of work by Nobel
Foundation; credit b: modification of work by Eugen Nesper; credit c: modification of work by “Kurzon”/Wikimedia Commons).
Based on his observations, here is what Thomson proposed and why: The particles are attracted by positive (+) charges and
repelled by negative (−) charges, so they must be negatively charged (like charges repel and unlike charges attract); they are less
massive than atoms and indistinguishable, regardless of the source material, so they must be fundamental, subatomic constituents
of all atoms. Although controversial at the time, Thomson’s idea was gradually accepted, and his cathode ray particle is what we

now call an electron, a negatively charged, subatomic particle with a mass more than one thousand-times less that of an atom. The
term “electron” was coined in 1891 by Irish physicist George Stoney, from “electric ion.”
In 1909, more information about the electron was uncovered by American physicist Robert A. Millikan via his “oil drop”
experiments. Millikan created microscopic oil droplets, which could be electrically charged by friction as they formed or by using
X-rays. These droplets initially fell due to gravity, but their downward progress could be slowed or even reversed by an electric
field lower in the apparatus. By adjusting the electric field strength and making careful measurements and appropriate calculations,
Millikan was able to determine the charge on individual drops (Figure 2.3.2).
Figure 2.3.2 : Millikan’s experiment measured the charge of individual oil drops. The tabulated data are examples of a few possible
values.
Looking at the charge data that Millikan gathered, you may have recognized that the charge of an oil droplet is always a multiple of
a specific charge, 1.6 × 10−19 C. Millikan concluded that this value must therefore be a fundamental charge—the charge of a single
electron—with his measured charges due to an excess of one electron (1 times 1.6 × 10−19 C), two electrons (2 times 1.6 × 10−19
C), three electrons (3 times 1.6 × 10−19 C), and so on, on a given oil droplet. Since the charge of an electron was now known due
to Millikan’s research, and the charge-to-mass ratio was already known due to Thomson’s research (1.759 × 1011 C/kg), it only
required a simple calculation to determine the mass of the electron as well.
−19
1 kg −31
Mass of electron = 1.602 × 10 C × = 9.107 × 10 kg (2.3.1)
11
1.759 × 10 C
Scientists had now established that the atom was not indivisible as Dalton had believed, and due to the work of Thomson, Millikan,
and others, the charge and mass of the negative, subatomic particles—the electrons—were known. However, the positively charged
part of an atom was not yet well understood. In 1904, Thomson proposed the “plum pudding” model of atoms, which described a
positively charged mass with an equal amount of negative charge in the form of electrons embedded in it, since all atoms are
electrically neutral. A competing model had been proposed in 1903 by Hantaro Nagaoka, who postulated a Saturn-like atom,
consisting of a positively charged sphere surrounded by a halo of electrons (Figure 2.3.3).
Figure 2.3.3 : (a) Thomson suggested that atoms resembled plum pudding, an English dessert consisting of moist cake with
embedded raisins (“plums”). (b) Nagaoka proposed that atoms resembled the planet Saturn, with a ring of electrons surrounding a
positive “planet.” (credit a: modification of work by “Man vyi”/Wikimedia Commons; credit b: modification of work by
“NASA”/Wikimedia Commons).

The next major development in understanding the atom came from Ernest Rutherford, a physicist from New Zealand who largely
spent his scientific career in Canada and England. He performed a series of experiments using a beam of high-speed, positively
charged alpha particles (α particles) that were produced by the radioactive decay of radium; α particles consist of two protons and
two neutrons (you will learn more about radioactive decay in the chapter on nuclear chemistry). Rutherford and his colleagues
Hans Geiger (later famous for the Geiger counter) and Ernest Marsden aimed a beam of α particles, the source of which was
embedded in a lead block to absorb most of the radiation, at a very thin piece of gold foil and examined the resultant scattering of
the α particles using a luminescent screen that glowed briefly where hit by an α particle.
What did they discover? Most particles passed right through the foil without being deflected at all. However, some were diverted
slightly, and a very small number were deflected almost straight back toward the source (Figure 2.3.4). Rutherford described
finding these results: “It was quite the most incredible event that has ever happened to me in my life. It was almost as incredible as
if you fired a 15-inch shell at a piece of tissue paper and it came back and hit you”1 (p. 68).
Figure 2.3.4 : Geiger and Rutherford fired α particles at a piece of gold foil and detected where those particles went, as shown in
this schematic diagram of their experiment. Most of the particles passed straight through the foil, but a few were deflected slightly
and a very small number were significantly deflected.
Here is what Rutherford deduced: Because most of the fast-moving α particles passed through the gold atoms undeflected, they
must have traveled through essentially empty space inside the atom. Alpha particles are positively charged, so deflections arose
when they encountered another positive charge (like charges repel each other). Since like charges repel one another, the few
positively charged α particles that changed paths abruptly must have hit, or closely approached, another body that also had a highly
concentrated, positive charge. Since the deflections occurred a small fraction of the time, this charge only occupied a small amount
of the space in the gold foil. Analyzing a series of such experiments in detail, Rutherford drew two conclusions:
1. The volume occupied by an atom must consist of a large amount of empty space.
2. A small, relatively heavy, positively charged body, the nucleus, must be at the center of each atom.
This analysis led Rutherford to propose a model in which an atom consists of a very small, positively charged nucleus, in which
most of the mass of the atom is concentrated, surrounded by the negatively charged electrons, so that the atom is electrically neutral
(Figure 2.3.5).

Figure 2.3.5 : The α particles are deflected only when they collide with or pass close to the much heavier, positively charged gold
nucleus. Because the nucleus is very small compared to the size of an atom, very few α particles are deflected. Most pass through
the relatively large region occupied by electrons, which are too light to deflect the rapidly moving particles.
After many more experiments, Rutherford also discovered that the nuclei of other elements contain the hydrogen nucleus as a
“building block,” and he named this more fundamental particle the proton, the positively charged, subatomic particle found in the
nucleus. With one addition, which you will learn next, this nuclear model of the atom, proposed over a century ago, is still used
today.
PhET: Rutherford Scattering
Another important finding was the discovery of isotopes. During the early 1900s, scientists identified several substances that
appeared to be new elements, isolating them from radioactive ores. For example, a “new element” produced by the radioactive
decay of thorium was initially given the name mesothorium. However, a more detailed analysis showed that mesothorium was
chemically identical to radium (another decay product), despite having a different atomic mass. This result, along with similar
findings for other elements, led the English chemist Frederick Soddy to realize that an element could have types of atoms with
different masses that were chemically indistinguishable. These different types are called isotopes—atoms of the same element that
differ in mass. Soddy was awarded the Nobel Prize in Chemistry in 1921 for this discovery.
One puzzle remained: The nucleus was known to contain almost all of the mass of an atom, with the number of protons only
providing half, or less, of that mass. Different proposals were made to explain what constituted the remaining mass, including the
existence of neutral particles in the nucleus. As you might expect, detecting uncharged particles is very challenging, and it was not
until 1932 that James Chadwick found evidence of neutrons, uncharged, subatomic particles with a mass approximately the same as
that of protons. The existence of the neutron also explained isotopes: They differ in mass because they have different numbers of
neutrons, but they are chemically identical because they have the same number of protons. This will be explained in more detail
later in this chapter.
Summary
Although no one has actually seen the inside of an atom, experiments have demonstrated much about atomic structure. Thomson’s
cathode ray tube showed that atoms contain small, negatively charged particles called electrons. Millikan discovered that there is a
fundamental electric charge—the charge of an electron. Rutherford’s gold foil experiment showed that atoms have a small, dense,
positively charged nucleus; the positively charged particles within the nucleus are called protons. Chadwick discovered that the
nucleus also contains neutral particles called neutrons. Soddy demonstrated that atoms of the same element can differ in mass;
these are called isotopes.

Footnotes
1. Ernest Rutherford, “The Development of the Theory of Atomic Structure,” ed. J. A. Ratcliffe, in Background to Modern
Science, eds. Joseph Needham and Walter Pagel, (Cambridge, UK: Cambridge University Press, 1938), 61–74. Accessed
September 22, 2014, https://ia600508.us.archive.org/3/it...e032734mbp.pdf.
Glossary
alpha particle (α particle)
positively charged particle consisting of two protons and two neutrons
electron
negatively charged, subatomic particle of relatively low mass located outside the nucleus
isotopes
atoms that contain the same number of protons but different numbers of neutrons
neutron
uncharged, subatomic particle located in the nucleus
proton
positively charged, subatomic particle located in the nucleus
nucleus
massive, positively charged center of an atom made up of protons and neutrons
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Write and interpret symbols that depict the atomic number, mass number, and charge of an atom or ion
Define the atomic mass unit and average atomic mass
Calculate average atomic mass and isotopic abundance
The development of modern atomic theory revealed much about the inner structure of atoms. It was learned that an atom contains a
very small nucleus composed of positively charged protons and uncharged neutrons, surrounded by a much larger volume of space
containing negatively charged electrons. The nucleus contains the majority of an atom’s mass because protons and neutrons are
much heavier than electrons, whereas electrons occupy almost all of an atom’s volume. The diameter of an atom is on the order of
10−10 m, whereas the diameter of the nucleus is roughly 10−15 m—about 100,000 times smaller. For a perspective about their
relative sizes, consider this: If the nucleus were the size of a blueberry, the atom would be about the size of a football stadium
(Figure 2.4.1).
Figure 2.4.1 : If an atom could be expanded to the size of a football stadium, the nucleus would be the size of a single blueberry.
(credit middle: modification of work by “babyknight”/Wikimedia Commons; credit right: modification of work by Paxson
Woelber).
The diagram on the left shows a picture of an atom with a nucleus. The central figure shows a photograph of an American football
stadium. The figure on the right shows a photograph of a handful of blueberries.
Atoms—and the protons, neutrons, and electrons that compose them—are extremely small. For example, a carbon atom weighs
less than 2 × 10−23 g, and an electron has a charge of less than 2 × 10−19 C (coulomb). When describing the properties of tiny
objects such as atoms, we use appropriately small units of measure, such as the atomic mass unit (amu) and the fundamental unit of
charge (e). The amu was originally defined based on hydrogen, the lightest element, then later in terms of oxygen. Since 1961, it
has been defined with regard to the most abundant isotope of carbon, atoms of which are assigned masses of exactly 12 amu. (This
isotope is known as “carbon-12” as will be discussed later in this module.) Thus, one amu is exactly 1/12 of the mass of one
carbon-12 atom: 1 amu = 1.6605 × 10−24 g. (The Dalton (Da) and the unified atomic mass unit (u) are alternative units that are
equivalent to the amu.) The fundamental unit of charge (also called the elementary charge) equals the magnitude of the charge of an
electron (e) with e = 1.602 × 10−19 C.
A proton has a mass of 1.0073 amu and a charge of 1+. A neutron is a slightly heavier particle with a mass 1.0087 amu and a
charge of zero; as its name suggests, it is neutral. The electron has a charge of 1− and is a much lighter particle with a mass of
about 0.00055 amu (it would take about 1800 electrons to equal the mass of one proton. The properties of these fundamental
particles are summarized in Table 2.4.1. (An observant student might notice that the sum of an atom’s subatomic particles does not
equal the atom’s actual mass: The total mass of six protons, six neutrons, and six electrons is 12.0993 amu, slightly larger than the
12.00 amu of an actual carbon-12 atom. This “missing” mass is known as the mass defect, and you will learn about it in the chapter
on nuclear chemistry.)
Table 2.4.1 : Properties of Subatomic Particles
Name Location Charge (C) Unit Charge Mass (amu) Mass (g)
electron outside nucleus −1.602 × 10

−19
1− 0.00055 0.00091 × 10
−24
proton nucleus 1.602 × 10

−19
1+ 1.00727 1.67262 × 10
−24

Name Location Charge (C) Unit Charge Mass (amu) Mass (g)
neutron nucleus 0 0 1.00866 1.67493 × 10

−24
The number of protons in the nucleus of an atom is its atomic number (Z ). This is the defining trait of an element: Its value
determines the identity of the atom. For example, any atom that contains six protons is the element carbon and has the atomic
number 6, regardless of how many neutrons or electrons it may have. A neutral atom must contain the same number of positive and
negative charges, so the number of protons equals the number of electrons. Therefore, the atomic number also indicates the number
of electrons in an atom. The total number of protons and neutrons in an atom is called its mass number (A). The number of
neutrons is therefore the difference between the mass number and the atomic number: A – Z = number of neutrons.
atomic number (Z) = number of protons
mass number (A) = number of protons + number of neutrons
A−Z = number of neutrons
Atoms are electrically neutral if they contain the same number of positively charged protons and negatively charged electrons.
When the numbers of these subatomic particles are not equal, the atom is electrically charged and is called an ion. The charge of an
atom is defined as follows:
Atomic charge = number of protons − number of electrons
As will be discussed in more detail later in this chapter, atoms (and molecules) typically acquire charge by gaining or losing
electrons. An atom that gains one or more electrons will exhibit a negative charge and is called an anion. Positively charged atoms
called cations are formed when an atom loses one or more electrons. For example, a neutral sodium atom (Z = 11) has 11 electrons.
If this atom loses one electron, it will become a cation with a 1+ charge (11 − 10 = 1+). A neutral oxygen atom (Z = 8) has eight
electrons, and if it gains two electrons it will become an anion with a 2− charge (8 − 10 = 2−).
 Example 2.4.1: Composition of an Atom
Iodine is an essential trace element in our diet; it is needed to produce thyroid hormone. Insufficient iodine in the diet can lead
to the development of a goiter, an enlargement of the thyroid gland (Figure 2.4.2).
Figure 2.4.2 : (a) Insufficient iodine in the diet can cause an enlargement of the thyroid gland called a goiter. (b) The addition
of small amounts of iodine to salt, which prevents the formation of goiters, has helped eliminate this concern in the US where
salt consumption is high. (credit a: modification of work by “Almazi”/Wikimedia Commons; credit b: modification of work by
Mike Mozart)
Figure A shows a photo of a person who has a very swollen thyroid in his or her neck. Figure B shows a photo of a canister of
Morton iodized salt.
The addition of small amounts of iodine to table salt (iodized salt) has essentially eliminated this health concern in the United
States, but as much as 40% of the world’s population is still at risk of iodine deficiency. The iodine atoms are added as anions,
and each has a 1− charge and a mass number of 127. Determine the numbers of protons, neutrons, and electrons in one of these
iodine anions.

Solution
The atomic number of iodine (53) tells us that a neutral iodine atom contains 53 protons in its nucleus and 53 electrons outside
its nucleus. Because the sum of the numbers of protons and neutrons equals the mass number, 127, the number of neutrons is
74 (127 − 53 = 74). Since the iodine is added as a 1− anion, the number of electrons is 54 [53 – (1–) = 54].
 Exercise 2.4.1
An ion of platinum has a mass number of 195 and contains 74 electrons. How many protons and neutrons does it contain, and
what is its charge?
Answer
78 protons; 117 neutrons; charge is 4+
Chemical Symbols
A chemical symbol is an abbreviation that we use to indicate an element or an atom of an element. For example, the symbol for
mercury is Hg (Figure 2.4.3). We use the same symbol to indicate one atom of mercury (microscopic domain) or to label a
container of many atoms of the element mercury (macroscopic domain).
Figure 2.4.3 : The symbol Hg represents the element mercury regardless of the amount; it could represent one atom of mercury or a
large amount of mercury. from Wikipedia (user: Materialscientist).
The symbols for several common elements and their atoms are listed in Table 2.4.2. Some symbols are derived from the common
name of the element; others are abbreviations of the name in another language. Symbols have one or two letters, for example, H for
hydrogen and Cl for chlorine. To avoid confusion with other notations, only the first letter of a symbol is capitalized. For example,
Co is the symbol for the element cobalt, but CO is the notation for the compound carbon monoxide, which contains atoms of the
elements carbon (C) and oxygen (O). All known elements and their symbols are in the periodic table.
Table 2.4.2 : Some Common Elements and Their Symbols
Element Symbol Element Symbol
aluminum Al iron Fe (from ferrum)
bromine Br lead Pb (from plumbum)
calcium Ca magnesium Mg
carbon C mercury Hg (from hydrargyrum)
chlorine Cl nitrogen N
chromium Cr oxygen O
cobalt Co potassium K (from kalium)
copper Cu (from cuprum) silicon Si
fluorine F silver Ag (from argentum)

Element Symbol Element Symbol
gold Au (from aurum) sodium Na (from natrium)
helium He sulfur S
hydrogen H tin Sn (from stannum)
iodine I zinc Zn
Traditionally, the discoverer (or discoverers) of a new element names the element. However, until the name is recognized by the
International Union of Pure and Applied Chemistry (IUPAC), the recommended name of the new element is based on the Latin
word(s) for its atomic number. For example, element 106 was called unnilhexium (Unh), element 107 was called unnilseptium
(Uns), and element 108 was called unniloctium (Uno) for several years. These elements are now named after scientists or locations;
for example, element 106 is now known as seaborgium (Sg) in honor of Glenn Seaborg, a Nobel Prize winner who was active in
the discovery of several heavy elements.
Isotopes
The symbol for a specific isotope of any element is written by placing the mass number as a superscript to the left of the element
symbol (Figure 2.4.4). The atomic number is sometimes written as a subscript preceding the symbol, but since this number defines
the element’s identity, as does its symbol, it is often omitted. For example, magnesium exists as a mixture of three isotopes, each
with an atomic number of 12 and with mass numbers of 24, 25, and 26, respectively. These isotopes can be identified as 24Mg,
25
Mg, and 26Mg. These isotope symbols are read as “element, mass number” and can be symbolized consistent with this reading.
For instance, 24Mg is read as “magnesium 24,” and can be written as “magnesium-24” or “Mg-24.” 25Mg is read as “magnesium
25,” and can be written as “magnesium-25” or “Mg-25.” All magnesium atoms have 12 protons in their nucleus. They differ only
because a 24Mg atom has 12 neutrons in its nucleus, a 25Mg atom has 13 neutrons, and a 26Mg has 14 neutrons.
Figure 2.4.4 : The symbol for an atom indicates the element via its usual two-letter symbol, the mass number as a left superscript,
the atomic number as a left subscript (sometimes omitted), and the charge as a right superscript.
This diagram shows the symbol for helium, “H e.” The number to the upper left of the symbol is the mass number, which is 4. The
number to the upper right of the symbol is the charge which is positive 2. The number to the lower left of the symbol is the atomic
number, which is 2. This number is often omitted. Also shown is “M g” which stands for magnesium It has a mass number of 24, a
charge of positive 2, and an atomic number of 12.
Information about the naturally occurring isotopes of elements with atomic numbers 1 through 10 is given in Table 2.4.2. Note that
in addition to standard names and symbols, the isotopes of hydrogen are often referred to using common names and accompanying
symbols. Hydrogen-2, symbolized 2H, is also called deuterium and sometimes symbolized D. Hydrogen-3, symbolized 3H, is also
called tritium and sometimes symbolized T.
Table 2.4.2 : Nuclear Compositions of Atoms of the Very Light Elements
Number of Number of % Natural
Element Symbol Atomic Number Mass (amu)
Protons Neutrons Abundance
1
H
1
1 1 0 1.0078 99.989
(protium)
2
H
hydrogen 1
1 1 1 2.0141 0.0115
(deuterium)
3
H
1
1 1 2 3.01605 — (trace)
(tritium)
3
2
He 2 2 1 3.01603 0.00013
helium
4
2
He 2 2 2 4.0026 100

Number of Number of % Natural
Element Symbol Atomic Number Mass (amu)
Protons Neutrons Abundance
6
3
Li 3 3 3 6.0151 7.59
lithium
7
3
Li 3 3 4 7.0160 92.41
beryllium 9
4
Be 4 4 5 9.0122 100
10
5
B 5 5 5 10.0129 19.9
boron
11
5
B 5 5 6 11.0093 80.1
12
6
C 6 6 6 12.0000 98.89
carbon 13
6
C 6 6 7 13.0034 1.11
14
6C
6 6 8 14.0032 — (trace)
14
7
N 7 7 7 14.0031 99.63
nitrogen
15
7
N 7 7 8 15.0001 0.37
16
8
O 8 8 8 15.9949 99.757
oxygen 17
8O
8 8 9 16.9991 0.038
18
8
O 8 8 10 17.9992 0.205
fluorine 19
9
F 9 9 10 18.9984 100
20
10
Ne 10 10 10 19.9924 90.48
neon 21
10
Ne 10 10 11 20.9938 0.27
22
10
Ne 10 10 12 21.9914 9.25
Atomic Mass
Because each proton and each neutron contribute approximately one amu to the mass of an atom, and each electron contributes far
less, the atomic mass of a single atom is approximately equal to its mass number (a whole number). However, the average masses
of atoms of most elements are not whole numbers because most elements exist naturally as mixtures of two or more isotopes.
The mass of an element shown in a periodic table or listed in a table of atomic masses is a weighted, average mass of all the
isotopes present in a naturally occurring sample of that element. This is equal to the sum of each individual isotope’s mass
multiplied by its fractional abundance.
average mass = ∑(f ractional abundance × isotopic mass)i
For example, the element boron is composed of two isotopes: About 19.9% of all boron atoms are 10B with a mass of 10.0129 amu,
and the remaining 80.1% are 11B with a mass of 11.0093 amu. The average atomic mass for boron is calculated to be:
boron average mass = (0.199 × 10.0129 amu) + (0.801 × 11.0093 amu)
= 1.99 amu + 8.82 amu
= 10.81 amu
It is important to understand that no single boron atom weighs exactly 10.8 amu; 10.8 amu is the average mass of all boron atoms,
and individual boron atoms weigh either approximately 10 amu or 11 amu.
 Example 2.4.2: Calculation of Average Atomic Mass

A meteorite found in central Indiana contains traces of the noble gas neon picked up from the solar wind during the meteorite’s
trip through the solar system. Analysis of a sample of the gas showed that it consisted of 91.84% 20Ne (mass 19.9924 amu),
0.47% 21Ne (mass 20.9940 amu), and 7.69% 22Ne (mass 21.9914 amu). What is the average mass of the neon in the solar
wind?

Solution
average mass = (0.9184 × 19.9924 amu) + (0.0047 × 20.9940 amu) + (0.0769 × 21.9914 amu)
= (18.36 + 0.099 + 1.69) amu
= 20.15 amu
The average mass of a neon atom in the solar wind is 20.15 amu. (The average mass of a terrestrial neon atom is 20.1796 amu.
This result demonstrates that we may find slight differences in the natural abundance of isotopes, depending on their origin.)
 Exercise 2.4.2
A sample of magnesium is found to contain 78.70% of 24Mg atoms (mass 23.98 amu), 10.13% of 25
Mg atoms (mass 24.99
amu), and 11.17% of 26Mg atoms (mass 25.98 amu). Calculate the average mass of a Mg atom.
Answer
24.31 amu
We can also do variations of this type of calculation, as shown in the next example.
 Example 2.4.3: Calculation of Percent Abundance
Naturally occurring chlorine consists of 35Cl (mass 34.96885 amu) and 37Cl (mass 36.96590 amu), with an average mass of
35.453 amu. What is the percent composition of Cl in terms of these two isotopes?
Solution
The average mass of chlorine is the fraction that is 35Cl times the mass of 35Cl plus the fraction that is 37Cl times the mass of
37Cl.
35 35 37 37
average mass = (f raction of Cl × mass of Cl) + (f raction of Cl × mass of Cl)
If we let x represent the fraction that is 35Cl, then the fraction that is 37Cl is represented by 1.00 − x.
(The fraction that is 35Cl + the fraction that is 37Cl must add up to 1, so the fraction of 37Cl must equal 1.00 − the fraction of
35Cl.)
Substituting this into the average mass equation, we have:

35.453 amu = (x × 34.96885 amu) + [(1.00 − x) × 36.96590 amu]
35.453 = 34.96885x + 36.96590 − 36.96590x
1.99705x = 1.513
1.513
x = = 0.7576
1.99705
35
So solving yields: x = 0.7576, which means that 1.00 − 0.7576 = 0.2424. Therefore, chlorine consists of 75.76% Cl and
24.24% 37Cl.
 Exercise 2.4.3
Naturally occurring copper consists of 63Cu (mass 62.9296 amu) and 65Cu (mass 64.9278 amu), with an average mass of
63.546 amu. What is the percent composition of Cu in terms of these two isotopes?
Answer
69.15% Cu-63 and 30.85% Cu-65

Figure 2.4.5 : Analysis of zirconium in a mass spectrometer produces a mass spectrum with peaks showing the different isotopes of
Zr.
The left diagram shows how a mass spectrometer works. The graph to the right of the spectrometer shows a mass spectrum of
zirconium. The relative abundance, as a percentage from 0 to 100, is graphed on the y axis, and the mass to charge ratio is graphed
on the x axis. The sample contains five different isomers of zirconium.
The occurrence and natural abundances of isotopes can be experimentally determined using an instrument called a mass
spectrometer. Mass spectrometry (MS) is widely used in chemistry, forensics, medicine, environmental science, and many other
fields to analyze and help identify the substances in a sample of material. In a typical mass spectrometer (Figure 2.4.5), the sample
is vaporized and exposed to a high-energy electron beam that causes the sample’s atoms (or molecules) to become electrically
charged, typically by losing one or more electrons. These cations then pass through a (variable) electric or magnetic field that
deflects each cation’s path to an extent that depends on both its mass and charge (similar to how the path of a large steel ball
bearing rolling past a magnet is deflected to a lesser extent that that of a small steel BB). The ions are detected, and a plot of the
relative number of ions generated versus their mass-to-charge ratios (a mass spectrum) is made. The height of each vertical feature
or peak in a mass spectrum is proportional to the fraction of cations with the specified mass-to-charge ratio. Since its initial use
during the development of modern atomic theory, MS has evolved to become a powerful tool for chemical analysis in a wide range
of applications.
Mass Spectrometry MS
Video 2.4.1 : Watch this video from the Royal Society for Chemistry for a brief description of the rudiments of mass spectrometry.
Summary
An atom consists of a small, positively charged nucleus surrounded by electrons. The nucleus contains protons and neutrons; its
diameter is about 100,000 times smaller than that of the atom. The mass of one atom is usually expressed in atomic mass units
(amu), which is referred to as the atomic mass. An amu is defined as exactly 1/12 of the mass of a carbon-12 atom and is equal to
1.6605 × 10−24 g.

Protons are relatively heavy particles with a charge of 1+ and a mass of 1.0073 amu. Neutrons are relatively heavy particles with no
charge and a mass of 1.0087 amu. Electrons are light particles with a charge of 1− and a mass of 0.00055 amu. The number of
protons in the nucleus is called the atomic number (Z) and is the property that defines an atom’s elemental identity. The sum of the
numbers of protons and neutrons in the nucleus is called the mass number and, expressed in amu, is approximately equal to the
mass of the atom. An atom is neutral when it contains equal numbers of electrons and protons.
Isotopes of an element are atoms with the same atomic number but different mass numbers; isotopes of an element, therefore, differ
from each other only in the number of neutrons within the nucleus. When a naturally occurring element is composed of several
isotopes, the atomic mass of the element represents the average of the masses of the isotopes involved. A chemical symbol
identifies the atoms in a substance using symbols, which are one-, two-, or three-letter abbreviations for the atoms.
Key Equations
average mass = ∑ (f ractional abundance × isotopic mass)i
i
Glossary
anion
negatively charged atom or molecule (contains more electrons than protons)
atomic mass
average mass of atoms of an element, expressed in amu
atomic mass unit (amu)

1
(also, unified atomic mass unit, u, or Dalton, Da) unit of mass equal to of the mass of a 12C atom
12
atomic number (Z)

number of protons in the nucleus of an atom
cation
positively charged atom or molecule (contains fewer electrons than protons)
chemical symbol
one-, two-, or three-letter abbreviation used to represent an element or its atoms
Dalton (Da)
alternative unit equivalent to the atomic mass unit
fundamental unit of charge

(also called the elementary charge) equals the magnitude of the charge of an electron (e) with e = 1.602 × 10−19 C
ion
electrically charged atom or molecule (contains unequal numbers of protons and electrons)
mass number (A)

sum of the numbers of neutrons and protons in the nucleus of an atom
unified atomic mass unit (u)
alternative unit equivalent to the atomic mass unit
[email protected]).

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Symbolize the composition of molecules using molecular formulas and empirical formulas
Represent the bonding arrangement of atoms within molecules using structural formulas
A molecular formula is a representation of a molecule that uses chemical symbols to indicate the types of atoms followed by
subscripts to show the number of atoms of each type in the molecule. (A subscript is used only when more than one atom of a given
type is present.) Molecular formulas are also used as abbreviations for the names of compounds.
The structural formula for a compound gives the same information as its molecular formula (the types and numbers of atoms in the
molecule) but also shows how the atoms are connected in the molecule. The structural formula for methane contains symbols for
one C atom and four H atoms, indicating the number of atoms in the molecule (Figure 2.5.1). The lines represent bonds that hold
the atoms together. (A chemical bond is an attraction between atoms or ions that holds them together in a molecule or a crystal.) We
will discuss chemical bonds and see how to predict the arrangement of atoms in a molecule later. For now, simply know that the
lines are an indication of how the atoms are connected in a molecule. A ball-and-stick model shows the geometric arrangement of
the atoms with atomic sizes not to scale, and a space-filling model shows the relative sizes of the atoms.
Figure 2.5.1 : A methane molecule can be represented as (a) a molecular formula, (b) a structural formula, (c) a ball-and-stick
model, and (d) a space-filling model. Carbon and hydrogen atoms are represented by black and white spheres, respectively.
Figure A shows C H subscript 4. Figure B shows a carbon atom that is bonded to four hydrogen atoms at right angles: one above,
one to the left, one to the right, and one below. Figure C shows a 3-D, ball-and-stick model of the carbon atom bonded to four
hydrogen atoms. Figure D shows a space-filling model of a carbon atom with hydrogen atoms partially embedded into the surface
of the carbon atom.
Although many elements consist of discrete, individual atoms, some exist as molecules made up of two or more atoms of the
element chemically bonded together. For example, most samples of the elements hydrogen, oxygen, and nitrogen are composed of
molecules that contain two atoms each (called diatomic molecules) and thus have the molecular formulas H2, O2, and N2,
respectively. Other elements commonly found as diatomic molecules are fluorine (F2), chlorine (Cl2), bromine (Br2), and iodine
(I2). The most common form of the element sulfur is composed of molecules that consist of eight atoms of sulfur; its molecular
formula is S8 (Figure 2.5.2).
Figure 2.5.2 : A molecule of sulfur is composed of eight sulfur atoms and is therefore written as S8. It can be represented as (a) a
structural formula, (b) a ball-and-stick model, and (c) a space-filling model. Sulfur atoms are represented by yellow spheres.
Figure A shows eight sulfur atoms, symbolized with the letter S, that are bonded to each other to form an octagon. Figure B shows
a 3-D, ball-and-stick model of the arrangement of the sulfur atoms. The shape is clearly not octagonal as it is represented in the
structural formula. Figure C is a space-filling model that shows each sulfur atom is partially embedded into the sulfur atom it bonds
with.
It is important to note that a subscript following a symbol and a number in front of a symbol do not represent the same thing; for
example, H2 and 2H represent distinctly different species. H2 is a molecular formula; it represents a diatomic molecule of
hydrogen, consisting of two atoms of the element that are chemically bonded together. The expression 2H, on the other hand,

indicates two separate hydrogen atoms that are not combined as a unit. The expression 2H2 represents two molecules of diatomic
hydrogen (Figure 2.5.3).
Figure 2.5.3 : The symbols H, 2H, H2, and 2H2 represent very different entities.
This figure shows four diagrams. The diagram for H shows a single, white sphere and is labeled one H atom. The diagram for 2 H
shows two white spheres that are not bonded together. It is labeled 2 H atoms. The diagram for H subscript 2 shows two white
spheres bonded together. It is labeled one H subscript 2 molecule. The diagram for 2 H subscript 2 shows two sets of bonded, white
spheres. It is labeled 2 H subscript 2 molecules.
Compounds are formed when two or more elements chemically combine, resulting in the formation of bonds. For example,
hydrogen and oxygen can react to form water, and sodium and chlorine can react to form table salt. We sometimes describe the
composition of these compounds with an empirical formula, which indicates the types of atoms present and the simplest whole-
number ratio of the number of atoms (or ions) in the compound. For example, titanium dioxide (used as pigment in white paint and
in the thick, white, blocking type of sunscreen) has an empirical formula of TiO2. This identifies the elements titanium (Ti) and
oxygen (O) as the constituents of titanium dioxide, and indicates the presence of twice as many atoms of the element oxygen as
atoms of the element titanium (Figure 2.5.4).
Figure 2.5.4 : (a) The white compound titanium dioxide provides effective protection from the sun. (b) A crystal of titanium
dioxide, TiO2, contains titanium and oxygen in a ratio of 1 to 2. The titanium atoms are gray and the oxygen atoms are red. (credit
a: modification of work by “osseous”/Flickr).
Figure A shows a photo of a person applying suntan lotion to his or her lower leg. Figure B shows a 3-D ball-and-stick model of
the molecule titanium dioxide, which involves a complicated interlocking of many titanium and oxygen atoms. The titanium atoms
in the molecule are shown as silver spheres and the oxygen atoms are shown as red spheres. There are twice as many oxygen atoms
as titanium atoms in the molecule.
As discussed previously, we can describe a compound with a molecular formula, in which the subscripts indicate the actual
numbers of atoms of each element in a molecule of the compound. In many cases, the molecular formula of a substance is derived
from experimental determination of both its empirical formula and its molecular mass (the sum of atomic masses for all atoms
composing the molecule). For example, it can be determined experimentally that benzene contains two elements, carbon (C) and
hydrogen (H), and that for every carbon atom in benzene, there is one hydrogen atom. Thus, the empirical formula is CH. An
experimental determination of the molecular mass reveals that a molecule of benzene contains six carbon atoms and six hydrogen
atoms, so the molecular formula for benzene is C6H6 (Figure 2.5.5).

Figure 2.5.5 : Benzene, C6H6, is produced during oil refining and has many industrial uses. A benzene molecule can be represented
as (a) a structural formula, (b) a ball-and-stick model, and (c) a space-filling model. (d) Benzene is a clear liquid. (credit d:
modification of work by Sahar Atwa).
Figure A shows that benzene is composed of six carbons shaped like a hexagon. Every other bond between the carbon atoms is a
double bond. Each carbon also has a single bonded hydrogen atom. Figure B shows a 3-D, ball-and-stick drawing of benzene. The
six carbon atoms are black spheres while the six hydrogen atoms are smaller, white spheres. Figure C is a space-filling model of
benzene which shows that most of the interior space is occupied by the carbon atoms. The hydrogen atoms are embedded in the
outside surface of the carbon atoms. Figure d shows a small vial filled with benzene which appears to be clear.
If we know a compound’s formula, we can easily determine the empirical formula. (This is somewhat of an academic exercise; the
reverse chronology is generally followed in actual practice.) For example, the molecular formula for acetic acid, the component
that gives vinegar its sharp taste, is C2H4O2. This formula indicates that a molecule of acetic acid (Figure 2.5.6) contains two
carbon atoms, four hydrogen atoms, and two oxygen atoms. The ratio of atoms is 2:4:2. Dividing by the lowest common
denominator (2) gives the simplest, whole-number ratio of atoms, 1:2:1, so the empirical formula is CH2O. Note that a molecular
formula is always a whole-number multiple of an empirical formula.
Figure 2.5.6 : (a) Vinegar contains acetic acid, C2H4O2, which has an empirical formula of CH2O. It can be represented as (b) a
structural formula and (c) as a ball-and-stick model. (credit a: modification of work by “HomeSpot HQ”/Flickr)
Figure A shows a jug of distilled, white vinegar. Figure B shows a structural formula for acetic acid which contains two carbon
atoms connected by a single bond. The left carbon atom forms single bonds with three hydrogen atoms. The right carbon atom
forms a double bond with an oxygen atom. The right carbon atom also forms a single bond with an oxygen atom. This oxygen
forms a single bond with a hydrogen atom. Figure C shows a 3-D ball-and-stick model of acetic acid.
 Example 2.5.1: Empirical and Molecular Formulas
Molecules of glucose (blood sugar) contain 6 carbon atoms, 12 hydrogen atoms, and 6 oxygen atoms. What are the molecular
and empirical formulas of glucose?
Solution
The molecular formula is C6H12O6 because one molecule actually contains 6 C, 12 H, and 6 O atoms. The simplest whole-
number ratio of C to H to O atoms in glucose is 1:2:1, so the empirical formula is CH2O.
 Exercise 2.5.1
A molecule of metaldehyde (a pesticide used for snails and slugs) contains 8 carbon atoms, 16 hydrogen atoms, and 4 oxygen
atoms. What are the molecular and empirical formulas of metaldehyde?
Answer
Molecular formula, C8H16O4; empirical formula, C2H4O

It is important to be aware that it may be possible for the same atoms to be arranged in different ways: Compounds with the same
molecular formula may have different atom-to-atom bonding and therefore different structures. For example, could there be another
compound with the same formula as acetic acid, C2H4O2? And if so, what would be the structure of its molecules?
If you predict that another compound with the formula C2H4O2 could exist, then you demonstrated good chemical insight and are
correct. Two C atoms, four H atoms, and two O atoms can also be arranged to form methyl formate, which is used in
manufacturing, as an insecticide, and for quick-drying finishes. Methyl formate molecules have one of the oxygen atoms between
the two carbon atoms, differing from the arrangement in acetic acid molecules. Acetic acid and methyl formate are examples of
isomers—compounds with the same chemical formula but different molecular structures (Figure 2.5.7). Note that this small
difference in the arrangement of the atoms has a major effect on their respective chemical properties. You would certainly not want
to use a solution of methyl formate as a substitute for a solution of acetic acid (vinegar) when you make salad dressing.
Figure 2.5.7 : Molecules of (a) acetic acid and methyl formate (b) are structural isomers; they have the same formula (C2H4O2) but
different structures (and therefore different chemical properties).
Figure A shows a structural diagram of acetic acid, C subscript 2 H subscript 4 O subscript 2. Acetic acid contains two carbon
atoms connected by a single bond. The left carbon atom forms single bonds with three hydrogen atoms. The carbon on the right
forms a double bond with an oxygen atom. The right carbon atom also forms a single bond to an oxygen atom which forms a single
bond with a hydrogen atom. Figure B shows a structural diagram of methyl formate, C subscript 2 H subscript 4 O subscript 2. This
molecule contains a carbon atom which forms single bonds with three hydrogen atoms, and a single bond with an oxygen atom.
The oxygen atom forms a single bond with another carbon atom which forms a double bond with another oxygen atom and a single
bond with a hydrogen atom.
Many types of isomers exist (Figure 2.5.8). Acetic acid and methyl formate are structural isomers, compounds in which the
molecules differ in how the atoms are connected to each other. There are also various types of spatial isomers, in which the relative
orientations of the atoms in space can be different. For example, the compound carvone (found in caraway seeds, spearmint, and
mandarin orange peels) consists of two isomers that are mirror images of each other. S-(+)-carvone smells like caraway, and R-(−)-
carvone smells like spearmint.

Figure 2.5.8 : Molecules of carvone are spatial isomers; they only differ in the relative orientations of the atoms in space. (credit
bottom left: modification of work by “Miansari66”/Wikimedia Commons; credit bottom right: modification of work by Forest &
Kim Starr)
Summary
A molecular formula uses chemical symbols and subscripts to indicate the exact numbers of different atoms in a molecule or
compound. An empirical formula gives the simplest, whole-number ratio of atoms in a compound. A structural formula indicates
the bonding arrangement of the atoms in the molecule. Ball-and-stick and space-filling models show the geometric arrangement of
atoms in a molecule. Isomers are compounds with the same molecular formula but different arrangements of atoms.
Glossary
empirical formula
formula showing the composition of a compound given as the simplest whole-number ratio of atoms
isomers
compounds with the same chemical formula but different structures
molecular formula
formula indicating the composition of a molecule of a compound and giving the actual number of atoms of each element in a
molecule of the compound.
spatial isomers
compounds in which the relative orientations of the atoms in space differ
structural isomer
one of two substances that have the same molecular formula but different physical and chemical properties because their atoms
are bonded differently
structural formula
shows the atoms in a molecule and how they are connected

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State the periodic law and explain the organization of elements in the periodic table
Predict the general properties of elements based on their location within the periodic table
Identify metals, nonmetals, and metalloids by their properties and/or location on the periodic table
As early chemists worked to purify ores and discovered more elements, they realized that various elements could be grouped
together by their similar chemical behaviors. One such grouping includes lithium (Li), sodium (Na), and potassium (K): These
elements all are shiny, conduct heat and electricity well, and have similar chemical properties. A second grouping includes calcium
(Ca), strontium (Sr), and barium (Ba), which also are shiny, good conductors of heat and electricity, and have chemical properties
in common. However, the specific properties of these two groupings are notably different from each other. For example: Li, Na,
and K are much more reactive than are Ca, Sr, and Ba; Li, Na, and K form compounds with oxygen in a ratio of two of their atoms
to one oxygen atom, whereas Ca, Sr, and Ba form compounds with one of their atoms to one oxygen atom. Fluorine (F), chlorine
(Cl), bromine (Br), and iodine (I) also exhibit similar properties to each other, but these properties are drastically different from
those of any of the elements above.
Dimitri Mendeleev in Russia (1869) and Lothar Meyer in Germany (1870) independently recognized that there was a periodic
relationship among the properties of the elements known at that time. Both published tables with the elements arranged according
to increasing atomic mass. But Mendeleev went one step further than Meyer: He used his table to predict the existence of elements
that would have the properties similar to aluminum and silicon, but were yet unknown. The discoveries of gallium (1875) and
germanium (1886) provided great support for Mendeleev’s work. Although Mendeleev and Meyer had a long dispute over priority,
Mendeleev’s contributions to the development of the periodic table are now more widely recognized (Figure 2.6.1).

Figure 2.6.1 : (a) Dimitri Mendeleev is widely credited with creating (b) the first periodic table of the elements. (credit a:
modification of work by Serge Lachinov; credit b: modification of work by “Den fjättrade ankan”/Wikimedia Commons)
Figure A shows a photograph of Dimitri Mendeleev. Figure B shows the first periodic table developed by Mendeleev, which had
eight groups and twelve periods. In the first group (—, R superscript plus sign 0) is the following information: H = 1, L i = 7, N a =
23, K = 39, (C u = 63), R b = 85, (A g = 108), C a = 183, (—),—, (A u = 199) —. Note that each of these entries corresponds to
one of the twelve periods respectively. The second group (—, R 0) contains the following information: (not entry for period 1) B o
= 9, 4, M g = 24, C a = 40, Z n = 65, S r = 87, C d = 112, B a = 187, —, —, H g = 200, —. Note the ach of these entries
corresponds to one of the twelve periods respectively. Group three (—, R superscript one 0 superscript nine) contains the
information: (no entry for period 1), B = 11, A l = 27, 8. — = 44, — = 68, ? Y t = 88, I n = 113, ? D I = 138, —, ? E r = 178, T l =
204, —. Note that each of these entries corresponds to one of the twelve periods respectively. Group four (RH superscript four, R0
superscript eight) contains the following information: (no entry for period 1), C = 12, B i = 28, T i = 48, — = 72, Z r = 90, S n =
118, ? C o = 140, ? L a = 180, P b = 207, T h = 231. Note that each of these entries corresponds to one of the twelve periods
respectively. Group five (R H superscript two, R superscript two 0 superscript five) contains the following information: (no entry
for period 1), N = 14, P = 31, V = 51, A s = 75, N b = 94, S b = 122, —, —, T a = 182, B l = 208, —. Note that each of these
entries corresponds to one of the twelve periods respectively. Group six (R H superscript two, R 0 superscript three) contains the
following information: (no entry for period 1), O = 16, S = 32, C r = 52, S o = 78, M o = 96, T o = 125, —, —, W = 184, —, U =
240. Note that each of these entries corresponds to one of the twelve periods respectively. Group seven (R H , R superscript plus
sing, 0 superscript 7) contains the following information: (no entry for period 1), F = 19, C l = 35, 5, M n = 55, B r = 80, — = 100,
J = 127, —, —, —, —, —. Note that each of these entries corresponds to one of the twelve periods respectively. Group 8 (—, R 0
superscript four) contains the following information: (no entry for periods 1, 2, 3), in period 4: F o = 56, C o = 59, N i = 59, C u =
63, no entry for period five, in period 6: R u = 104, R h = 104, P d = 106, A g = 108, no entries for periods 7, 8 , or 9, in period 10:
O s = 195, I r = 197, P t = 198, A u = 199, no entries for periods 11 or 12.
By the twentieth century, it became apparent that the periodic relationship involved atomic numbers rather than atomic masses. The
modern statement of this relationship, the periodic law, is as follows: the properties of the elements are periodic functions of their
atomic numbers. A modern periodic table arranges the elements in increasing order of their atomic numbers and groups atoms with
similar properties in the same vertical column (Figure 2.6.2). Each box represents an element and contains its atomic number,
symbol, average atomic mass, and (sometimes) name. The elements are arranged in seven horizontal rows, called periods or series,
and 18 vertical columns, called groups. Groups are labeled at the top of each column. In the United States, the labels traditionally
were numerals with capital letters. However, IUPAC recommends that the numbers 1 through 18 be used, and these labels are more
common. For the table to fit on a single page, parts of two of the rows, a total of 14 columns, are usually written below the main
body of the table.

Figure 2.6.2 : Elements in the periodic table are organized according to their properties.
The Periodic Table of Elements is shown. The 18 columns are labeled “Group” and the 7 rows are labeled “Period.” Below the
table to the right is a box labeled “Color Code” with different colors for metals, metalloids, and nonmetals, as well as solids,
liquids, and gases. To the left of this box is an enlarged picture of the upper-left most box on the table. The number 1 is in its upper-
left hand corner and is labeled “Atomic number.” The letter “H” is in the middle in red indicating that it is a gas. It is labeled
“Symbol.” Below that is the number 1.008 which is labeled “Atomic Mass.” Below that is the word hydrogen which is labeled
“name.” The color of the box indicates that it is a nonmetal. Each element will be described in this order: atomic number; name;
symbol; whether it is a metal, metalloid, or nonmetal; whether it is a solid, liquid, or gas; and atomic mass. Beginning at the top left
of the table, or period 1, group 1, is a box containing “1; hydrogen; H; nonmetal; gas; and 1.008.” There is only one other element
box in period 1, group 18, which contains “2; helium; H e; nonmetal; gas; and 4.003.” Period 2, group 1 contains “3; lithium; L i;
metal; solid; and 6.94” Group 2 contains “4; beryllium; B e; metal; solid; and 9.012.” Groups 3 through 12 are skipped and group
13 contains “5; boron; B; metalloid; solid; 10.81.” Group 14 contains “6; carbon; C; nonmetal; solid; and 12.01.” Group 15
contains “7; nitrogen; N; nonmetal; gas; and 14.01.” Group 16 contains “8; oxygen; O; nonmetal; gas; and 16.00.” Group 17
contains “9; fluorine; F; nonmetal; gas; and 19.00.” Group 18 contains “10; neon; N e; nonmetal; gas; and 20.18.” Period 3, group
1 contains “11; sodium; N a; metal; solid; and 22.99.” Group 2 contains “12; magnesium; M g; metal; solid; and 24.31.” Groups 3
through 12 are skipped again in period 3 and group 13 contains “13; aluminum; A l; metal; solid; and 26.98.” Group 14 contains
“14; silicon; S i; metalloid; solid; and 28.09.” Group 15 contains “15; phosphorous; P; nonmetal; solid; and 30.97.” Group 16
contains “16; sulfur; S; nonmetal; solid; and 32.06.” Group 17 contains “17; chlorine; C l; nonmetal; gas; and 35.45.” Group 18
contains “18; argon; A r; nonmetal; gas; and 39.95.” Period 4, group 1 contains “19; potassium; K; metal; solid; and 39.10.” Group
2 contains “20; calcium; C a; metal; solid; and 40.08.” Group 3 contains “21; scandium; S c; metal; solid; and 44.96.” Group 4
contains “22; titanium; T i; metal; solid; and 47.87.” Group 5 contains “23; vanadium; V; metal; solid; and 50.94.” Group 6
contains “24; chromium; C r; metal; solid; and 52.00.” Group 7 contains “25; manganese; M n; metal; solid; and 54.94.” Group 8
contains “26; iron; F e; metal; solid; and 55.85.” Group 9 contains “27; cobalt; C o; metal; solid; and 58.93.” Group 10 contains
“28; nickel; N i; metal; solid; and 58.69.” Group 11 contains “29; copper; C u; metal; solid; and 63.55.” Group 12 contains “30;
zinc; Z n; metal; solid; and 65.38.” Group 13 contains “31; gallium; G a; metal; solid; and 69.72.” Group 14 contains “32;
germanium; G e; metalloid; solid; and 72.63.” Group 15 contains “33; arsenic; A s; metalloid; solid; and 74.92.” Group 16 contains
“34; selenium; S e; nonmetal; solid; and 78.97.” Group 17 contains “35; bromine; B r; nonmetal; liquid; and 79.90.” Group 18
contains “36; krypton; K r; nonmetal; gas; and 83.80.” Period 5, group 1 contains “37; rubidium; R b; metal; solid; and 85.47.”
Group 2 contains “38; strontium; S r; metal; solid; and 87.62.” Group 3 contains “39; yttrium; Y; metal; solid; and 88.91.” Group 4
contains “40; zirconium; Z r; metal; solid; and 91.22.” Group 5 contains “41; niobium; N b; metal; solid; and 92.91.” Group 6
contains “42; molybdenum; M o; metal; solid; and 95.95.” Group 7 contains “43; technetium; T c; metal; solid; and 97.” Group 8
contains “44; ruthenium; R u; metal; solid; and 101.1.” Group 9 contains “45; rhodium; R h; metal; solid; and 102.9.” Group 10
contains “46; palladium; P d; metal; solid; and 106.4.” Group 11 contains “47; silver; A g; metal; solid; and 107.9.” Group 12
contains “48; cadmium; C d; metal; solid; and 112.4.” Group 13 contains “49; indium; I n; metal; solid; and 114.8.” Group 14
contains “50; tin; S n; metal; solid; and 118.7.” Group 15 contains “51; antimony; S b; metalloid; solid; and 121.8.” Group 16
contains “52; tellurium; T e; metalloid; solid; and 127.6.” Group 17 contains “53; iodine; I; nonmetal; solid; and 126.9.” Group 18
contains “54; xenon; X e; nonmetal; gas; and 131.3.” Period 6, group 1 contains “55; cesium; C s; metal; solid; and 132.9.” Group
2 contains “56; barium; B a; metal; solid; and 137.3.” Group 3 breaks the pattern. The box has a large arrow pointing to a row of
elements below the table with atomic numbers ranging from 57-71. In sequential order by atomic number, the first box in this row

contains “57; lanthanum; L a; metal; solid; and 138.9.” To its right, the next is “58; cerium; C e; metal; solid; and 140.1.” Next is
“59; praseodymium; P r; metal; solid; and 140.9.” Next is “60; neodymium; N d; metal; solid; and 144.2.” Next is “61;
promethium; P m; metal; solid; and 145.” Next is “62; samarium; S m; metal; solid; and 150.4.” Next is “63; europium; E u; metal;
solid; and 152.0.” Next is “64; gadolinium; G d; metal; solid; and 157.3.” Next is “65; terbium; T b; metal; solid; and 158.9.” Next
is “66; dysprosium; D y; metal; solid; and 162.5.” Next is “67; holmium; H o; metal; solid; and 164.9.” Next is “68; erbium; E r;
metal; solid; and 167.3.” Next is “69; thulium; T m; metal; solid; and 168.9.” Next is “70; ytterbium; Y b; metal; solid; and 173.1.”
The last in this special row is “71; lutetium; L u; metal; solid; and 175.0.” Continuing in period 6, group 4 contains “72; hafnium;
H f; metal; solid; and 178.5.” Group 5 contains “73; tantalum; T a; metal; solid; and 180.9.” Group 6 contains “74; tungsten; W;
metal; solid; and 183.8.” Group 7 contains “75; rhenium; R e; metal; solid; and 186.2.” Group 8 contains “76; osmium; O s; metal;
solid; and 190.2.” Group 9 contains “77; iridium; I r; metal; solid; and 192.2.” Group 10 contains “78; platinum; P t; metal; solid;
and 195.1.” Group 11 contains “79; gold; A u; metal; solid; and 197.0.” Group 12 contains “80; mercury; H g; metal; liquid; and
200.6.” Group 13 contains “81; thallium; T l; metal; solid; and 204.4.” Group 14 contains “82; lead; P b; metal; solid; and 207.2.”
Group 15 contains “83; bismuth; B i; metal; solid; and 209.0.” Group 16 contains “84; polonium; P o; metal; solid; and 209.”
Group 17 contains “85; astatine; A t; metalloid; solid; and 210.” Group 18 contains “86; radon; R n; nonmetal; gas; and 222.”
Period 7, group 1 contains “87; francium; F r; metal; solid; and 223.” Group 2 contains “88; radium; R a; metal; solid; and 226.”
Group 3 breaks the pattern much like what occurs in period 6. A large arrow points from the box in period 7, group 3 to a special
row containing the elements with atomic numbers ranging from 89-103, just below the row which contains atomic numbers 57-71.
In sequential order by atomic number, the first box in this row contains “89; actinium; A c; metal; solid; and 227.” To its right, the
next is “90; thorium; T h; metal; solid; and 232.0.” Next is “91; protactinium; P a; metal; solid; and 231.0.” Next is “92; uranium;
U; metal; solid; and 238.0.” Next is “93; neptunium; N p; metal; solid; and N p.” Next is “94; plutonium; P u; metal; solid; and
244.” Next is “95; americium; A m; metal; solid; and 243.” Next is “96; curium; C m; metal; solid; and 247.” Next is “97;
berkelium; B k; metal; solid; and 247.” Next is “98; californium; C f; metal; solid; and 251.” Next is “99; einsteinium; E s; metal;
solid; and 252.” Next is “100; fermium; F m; metal; solid; and 257.” Next is “101; mendelevium; M d; metal; solid; and 258.” Next
is “102; nobelium; N o; metal; solid; and 259.” The last in this special row is “103; lawrencium; L r; metal; solid; and 262.”
Continuing in period 7, group 4 contains “104; rutherfordium; R f; metal; solid; and 267.” Group 5 contains “105; dubnium; D b;
metal; solid; and 270.” Group 6 contains “106; seaborgium; S g; metal; solid; and 271.” Group 7 contains “107; bohrium; B h;
metal; solid; and 270.” Group 8 contains “108; hassium; H s; metal; solid; and 277.” Group 9 contains “109; meitnerium; M t; not
indicated; solid; and 276.” Group 10 contains “110; darmstadtium; D s; not indicated; solid; and 281.” Group 11 contains “111;
roentgenium; R g; not indicated; solid; and 282.” Group 12 contains “112; copernicium; C n; metal; liquid; and 285.” Group 13
contains “113; ununtrium; U u t; not indicated; solid; and 285.” Group 14 contains “114; flerovium; F l; not indicated; solid; and
289.” Group 15 contains “115; ununpentium; U u p; not indicated; solid; and 288.” Group 16 contains “116; livermorium; L v; not
indicated; solid; and 293.” Group 17 contains “117; ununseptium; U u s; not indicated; solid; and 294.” Group 18 contains “118;
ununoctium; U u o; not indicated; solid; and 294.”
Many elements differ dramatically in their chemical and physical properties, but some elements are similar in their behaviors. For
example, many elements appear shiny, are malleable (able to be deformed without breaking) and ductile (can be drawn into wires),
and conduct heat and electricity well. Other elements are not shiny, malleable, or ductile, and are poor conductors of heat and
electricity. We can sort the elements into large classes with common properties: metals (elements that are shiny, malleable, good
conductors of heat and electricity—shaded yellow); nonmetals (elements that appear dull, poor conductors of heat and electricity—
shaded green); and metalloids (elements that conduct heat and electricity moderately well, and possess some properties of metals
and some properties of nonmetals—shaded purple).
The elements can also be classified into the main-group elements (or representative elements) in the columns labeled 1, 2, and 13–
18; the transition metals in the columns labeled 3–12; and inner transition metals in the two rows at the bottom of the table (the top-
row elements are called lanthanides and the bottom-row elements are actinides; Figure 2.6.3). The elements can be subdivided
further by more specific properties, such as the composition of the compounds they form. For example, the elements in group 1 (the
first column) form compounds that consist of one atom of the element and one atom of hydrogen. These elements (except
hydrogen) are known as alkali metals, and they all have similar chemical properties. The elements in group 2 (the second column)
form compounds consisting of one atom of the element and two atoms of hydrogen: These are called alkaline earth metals, with
similar properties among members of that group. Other groups with specific names are the pnictogens (group 15), chalcogens
(group 16), halogens (group 17), and the noble gases (group 18, also known as inert gases). The groups can also be referred to by
the first element of the group: For example, the chalcogens can be called the oxygen group or oxygen family. Hydrogen is a unique,
nonmetallic element with properties similar to both group 1 and group 17 elements. For that reason, hydrogen may be shown at the
top of both groups, or by itself.

Figure 2.6.3 : The periodic table organizes elements with similar properties into groups.
This diagram combines the groups and periods of the periodic table based on their similar properties. Group 1 contains the alkali
metals, group 2 contains the earth alkaline metals, group 15 contains the pnictogens, group 16 contains the chalcogens, group 17
contains the halogens and group 18 contains the noble gases. The main group elements consist of groups 1, 2, and 12 through 18.
Therefore, most of the transition metals, which are contained in groups 3 through 11, are not main group elements. The lanthanides
and actinides are called out at the bottom of the periodic table.
 Example 2.6.1: Naming Groups of Elements
Atoms of each of the following elements are essential for life. Give the group name for the following elements:
a. chlorine
b. calcium
c. sodium
d. sulfur
Solution
The family names are as follows:
a. halogen
b. alkaline earth metal
c. alkali metal
d. chalcogen
 Exercise 2.6.1
Give the group name for each of the following elements:

a. krypton
b. selenium
c. barium
d. lithium
Answer a

noble gas
Answer b
chalcogen
Answer c
alkaline earth metal
Answer d
alkali metal
In studying the periodic table, you might have noticed something about the atomic masses of some of the elements. Element 43
(technetium), element 61 (promethium), and most of the elements with atomic number 84 (polonium) and higher have their atomic
mass given in square brackets. This is done for elements that consist entirely of unstable, radioactive isotopes (you will learn more
about radioactivity in the nuclear chemistry chapter). An average atomic weight cannot be determined for these elements because
their radioisotopes may vary significantly in relative abundance, depending on the source, or may not even exist in nature. The
number in square brackets is the atomic mass number (and approximate atomic mass) of the most stable isotope of that element.
Summary
The discovery of the periodic recurrence of similar properties among the elements led to the formulation of the periodic table, in
which the elements are arranged in order of increasing atomic number in rows known as periods and columns known as groups.
Elements in the same group of the periodic table have similar chemical properties. Elements can be classified as metals, metalloids,
and nonmetals, or as a main-group elements, transition metals, and inner transition metals. Groups are numbered 1–18 from left to
right. The elements in group 1 are known as the alkali metals; those in group 2 are the alkaline earth metals; those in 15 are the
pnictogens; those in 16 are the chalcogens; those in 17 are the halogens; and those in 18 are the noble gases.
Glossary
actinide
inner transition metal in the bottom of the bottom two rows of the periodic table
alkali metal
element in group 1
alkaline earth metal

element in group 2
chalcogen
element in group 16
group
vertical column of the periodic table
halogen
element in group 17
inert gas
(also, noble gas) element in group 18
inner transition metal

(also, lanthanide or actinide) element in the bottom two rows; if in the first row, also called lanthanide, or if in the second row,
also called actinide
lanthanide

inner transition metal in the top of the bottom two rows of the periodic table
main-group element
(also, representative element) element in columns 1, 2, and 12–18
metal
element that is shiny, malleable, good conductor of heat and electricity
metalloid
element that conducts heat and electricity moderately well, and possesses some properties of metals and some properties of
nonmetals
noble gas
(also, inert gas) element in group 18
nonmetal
element that appears dull, poor conductor of heat and electricity
period
(also, series) horizontal row of the periodic table
periodic law
properties of the elements are periodic function of their atomic numbers.
periodic table
table of the elements that places elements with similar chemical properties close together
pnictogen
element in group 15
representative element
(also, main-group element) element in columns 1, 2, and 12–18
transition metal
element in columns 3–11
series
(also, period) horizontal row of the period table
This page titled 2.6: The Periodic Table is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
2.5: The Periodic Table is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

Define ionic and molecular (covalent) compounds
Predict the type of compound formed from elements based on their location within the periodic table
Determine formulas for simple ionic compounds
In ordinary chemical reactions, the nucleus of each atom (and thus the identity of the element) remains unchanged. Electrons,
however, can be added to atoms by transfer from other atoms, lost by transfer to other atoms, or shared with other atoms. The
transfer and sharing of electrons among atoms govern the chemistry of the elements. During the formation of some compounds,
atoms gain or lose electrons, and form electrically charged particles called ions (Figure 2.7.1).
Figure 2.7.1 : (a) A sodium atom (Na) has equal numbers of protons and electrons (11) and is uncharged. (b) A sodium cation (Na+)
has lost an electron, so it has one more proton (11) than electrons (10), giving it an overall positive charge, signified by a
superscripted plus sign.
Figure A shows a sodium atom which has a nucleus containing 11 protons, 12 neutrons, and 11 electrons. Figure B shows a sodium
ion. Its nucleus contains 11 protons, 12 neutrons, and 11 electrons.
You can use the periodic table to predict whether an atom will form an anion or a cation, and you can often predict the charge of the
resulting ion. Atoms of many main-group metals lose enough electrons to leave them with the same number of electrons as an atom
of the preceding noble gas. To illustrate, an atom of an alkali metal (group 1) loses one electron and forms a cation with a 1+
charge; an alkaline earth metal (group 2) loses two electrons and forms a cation with a 2+ charge, and so on. For example, a neutral
calcium atom, with 20 protons and 20 electrons, readily loses two electrons. This results in a cation with 20 protons, 18 electrons,
and a 2+ charge. It has the same number of electrons as atoms of the preceding noble gas, argon, and is symbolized Ca2+. The name
of a metal ion is the same as the name of the metal atom from which it forms, so Ca2+ is called a calcium ion.
When atoms of nonmetal elements form ions, they generally gain enough electrons to give them the same number of electrons as an
atom of the next noble gas in the periodic table. Atoms of group 17 gain one electron and form anions with a 1− charge; atoms of
group 16 gain two electrons and form ions with a 2− charge, and so on. For example, the neutral bromine atom, with 35 protons
and 35 electrons, can gain one electron to provide it with 36 electrons. This results in an anion with 35 protons, 36 electrons, and a
1− charge. It has the same number of electrons as atoms of the next noble gas, krypton, and is symbolized Br−. (A discussion of the
theory supporting the favored status of noble gas electron numbers reflected in these predictive rules for ion formation is provided
in a later chapter of this text.)
Note the usefulness of the periodic table in predicting likely ion formation and charge (Figure 2.7.2). Moving from the far left to
the right on the periodic table, main-group elements tend to form cations with a charge equal to the group number. That is, group 1
elements form 1+ ions; group 2 elements form 2+ ions, and so on. Moving from the far right to the left on the periodic table,
elements often form anions with a negative charge equal to the number of groups moved left from the noble gases. For example,
group 17 elements (one group left of the noble gases) form 1− ions; group 16 elements (two groups left) form 2− ions, and so on.
This trend can be used as a guide in many cases, but its predictive value decreases when moving toward the center of the periodic
table. In fact, transition metals and some other metals often exhibit variable charges that are not predictable by their location in the
table. For example, copper can form ions with a 1+ or 2+ charge, and iron can form ions with a 2+ or 3+ charge.

Figure 2.7.2 : Some elements exhibit a regular pattern of ionic charge when they form ions.
This periodic table shows the charges of ions corresponding with the group number. Starting with a charge of positive one for
group 1, positive 2 for group 2, and negative 4, 3, 2, and 1 for groups 14, 15, 16, and 17 respectively. Noble gases on the far right
do not have any charges. Some of the ions of transition metals are shown, with multiple charges existing for certain metals.
 Example 2.7.1: Composition of Ions
An ion found in some compounds used as antiperspirants contains 13 protons and 10 electrons. What is its symbol?
Solution
Because the number of protons remains unchanged when an atom forms an ion, the atomic number of the element must be 13.
Knowing this lets us use the periodic table to identify the element as Al (aluminum). The Al atom has lost three electrons and
thus has three more positive charges (13) than it has electrons (10). This is the aluminum cation, Al3+.
 Exercise 2.7.1
Give the symbol and name for the ion with 34 protons and 36 electrons.
Answer
Se2−, the selenide ion
 Example 2.7.2: Formation of Ions
Magnesium and nitrogen react to form an ionic compound. Predict which forms an anion, which forms a cation, and the
charges of each ion. Write the symbol for each ion and name them.
Solution
Magnesium’s position in the periodic table (group 2) tells us that it is a metal. Metals form positive ions (cations). A
magnesium atom must lose two electrons to have the same number electrons as an atom of the previous noble gas, neon. Thus,
a magnesium atom will form a cation with two fewer electrons than protons and a charge of 2+. The symbol for the ion is
Mg2+, and it is called a magnesium ion.

Nitrogen’s position in the periodic table (group 15) reveals that it is a nonmetal. Nonmetals form negative ions (anions). A
nitrogen atom must gain three electrons to have the same number of electrons as an atom of the following noble gas, neon.
Thus, a nitrogen atom will form an anion with three more electrons than protons and a charge of 3−. The symbol for the ion is
N3−, and it is called a nitride ion.
 Exercise 2.7.2
Aluminum and carbon react to form an ionic compound. Predict which forms an anion, which forms a cation, and the charges
of each ion. Write the symbol for each ion and name them.
Answer
Al will form a cation with a charge of 3+: Al3+, an aluminum ion. Carbon will form an anion with a charge of 4−: C4−, a
carbide ion.
The ions that we have discussed so far are called monatomic ions, that is, they are ions formed from only one atom. We also find
many polyatomic ions. These ions, which act as discrete units, are electrically charged molecules (a group of bonded atoms with an
overall charge). Some of the more important polyatomic ions are listed in Table 2.7.1. Oxyanions are polyatomic ions that contain
one or more oxygen atoms. At this point in your study of chemistry, you should memorize the names, formulas, and charges of the
most common polyatomic ions. Because you will use them repeatedly, they will soon become familiar.
Table 2.7.1 : Common Polyatomic Ions
Name Formula Related Acid Formula
ammonium NH
+
hydronium H O
3
+
oxide O
2 −
peroxide O
2 −
2
hydroxide OH
−
acetate CH COO
3
−
acetic acid CH COOH
3
cyanide CN
−
hydrocyanic acid HCN
azide N
−
3
hydrazoic acid HN
3
carbonate CO
2 −
3
carbonic acid H CO
2 3
bicarbonate HCO
−
3
nitrate NO
−
3
nitric acid HNO
3
nitrite NO
−
2
nitrous acid HNO
2
sulfate SO
2 −
4
sulfuric acid H SO
2 4
hydrogen sulfate HSO

−
4
sulfite SO
2 −
3
sulfurous acid H SO
2 3
hydrogen sulfite HSO

−
3
phosphate PO
3 −
4
phosphoric acid H PO
3 4
hydrogen phosphate HPO

2 −
4
dihydrogen phosphate H PO
2
−
4
perchlorate ClO
−
4
perchloric acid HClO
4
chlorate ClO
−
3
chloric acid HClO
3

Name Formula Related Acid Formula
chlorite ClO
−
2
chlorous acid HClO
2
hypochlorite ClO
−
hypochlorous acid HClO
chromate CrO
2 −
4
chromic acid H CrO
2 4
dichromate Cr O
2
2 −
7
dichromic acid H Cr O
2 2 7
permanganate MnO
−
4
permanganic acid HMnO
4
Note that there is a system for naming some polyatomic ions; -ate and -ite are suffixes designating polyatomic ions containing
more or fewer oxygen atoms. Per- (short for “hyper”) and hypo- (meaning “under”) are prefixes meaning more oxygen atoms than
-ate and fewer oxygen atoms than -ite, respectively. For example, perchlorate is ClO , chlorate is ClO , chlorite is ClO and
−
4
−
3
−
2
hypochlorite is ClO−. Unfortunately, the number of oxygen atoms corresponding to a given suffix or prefix is not consistent; for
example, nitrate is NO while sulfate is SO . This will be covered in more detail in the next module on nomenclature.
−
3
2 −
4
The nature of the attractive forces that hold atoms or ions together within a compound is the basis for classifying chemical bonding.
When electrons are transferred and ions form, ionic bonds result. Ionic bonds are electrostatic forces of attraction, that is, the
attractive forces experienced between objects of opposite electrical charge (in this case, cations and anions). When electrons are
“shared” and molecules form, covalent bonds result. Covalent bonds are the attractive forces between the positively charged nuclei
of the bonded atoms and one or more pairs of electrons that are located between the atoms. Compounds are classified as ionic or
molecular (covalent) on the basis of the bonds present in them.
Ionic Compounds
When an element composed of atoms that readily lose electrons (a metal) reacts with an element composed of atoms that readily
gain electrons (a nonmetal), a transfer of electrons usually occurs, producing ions. The compound formed by this transfer is
stabilized by the electrostatic attractions (ionic bonds) between the ions of opposite charge present in the compound. For example,
when each sodium atom in a sample of sodium metal (group 1) gives up one electron to form a sodium cation, Na+, and each
chlorine atom in a sample of chlorine gas (group 17) accepts one electron to form a chloride anion, Cl−, the resulting compound,
NaCl, is composed of sodium ions and chloride ions in the ratio of one Na+ ion for each Cl− ion. Similarly, each calcium atom
(group 2) can give up two electrons and transfer one to each of two chlorine atoms to form CaCl2, which is composed of Ca2+ and
Cl− ions in the ratio of one Ca2+ ion to two Cl− ions.
A compound that contains ions and is held together by ionic bonds is called an ionic compound. The periodic table can help us
recognize many of the compounds that are ionic: When a metal is combined with one or more nonmetals, the compound is usually
ionic. This guideline works well for predicting ionic compound formation for most of the compounds typically encountered in an
introductory chemistry course. However, it is not always true (for example, aluminum chloride, AlCl3, is not ionic).
You can often recognize ionic compounds because of their properties. Ionic compounds are solids that typically melt at high
temperatures and boil at even higher temperatures. For example, sodium chloride melts at 801 °C and boils at 1413 °C. (As a
comparison, the molecular compound water melts at 0 °C and boils at 100 °C.) In solid form, an ionic compound is not electrically
conductive because its ions are unable to flow (“electricity” is the flow of charged particles). When molten, however, it can conduct
electricity because its ions are able to move freely through the liquid (Figure 2.7.3).

Figure 2.7.3 : Sodium chloride melts at 801 °C and conducts electricity when molten. (credit: modification of work by Mark Blaser
and Matt Evans)
This figure shows three photos connected by right-facing arrows. The first shows a light bulb as part of a complex lab equipment
setup. The light bulb is not lit. The second photo shows a substances being heated or set on fire. The third shows the light bulb
again which is lit.
In every ionic compound, the total number of positive charges of the cations equals the total number of negative charges of the
anions. Thus, ionic compounds are electrically neutral overall, even though they contain positive and negative ions. We can use this
observation to help us write the formula of an ionic compound. The formula of an ionic compound must have a ratio of ions such
that the numbers of positive and negative charges are equal.
 Example 2.7.3: Predicting the Formula of an Ionic Compound
The gemstone sapphire (Figure 2.7.4) is mostly a compound of aluminum and oxygen that contains aluminum cations, Al3+,
and oxygen anions, O2−. What is the formula of this compound?
Figure 2.7.4 : Although pure aluminum oxide is colorless, trace amounts of iron and titanium give blue sapphire its
characteristic color. (credit: modification of work by Stanislav Doronenko)
Solution Because the ionic compound must be electrically neutral, it must have the same number of positive and negative
charges. Two aluminum ions, each with a charge of 3+, would give us six positive charges, and three oxide ions, each with a
charge of 2−, would give us six negative charges. The formula would be Al2O3.
 Exercise 2.7.3
Predict the formula of the ionic compound formed between the sodium cation, Na+, and the sulfide anion, S2−.
Answer
Na2S
Many ionic compounds contain polyatomic ions (Table 2.7.1) as the cation, the anion, or both. As with simple ionic compounds,
these compounds must also be electrically neutral, so their formulas can be predicted by treating the polyatomic ions as discrete
units. We use parentheses in a formula to indicate a group of atoms that behave as a unit. For example, the formula for calcium
phosphate, one of the minerals in our bones, is Ca3(PO4)2. This formula indicates that there are three calcium ions (Ca2+) for every
two phosphate (PO ) groups. The PO
3 −
4
groups are discrete units, each consisting of one phosphorus atom and four oxygen
3 −
4

atoms, and having an overall charge of 3−. The compound is electrically neutral, and its formula shows a total count of three Ca,
two P, and eight O atoms.
 Example 2.7.4: Predicting the Formula of a Compound with a Polyatomic Anion
Baking powder contains calcium dihydrogen phosphate, an ionic compound composed of the ions Ca2+ and H 2
−
PO4 . What is
the formula of this compound?
Solution
The positive and negative charges must balance, and this ionic compound must be electrically neutral. Thus, we must have two
negative charges to balance the 2+ charge of the calcium ion. This requires a ratio of one Ca2+ ion to two H PO ions. We
2
−
4
designate this by enclosing the formula for the dihydrogen phosphate ion in parentheses and adding a subscript 2. The formula
is Ca(H2PO4)2.
 Exercise 2.7.4
Predict the formula of the ionic compound formed between the lithium ion and the peroxide ion, O 2−
2
(Hint: Use the periodic
table to predict the sign and the charge on the lithium ion.)
Answer
Li2O2
Because an ionic compound is not made up of single, discrete molecules, it may not be properly symbolized using a molecular
formula. Instead, ionic compounds must be symbolized by a formula indicating the relative numbers of its constituent ions. For
compounds containing only monatomic ions (such as NaCl) and for many compounds containing polyatomic ions (such as CaSO4),
these formulas are just the empirical formulas introduced earlier in this chapter. However, the formulas for some ionic compounds
containing polyatomic ions are not empirical formulas. For example, the ionic compound sodium oxalate is comprised of Na+ and
C O
2
2−
4
ions combined in a 2:1 ratio, and its formula is written as Na2C2O4. The subscripts in this formula are not the smallest-
possible whole numbers, as each can be divided by 2 to yield the empirical formula, NaCO2. This is not the accepted formula for
sodium oxalate, however, as it does not accurately represent the compound’s polyatomic anion, C O .2
2−
Molecular Compounds
Many compounds do not contain ions but instead consist solely of discrete, neutral molecules. These molecular compounds
(covalent compounds) result when atoms share, rather than transfer (gain or lose), electrons. Covalent bonding is an important and
extensive concept in chemistry, and it will be treated in considerable detail in a later chapter of this text. We can often identify
molecular compounds on the basis of their physical properties. Under normal conditions, molecular compounds often exist as
gases, low-boiling liquids, and low-melting solids, although many important exceptions exist.
Whereas ionic compounds are usually formed when a metal and a nonmetal combine, covalent compounds are usually formed by a
combination of nonmetals. Thus, the periodic table can help us recognize many of the compounds that are covalent. While we can
use the positions of a compound’s elements in the periodic table to predict whether it is ionic or covalent at this point in our study
of chemistry, you should be aware that this is a very simplistic approach that does not account for a number of interesting
exceptions. Shades of gray exist between ionic and molecular compounds, and you’ll learn more about those later.
 Example 2.7.5: Predicting the Type of Bonding in Compounds
Predict whether the following compounds are ionic or molecular:

a. KI, the compound used as a source of iodine in table salt
b. H2O2, the bleach and disinfectant hydrogen peroxide
c. CHCl3, the anesthetic chloroform

d. Li2CO3, a source of lithium in antidepressants
Solution
a. Potassium (group 1) is a metal, and iodine (group 17) is a nonmetal; KI is predicted to be ionic.
b. Hydrogen (group 1) is a nonmetal, and oxygen (group 16) is a nonmetal; H2O2 is predicted to be molecular.
c. Carbon (group 14) is a nonmetal, hydrogen (group 1) is a nonmetal, and chlorine (group 17) is a nonmetal; CHCl3 is
predicted to be molecular.
d. Lithium (group 1) is a metal, and carbonate is a polyatomic ion; Li2CO3 is predicted to be ionic.
 Exercise 2.7.5
Using the periodic table, predict whether the following compounds are ionic or covalent:
a. SO2
b. CaF2
c. N2H4
d. Al2(SO4)3
Answer a
molecular
Answer b
ionic
Answer c
molecular
Answer d
ionic
Summary
Metals (particularly those in groups 1 and 2) tend to lose the number of electrons that would leave them with the same number of
electrons as in the preceding noble gas in the periodic table. By this means, a positively charged ion is formed. Similarly, nonmetals
(especially those in groups 16 and 17, and, to a lesser extent, those in Group 15) can gain the number of electrons needed to
provide atoms with the same number of electrons as in the next noble gas in the periodic table. Thus, nonmetals tend to form
negative ions. Positively charged ions are called cations, and negatively charged ions are called anions. Ions can be either
monatomic (containing only one atom) or polyatomic (containing more than one atom).
Compounds that contain ions are called ionic compounds. Ionic compounds generally form from metals and nonmetals.
Compounds that do not contain ions, but instead consist of atoms bonded tightly together in molecules (uncharged groups of atoms
that behave as a single unit), are called covalent compounds. Covalent compounds usually form from two or more nonmetals.
Glossary
covalent bond
attractive force between the nuclei of a molecule’s atoms and pairs of electrons between the atoms
covalent compound
(also, molecular compound) composed of molecules formed by atoms of two or more different elements
ionic bond
electrostatic forces of attraction between the oppositely charged ions of an ionic compound

ionic compound
compound composed of cations and anions combined in ratios, yielding an electrically neutral substance
molecular compound
(also, covalent compound) composed of molecules formed by atoms of two or more different elements
monatomic ion
ion composed of a single atom
polyatomic ion
ion composed of more than one atom
oxyanion
polyatomic anion composed of a central atom bonded to oxygen atoms
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Derive names for common types of inorganic compounds using a systematic approach.
Describe how to name binary covalent compounds including acids and oxyacids.
Nomenclature, a collection of rules for naming things, is important in science and in many other situations. This module describes
an approach that is used to name simple ionic and molecular compounds, such as NaCl, CaCO3, and N2O4. The simplest of these
are binary compounds, those containing only two elements, but we will also consider how to name ionic compounds containing
polyatomic ions, and one specific, very important class of compounds known as acids (subsequent chapters in this text will focus
on these compounds in great detail). We will limit our attention here to inorganic compounds, compounds that are composed
principally of elements other than carbon, and will follow the nomenclature guidelines proposed by IUPAC. The rules for organic
compounds, in which carbon is the principle element, will be treated in a later chapter on organic chemistry.
Ionic Compounds
To name an inorganic compound, we need to consider the answers to several questions. First, is the compound ionic or molecular?
If the compound is ionic, does the metal form ions of only one type (fixed charge) or more than one type (variable charge)? Are the
ions monatomic or polyatomic? If the compound is molecular, does it contain hydrogen? If so, does it also contain oxygen? From
the answers we derive, we place the compound in an appropriate category and then name it accordingly. We will begin with the
nomenclature rules for ionic compounds.
Compounds Containing Only Monatomic Ions

The name of a binary compound containing monatomic ions consists of the name of the cation (the name of the metal) followed by
the name of the anion (the name of the nonmetallic element with its ending replaced by the suffix –ide). Some examples are given
in Table 2.8.2.
Table 2.8.1 : Names of Some Ionic Compounds
NaCl, sodium chloride Na2O, sodium oxide
KBr, potassium bromide CdS, cadmium sulfide
CaI2, calcium iodide Mg3N2, magnesium nitride
CsF, cesium fluoride Ca3P2, calcium phosphide
LiCl, lithium chloride Al4C3, aluminum carbide
Compounds Containing Polyatomic Ions

Compounds containing polyatomic ions are named similarly to those containing only monatomic ions, except there is no need to
change to an –ide ending, since the suffix is already present in the name of the anion. Examples are shown in Table 2.8.2.
CL, ammonium chloride, C a S O subscript 4 calcium sulfate, and M g subscript 3 ( P O subscript 4 ) subscript 2 magnesium
phosphate." data-quail-id="54" data-mt-width="1246">
Table 2.8.2 : Names of Some Polyatomic Ionic Compounds
KC2H3O2, potassium acetate (NH4)Cl, ammonium chloride
NaHCO3, sodium bicarbonate CaSO4, calcium sulfate
Al2(CO3)3, aluminum carbonate Mg3(PO4)2, magnesium phosphate

 Ionic Compounds in Your Cabinets
Every day you encounter and use a large number of ionic compounds. Some of these compounds, where they are found, and
what they are used for are listed in Table 2.8.3. Look at the label or ingredients list on the various products that you use during
the next few days, and see if you run into any of those in this table, or find other ionic compounds that you could now name or
write as a formula.
Table 2.8.3 : Everyday Ionic Compounds
Ionic Compound Name Use
NaCl sodium chloride ordinary table salt
KI potassium iodide added to “iodized” salt for thyroid health
NaF sodium fluoride ingredient in toothpaste
baking soda; used in cooking (and in

NaHCO3 sodium bicarbonate
antacids)
Na2CO3 sodium carbonate washing soda; used in cleaning agents
NaOCl sodium hypochlorite active ingredient in household bleach
CaCO3 calcium carbonate ingredient in antacids
Mg(OH)2 magnesium hydroxide ingredient in antacids
Al(OH)3 aluminum hydroxide ingredient in antacids
NaOH sodium hydroxide lye; used as drain cleaner
K3PO4 potassium phosphate food additive (many purposes)
MgSO4 magnesium sulfate added to purified water
Na2HPO4 sodium hydrogen phosphate anti-caking agent; used in powdered products
Na2SO3 sodium sulfite preservative
Compounds Containing a Metal Ion with a Variable Charge

Most of the transition metals can form two or more cations with different charges. Compounds of these metals with nonmetals are
named with the same method as compounds in the first category, except the charge of the metal ion is specified by a Roman
numeral in parentheses after the name of the metal. The charge of the metal ion is determined from the formula of the compound
and the charge of the anion. For example, consider binary ionic compounds of iron and chlorine. Iron typically exhibits a charge of
either 2+ or 3+, and the two corresponding compound formulas are FeCl2 and FeCl3. The simplest name, “iron chloride,” will, in
this case, be ambiguous, as it does not distinguish between these two compounds. In cases like this, the charge of the metal ion is
included as a Roman numeral in parentheses immediately following the metal name. These two compounds are then
unambiguously named iron(II) chloride and iron(III) chloride, respectively. Other examples are provided in Table 2.8.4.
Table 2.8.4 : Names of Some Transition Metal Ionic Compounds
Transition Metal Ionic Compound Name
FeCl3 iron(III) chloride
Hg2O mercury(I) oxide
HgO mercury(II) oxide
Cu3(PO4)2 copper(II) phosphate
Out-of-date nomenclature used the suffixes –ic and –ous to designate metals with higher and lower charges, respectively: Iron(III)
chloride, FeCl3, was previously called ferric chloride, and iron(II) chloride, FeCl2, was known as ferrous chloride. Though this
naming convention has been largely abandoned by the scientific community, it remains in use by some segments of industry. For
example, you may see the words stannous fluoride on a tube of toothpaste. This represents the formula SnF2, which is more

properly named tin(II) fluoride. The other fluoride of tin is SnF4, which was previously called stannic fluoride but is now named
tin(IV) fluoride.
 Example 2.8.1: Naming Ionic Compounds
Name the following ionic compounds, which contain a metal that can have more than one ionic charge:
a. Fe2S3
b. CuSe
c. GaN
d. CrCl3
e. Ti2(SO4)3
Solution
The anions in these compounds have a fixed negative charge (S2−, Se2− , N3−, Cl−, and SO ), and the compounds must be
2−
neutral. Because the total number of positive charges in each compound must equal the total number of negative charges, the
positive ions must be Fe3+, Cu2+, Ga3+, Cr3+, and Ti3+. These charges are used in the names of the metal ions:
a. iron(III) sulfide
b. copper(II) selenide
c. gallium(III) nitride
d. chromium(III) chloride
e. titanium(III) sulfate
 Exercise 2.8.1
Write the formulas of the following ionic compounds:

a. chromium(III) phosphide
b. mercury(II) sulfide
c. manganese(II) phosphate
d. copper(I) oxide
e. chromium(VI) fluoride
Answer a
CrP
Answer b
HgS
Answer c
Mn3(PO4)2
Answer d
Cu2O
Answer e
CrF6
 Erin Brokovich and Chromium Contamination
In the early 1990s, legal file clerk Erin Brockovich (Figure 2.8.2) discovered a high rate of serious illnesses in the small town
of Hinckley, California. Her investigation eventually linked the illnesses to groundwater contaminated by Cr(VI) used by
Pacific Gas & Electric (PG&E) to fight corrosion in a nearby natural gas pipeline. As dramatized in the film Erin Brokovich
(for which Julia Roberts won an Oscar), Erin and lawyer Edward Masry sued PG&E for contaminating the water near Hinckley

in 1993. The settlement they won in 1996—$333 million—was the largest amount ever awarded for a direct-action lawsuit in
the US at that time.
Figure 2.8.2: (a) Erin Brockovich found that Cr(VI), used by PG&E, had contaminated the Hinckley, California, water supply.
(b) The Cr(VI) ion is often present in water as the polyatomic ions chromate, CrO (left), and dichromate, Cr O (right).
2−
4 2
2−
Chromium compounds are widely used in industry, such as for chrome plating, in dye-making, as preservatives, and to prevent
corrosion in cooling tower water, as occurred near Hinckley. In the environment, chromium exists primarily in either the
Cr(III) or Cr(VI) forms. Cr(III), an ingredient of many vitamin and nutritional supplements, forms compounds that are not very
soluble in water, and it has low toxicity. Cr(VI), on the other hand, is much more toxic and forms compounds that are
reasonably soluble in water. Exposure to small amounts of Cr(VI) can lead to damage of the respiratory, gastrointestinal, and
immune systems, as well as the kidneys, liver, blood, and skin.
Despite cleanup efforts, Cr(VI) groundwater contamination remains a problem in Hinckley and other locations across the
globe. A 2010 study by the Environmental Working Group found that of 35 US cities tested, 31 had higher levels of Cr(VI) in
their tap water than the public health goal of 0.02 parts per billion set by the California Environmental Protection Agency.
Molecular (Covalent) Compounds

The bonding characteristics of inorganic molecular compounds are different from ionic compounds, and they are named using a
different system as well. The charges of cations and anions dictate their ratios in ionic compounds, so specifying the names of the
ions provides sufficient information to determine chemical formulas. However, because covalent bonding allows for significant
variation in the combination ratios of the atoms in a molecule, the names for molecular compounds must explicitly identify these
ratios.
Compounds Composed of Two Elements

When two nonmetallic elements form a molecular compound, several combination ratios are often possible. For example, carbon
and oxygen can form the compounds CO and CO2. Since these are different substances with different properties, they cannot both
have the same name (they cannot both be called carbon oxide). To deal with this situation, we use a naming method that is
somewhat similar to that used for ionic compounds, but with added prefixes to specify the numbers of atoms of each element. The
name of the more metallic element (the one farther to the left and/or bottom of the periodic table) is first, followed by the name of
the more nonmetallic element (the one farther to the right and/or top) with its ending changed to the suffix –ide. The numbers of
atoms of each element are designated by the Greek prefixes shown in Table 2.8.5.
Table 2.8.5 : Nomenclature Prefixes
Number Prefix Number Prefix
1 (sometimes omitted) mono- 6 hexa-
2 di- 7 hepta-
3 tri- 8 octa-
4 tetra- 9 nona-
5 penta- 10 deca-

When only one atom of the first element is present, the prefix mono- is usually deleted from that part. Thus, CO is named carbon
monoxide, and CO is called carbon dioxide. When two vowels are adjacent, the a in the Greek prefix is usually dropped. Some
2
other examples are shown in Table 2.8.6.

Table 2.8.6 : Names of Some Molecular Compounds Composed of Two Elements
Compound Name Compound Name
SO2 sulfur dioxide BCl3 boron trichloride
SO3 sulfur trioxide SF6 sulfur hexafluoride
NO2 nitrogen dioxide PF5 phosphorus pentafluoride
N2O4 dinitrogen tetroxide P4O10 tetraphosphorus decaoxide
N2O5 dinitrogen pentoxide IF7 iodine heptafluoride
There are a few common names that you will encounter as you continue your study of chemistry. For example, although NO is
often called nitric oxide, its proper name is nitrogen monoxide. Similarly, N2O is known as nitrous oxide even though our rules
would specify the name dinitrogen monoxide. (And H2O is usually called water, not dihydrogen monoxide.) You should commit to
memory the common names of compounds as you encounter them.
 Example 2.8.2: Naming Covalent Compounds
Name the following covalent compounds:

a. SF6
b. N2O3
c. Cl2O7
d. P4O6
Solution
Because these compounds consist solely of nonmetals, we use prefixes to designate the number of atoms of each element:
a. sulfur hexafluoride
b. dinitrogen trioxide
c. dichlorine heptoxide
d. tetraphosphorus hexoxide
 Exercise 2.8.2
Write the formulas for the following compounds:

a. phosphorus pentachloride
b. dinitrogen monoxide
c. iodine heptafluoride
d. carbon tetrachloride
Answer a
PCl5
Answer b
N2O
Answer c
IF7
Answer d
CCl4

Binary Acids
Some compounds containing hydrogen are members of an important class of substances known as acids. The chemistry of these
compounds is explored in more detail in later chapters of this text, but for now, it will suffice to note that many acids release
hydrogen ions, H+, when dissolved in water. To denote this distinct chemical property, a mixture of water with an acid is given a
name derived from the compound’s name. If the compound is a binary acid (comprised of hydrogen and one other nonmetallic
element):
1. The word “hydrogen” is changed to the prefix hydro-
2. The other nonmetallic element name is modified by adding the suffix -ic
3. The word “acid” is added as a second word
For example, when the gas HCl (hydrogen chloride) is dissolved in water, the solution is called hydrochloric acid. Several other
examples of this nomenclature are shown in Table 2.8.7.
Table 2.8.7 : Names of Some Simple Acids
Name of Gas Name of Acid
HF(g), hydrogen fluoride HF(aq), hydrofluoric acid
HCl(g), hydrogen chloride HCl(aq), hydrochloric acid
HBr(g), hydrogen bromide HBr(aq), hydrobromic acid
HI(g), hydrogen iodide HI(aq), hydroiodic acid
H2S(g), hydrogen sulfide H2S(aq), hydrosulfuric acid
Oxyacids
Many compounds containing three or more elements (such as organic compounds or coordination compounds) are subject to
specialized nomenclature rules that you will learn later. However, we will briefly discuss the important compounds known as
oxyacids, compounds that contain hydrogen, oxygen, and at least one other element, and are bonded in such a way as to impart
acidic properties to the compound (you will learn the details of this in a later chapter). Typical oxyacids consist of hydrogen
combined with a polyatomic, oxygen-containing ion. To name oxyacids:
1. Omit “hydrogen”
2. Start with the root name of the anion
3. Replace –ate with –ic, or –ite with –ous
4. Add “acid”
For example, consider H2CO3 (which you might be tempted to call “hydrogen carbonate”). To name this correctly, “hydrogen” is
omitted; the –ate of carbonate is replace with –ic; and acid is added—so its name is carbonic acid. Other examples are given in
Table 2.8.8. There are some exceptions to the general naming method (e.g., H2SO4 is called sulfuric acid, not sulfic acid, and
H2SO3 is sulfurous, not sulfous, acid).
Table 2.8.8 : Names of Common Oxyacids
Formula Anion Name Acid Name
HC2H3O2 acetate acetic acid
HNO3 nitrate nitric acid
HNO2 nitrite nitrous acid
HClO4 perchlorate perchloric acid
H2CO3 carbonate carbonic acid
H2SO4 sulfate sulfuric acid
H2SO3 sulfite sulfurous acid

Formula Anion Name Acid Name
H3PO4 phosphate phosphoric acid
Summary
Chemists use nomenclature rules to clearly name compounds. Ionic and molecular compounds are named using somewhat-different
methods. Binary ionic compounds typically consist of a metal and a nonmetal. The name of the metal is written first, followed by
the name of the nonmetal with its ending changed to –ide. For example, K2O is called potassium oxide. If the metal can form ions
with different charges, a Roman numeral in parentheses follows the name of the metal to specify its charge. Thus, FeCl2 is iron(II)
chloride and FeCl3 is iron(III) chloride. Some compounds contain polyatomic ions; the names of common polyatomic ions should
be memorized. Molecular compounds can form compounds with different ratios of their elements, so prefixes are used to specify
the numbers of atoms of each element in a molecule of the compound. Examples include SF6, sulfur hexafluoride, and N2O4,
dinitrogen tetroxide. Acids are an important class of compounds containing hydrogen and having special nomenclature rules.
Binary acids are named using the prefix hydro-, changing the –ide suffix to –ic, and adding “acid;” HCl is hydrochloric acid.
Oxyacids are named by changing the ending of the anion (-ate to –ic, and -ite to -ous) and adding “acid;” H2CO3 is carbonic acid.
Glossary
binary acid
compound that contains hydrogen and one other element, bonded in a way that imparts acidic properties to the compound
(ability to release H+ ions when dissolved in water)
binary compound
compound containing two different elements.
oxyacid
compound that contains hydrogen, oxygen, and one other element, bonded in a way that imparts acidic properties to the
compound (ability to release H+ ions when dissolved in water)
nomenclature
system of rules for naming objects of interest
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In the following drawing, the green spheres represent atoms of a certain element. The purple spheres represent atoms of another
element. If the spheres of different elements touch, they are part of a single unit of a compound. The following chemical change
represented by these spheres may violate one of the ideas of Dalton’s atomic theory. Which one?
This equation contains the starting materials of a single, green sphere plus two smaller, purple spheres bonded together. When the starting materials are added together the products of the change are one purple sphere
bonded with one green sphere plus one purple sphere bonded with one green sphere.
The starting materials consist of one green sphere and two purple spheres. The products consist of two green spheres and two
purple spheres. This violates Dalton’s postulate that that atoms are not created during a chemical change, but are merely
redistributed.
Which postulate of Dalton’s theory is consistent with the following observation concerning the weights of reactants and products?
When 100 grams of solid calcium carbonate is heated, 44 grams of carbon dioxide and 56 grams of calcium oxide are produced.
Identify the postulate of Dalton’s theory that is violated by the following observations: 59.95% of one sample of titanium dioxide is
titanium; 60.10% of a different sample of titanium dioxide is titanium.
This statement violates Dalton’s fourth postulate: In a given compound, the numbers of atoms of each type (and thus also the
percentage) always have the same ratio.
Samples of compound X, Y, and Z are analyzed, with results shown here.
Compound Description Mass of Carbon Mass of Hydrogen
clear, colorless, liquid with strong

X 1.776 g 0.148 g
odor

Y 1.974 g 0.329 g
odor

Z 7.812 g 0.651 g
odor
Do these data provide example(s) of the law of definite proportions, the law of multiple proportions, neither, or both? What do
these data tell you about compounds X, Y, and Z?
Exercises
1. The existence of isotopes violates one of the original ideas of Dalton’s atomic theory. Which one?
2. How are electrons and protons similar? How are they different?
3. How are protons and neutrons similar? How are they different?
4. Predict and test the behavior of α particles fired at a “plum pudding” model atom.
a. Predict the paths taken by α particles that are fired at atoms with a Thomson’s plum pudding model structure. Explain why
you expect the α particles to take these paths.
b. If α particles of higher energy than those in (a) are fired at plum pudding atoms, predict how their paths will differ from the
lower-energy α particle paths. Explain your reasoning.
c. Now test your predictions from (a) and (b). Open the Rutherford Scattering simulation and select the “Plum Pudding Atom”
tab. Set “Alpha Particles Energy” to “min,” and select “show traces.” Click on the gun to start firing α particles. Does this
match your prediction from (a)? If not, explain why the actual path would be that shown in the simulation. Hit the pause
button, or “Reset All.” Set “Alpha Particles Energy” to “max,” and start firing α particles. Does this match your prediction
from (b)? If not, explain the effect of increased energy on the actual paths as shown in the simulation.
5. Predict and test the behavior of α particles fired at a Rutherford atom model.
a. (a) Predict the paths taken by α particles that are fired at atoms with a Rutherford atom model structure. Explain why you
expect the α particles to take these paths.

b. (b) If α particles of higher energy than those in (a) are fired at Rutherford atoms, predict how their paths will differ from the
lower-energy α particle paths. Explain your reasoning.
c. (c) Predict how the paths taken by the α particles will differ if they are fired at Rutherford atoms of elements other than gold.
What factor do you expect to cause this difference in paths, and why?
d. (d) Now test your predictions from (a), (b), and (c). Open the Rutherford Scattering simulation and select the “Rutherford
Atom” tab. Due to the scale of the simulation, it is best to start with a small nucleus, so select “20” for both protons and
neutrons, “min” for energy, show traces, and then start firing α particles. Does this match your prediction from (a)? If not,
explain why the actual path would be that shown in the simulation. Pause or reset, set energy to “max,” and start firing α
particles. Does this match your prediction from (b)? If not, explain the effect of increased energy on the actual path as
shown in the simulation. Pause or reset, select “40” for both protons and neutrons, “min” for energy, show traces, and fire
away. Does this match your prediction from (c)? If not, explain why the actual path would be that shown in the simulation.
Repeat this with larger numbers of protons and neutrons. What generalization can you make regarding the type of atom and
effect on the path of α particles? Be clear and specific.
Solutions
1 Dalton originally thought that all atoms of a particular element had identical properties, including mass. Thus, the concept of
isotopes, in which an element has different masses, was a violation of the original idea. To account for the existence of isotopes, the
second postulate of his atomic theory was modified to state that atoms of the same element must have identical chemical properties.
2 Both are subatomic particles that reside in an atom’s nucleus. Both have approximately the same mass. Protons are positively
charged, whereas neutrons are uncharged.
3 Both are subatomic particles that reside in an atom’s nucleus. Both have approximately the same mass. Protons are positively
charged, whereas neutrons are uncharged.
4. (a) The plum pudding model indicates that the positive charge is spread uniformly throughout the atom, so we expect the α
particles to (perhaps) be slowed somewhat by the positive-positive repulsion, but to follow straight-line paths (i.e., not to be
deflected) as they pass through the atoms. (b) Higher-energy α particles will be traveling faster (and perhaps slowed less) and will
also follow straight-line paths through the atoms. (c) The α particles followed straight-line paths through the plum pudding atom.
There was no apparent slowing of the α particles as they passed through the atoms.
5. (a) The Rutherford atom has a small, positively charged nucleus, so most α particles will pass through empty space far from the
nucleus and be undeflected. Those α particles that pass near the nucleus will be deflected from their paths due to positive-positive
repulsion. The more directly toward the nucleus the α particles are headed, the larger the deflection angle will be. (b) Higher-energy
α particles that pass near the nucleus will still undergo deflection, but the faster they travel, the less the expected angle of
deflection. (c) If the nucleus is smaller, the positive charge is smaller and the expected deflections are smaller—both in terms of
how closely the α particles pass by the nucleus undeflected and the angle of deflection. If the nucleus is larger, the positive charge
is larger and the expected deflections are larger—more α particles will be deflected, and the deflection angles will be larger. (d) The
paths followed by the α particles match the predictions from (a), (b), and (c).

In what way are isotopes of a given element always different? In what way(s) are they always the same?
Write the symbol for each of the following ions:
1. (a) the ion with a 1+ charge, atomic number 55, and mass number 133
2. (b) the ion with 54 electrons, 53 protons, and 74 neutrons
3. (c) the ion with atomic number 15, mass number 31, and a 3− charge
4. (d) the ion with 24 electrons, 30 neutrons, and a 3+ charge
1.
(a) 133Cs+; (b) 127I−; (c) 31P3−; (d) 57Co3+
Write the symbol for each of the following ions:
1. (a) the ion with a 3+ charge, 28 electrons, and a mass number of 71
2. (b) the ion with 36 electrons, 35 protons, and 45 neutrons
3. (c) the ion with 86 electrons, 142 neutrons, and a 4+ charge

4. (d) the ion with a 2+ charge, atomic number 38, and mass number 87
Open the Build an Atom simulation and click on the Atom icon.
1. (a) Pick any one of the first 10 elements that you would like to build and state its symbol.
2. (b) Drag protons, neutrons, and electrons onto the atom template to make an atom of your element. State the numbers of
protons, neutrons, and electrons in your atom, as well as the net charge and mass number.
3. (c) Click on “Net Charge” and “Mass Number,” check your answers to (b), and correct, if needed.
4. (d) Predict whether your atom will be stable or unstable. State your reasoning.
5. (e) Check the “Stable/Unstable” box. Was your answer to (d) correct? If not, first predict what you can do to make a stable atom
of your element, and then do it and see if it works. Explain your reasoning.
(a) Carbon-12, 12C; (b) This atom contains six protons and six neutrons. There are six electrons in a neutral 12C atom. The net
charge of such a neutral atom is zero, and the mass number is 12. (c) The preceding answers are correct. (d) The atom will be stable
since C-12 is a stable isotope of carbon. (e) The preceding answer is correct. Other answers for this exercise are possible if a
different element of isotope is chosen.
Open the Build an Atom simulation
(a) Drag protons, neutrons, and electrons onto the atom template to make a neutral atom of Oxygen-16 and give the isotope symbol
for this atom.
(b) Now add two more electrons to make an ion and give the symbol for the ion you have created.
Open the Build an Atom simulation
(a) Drag protons, neutrons, and electrons onto the atom template to make a neutral atom of Lithium-6 and give the isotope symbol
for this atom.
(b) Now remove one electron to make an ion and give the symbol for the ion you have created.
(a) Lithium-6 contains three protons, three neutrons, and three electrons. The isotope symbol is 6Li or 6
3
Li . (b) 6Li+ or 6
3
Li
+
Determine the number of protons, neutrons, and electrons in the following isotopes that are used in medical diagnoses:
(a) atomic number 9, mass number 18, charge of 1−
(b) atomic number 43, mass number 99, charge of 7+
(c) atomic number 53, atomic mass number 131, charge of 1−
(d) atomic number 81, atomic mass number 201, charge of 1+
(e) Name the elements in parts (a), (b), (c), and (d).
The following are properties of isotopes of two elements that are essential in our diet. Determine the number of protons, neutrons
and electrons in each and name them.
(a) atomic number 26, mass number 58, charge of 2+
(b) atomic number 53, mass number 127, charge of 1−
(a) Iron, 26 protons, 24 electrons, and 32 neutrons; (b) iodine, 53 protons, 54 electrons, and 74 neutrons
Give the number of protons, electrons, and neutrons in neutral atoms of each of the following isotopes:
(a) 10
5
B
(b) 199
80
Hg
(c) 63
29
Cu
(d) 13
6
C
(e) 77
34
Se
Give the number of protons, electrons, and neutrons in neutral atoms of each of the following isotopes:
(a) 7
3
Li

(b) 125
52
Te
(c) 109
47
Ag
(d) 15
7
N
(e) 31
15
P
(a) 3 protons, 3 electrons, 4 neutrons; (b) 52 protons, 52 electrons, 73 neutrons; (c) 47 protons, 47 electrons, 62 neutrons; (d) 7
protons, 7 electrons, 8 neutrons; (e) 15 protons, 15 electrons, 16 neutrons
Click on the site and select the “Mix Isotopes” tab, hide the “Percent Composition” and “Average Atomic Mass” boxes, and then
select the element boron.
(a) Write the symbols of the isotopes of boron that are shown as naturally occurring in significant amounts.
(b) Predict the relative amounts (percentages) of these boron isotopes found in nature. Explain the reasoning behind your choice.
(c) Add isotopes to the black box to make a mixture that matches your prediction in (b). You may drag isotopes from their bins or
click on “More” and then move the sliders to the appropriate amounts.
(d) Reveal the “Percent Composition” and “Average Atomic Mass” boxes. How well does your mixture match with your
prediction? If necessary, adjust the isotope amounts to match your prediction.
(e) Select “Nature’s” mix of isotopes and compare it to your prediction. How well does your prediction compare with the naturally
occurring mixture? Explain. If necessary, adjust your amounts to make them match “Nature’s” amounts as closely as possible.
Repeat Exercise using an element that has three naturally occurring isotopes.
Let us use neon as an example. Since there are three isotopes, there is no way to be sure to accurately predict the abundances to
make the total of 20.18 amu average atomic mass. Let us guess that the abundances are 9% Ne-22, 91% Ne-20, and only a trace of
Ne-21. The average mass would be 20.18 amu. Checking the nature’s mix of isotopes shows that the abundances are 90.48% Ne-
20, 9.25% Ne-22, and 0.27% Ne-21, so our guessed amounts have to be slightly adjusted.
An element has the following natural abundances and isotopic masses: 90.92% abundance with 19.99 amu, 0.26% abundance with
20.99 amu, and 8.82% abundance with 21.99 amu. Calculate the average atomic mass of this element.
Average atomic masses listed by IUPAC are based on a study of experimental results. Bromine has two isotopes 79Br and 81Br,
whose masses (78.9183 and 80.9163 amu) and abundances (50.69% and 49.31%) were determined in earlier experiments.
Calculate the average atomic mass of bromine based on these experiments.
79.904 amu
Variations in average atomic mass may be observed for elements obtained from different sources. Lithium provides an example of
this. The isotopic composition of lithium from naturally occurring minerals is 7.5% 6Li and 92.5% 7Li, which have masses of
6.01512 amu and 7.01600 amu, respectively. A commercial source of lithium, recycled from a military source, was 3.75% 6Li (and
the rest 7Li). Calculate the average atomic mass values for each of these two sources.
The average atomic masses of some elements may vary, depending upon the sources of their ores. Naturally occurring boron
consists of two isotopes with accurately known masses (10B, 10.0129 amu and 11B, 11.0931 amu). The actual atomic mass of boron
can vary from 10.807 to 10.819, depending on whether the mineral source is from Turkey or the United States. Calculate the
percent abundances leading to the two values of the average atomic masses of boron from these two countries.
Turkey source: 0.2649 (of 10.0129 amu isotope); US source: 0.2537 (of 10.0129 amu isotope)
The 18O:16O abundance ratio in some meteorites is greater than that used to calculate the average atomic mass of oxygen on earth.
Is the average mass of an oxygen atom in these meteorites greater than, less than, or equal to that of a terrestrial oxygen atom?

Explain why the symbol for an atom of the element oxygen and the formula for a molecule of oxygen differ.
The symbol for the element oxygen, O, represents both the element and one atom of oxygen. A molecule of oxygen, O2, contains
two oxygen atoms; the subscript 2 in the formula must be used to distinguish the diatomic molecule from two single oxygen atoms.
Explain why the symbol for the element sulfur and the formula for a molecule of sulfur differ.

Write the molecular and empirical formulas of the following compounds:
(a)
Figure A shows a carbon atom that forms two, separate double bonds with two oxygen atoms.
(b)
Figure B shows a hydrogen atom which forms a single bond with a carbon atom. The carbon atom forms a triple bond with another carbon atom. The second carbon atom forms a single bond with a hydrogen atom.
(c)
Figure C shows a carbon atom forming a double bond with another carbon atom. Each carbon atom forms a single bond with two hydrogen atoms.
(d)
Figure D shows a sulfur atom forming single bonds with four oxygen atoms. Two of the oxygen atoms form a single bond with a hydrogen atom.
(a) molecular CO2, empirical CO2; (b) molecular C2H2, empirical CH; (c) molecular C2H4, empirical CH2; (d) molecular H2SO4,
empirical H2SO4
Write the molecular and empirical formulas of the following compounds:
(a)
Figure A shows a structural diagram of four carbon atoms bonded together into a chain. The two carbon atoms on the left form a double bond with each other. All of the remaining carbon atoms form single bonds with
each other. The leftmost carbon also forms single bonds with two hydrogen. The second carbon in the chain forms a single bond with a hydrogen atom. The third carbon in the chain forms a single bond with two
hydrogen atoms each. The rightmost carbon forms a single bond with three hydrogen atoms each.
(b)
Figure B shows a structural diagram of a molecule that has a chain of four carbon atoms. The leftmost carbon atom forms a single bond with three hydrogen atoms each and single bond with the second carbon atom.
The second carbon atom forms a triple bond with the third carbon atom. The third carbon atom forms a single bond to the fourth carbon atom. The fourth carbon atom forms a single bond to three hydrogen atoms each.
(c)
Figure C shows a structural diagram of two silicon atoms are bonded together with a single bond. Each of the silicon atoms form single bonds to two chlorine atoms each and one hydrogen atom.
(d)
Figure D shows a structural diagram of a phosphorus atom that forms a single bond to four oxygen atoms each. Three of the oxygen atoms each have a single bond to a hydrogen atom.
Determine the empirical formulas for the following compounds:

1. (a) caffeine, C8H10N4O2
2. (b) fructose, C12H22O11
3. (c) hydrogen peroxide, H2O2
4. (d) glucose, C6H12O6
5. (e) ascorbic acid (vitamin C), C6H8O6
(a) C4H5N2O; (b) C12H22O11; (c) HO; (d) CH2O; (e) C3H4O3
Determine the empirical formulas for the following compounds:
1. (a) acetic acid, C2H4O2
2. (b) citric acid, C6H8O7
3. (c) hydrazine, N2H4
4. (d) nicotine, C10H14N2
5. (e) butane, C4H10
Write the empirical formulas for the following compounds:
(a)
Figure A shows a structural diagram of two carbon atoms that form a single bond with each other. The left carbon atom forms single bonds with hydrogen atoms each. The right carbon forms a double bond to an
oxygen atom. The right carbon also forms a single bonded to another oxygen atom. This oxygen atom also forms a single bond to a hydrogen atom.
(b)
Figure B shows a structural diagram containing a leftmost carbon that forms single bonds to three hydrogen atoms each. This leftmost carbon also forms a single bond to a second carbon atom. The second carbon
atom forms a double bond with an oxygen atom. The second carbon also forms a single bond to a second oxygen atom. This oxygen atom forms a single bond to a third carbon atom. This third carbon atom forms single
bonds with two hydrogen atoms each as well as a single bond with another carbon atom. The rightmost carbon atom forms a single bond with three hydrogen atoms each.
(a) CH2O; (b) C2H4O

Open the Build a Molecule simulation and select the “Larger Molecules” tab. Select an appropriate atoms “Kit” to build a molecule
with two carbon and six hydrogen atoms. Drag atoms into the space above the “Kit” to make a molecule. A name will appear when
you have made an actual molecule that exists (even if it is not the one you want). You can use the scissors tool to separate atoms if
you would like to change the connections. Click on “3D” to see the molecule, and look at both the space-filling and ball-and-stick
possibilities.
1. (a) Draw the structural formula of this molecule and state its name.
2. (b) Can you arrange these atoms in any way to make a different compound?
Use the Build a Molecule simulation to repeat Exercise, but build a molecule with two carbons, six hydrogens, and one oxygen.
1. (a) Draw the structural formula of this molecule and state its name.
2. (b) Can you arrange these atoms to make a different molecule? If so, draw its structural formula and state its name.
3. (c) How are the molecules drawn in (a) and (b) the same? How do they differ? What are they called (the type of relationship
between these molecules, not their names).
(a) ethanol
A Lewis Structure is shown. An oxygen atom is bonded to a hydrogen atom and a carbon atom. The carbon atom is bonded to two hydrogen atoms and another carbon atom. That carbon atom is bonded to three more
hydrogen atoms. There are a total of two carbon atoms, six hydrogen atoms, and one oxygen atoms.
(b) methoxymethane, more commonly known as dimethyl ether

A Lewis Structure is shown. An oxygen atom is bonded to two carbon atoms. Each carbon atom is bonded to three different hydrogen atoms. There are a total of two carbon atoms, six hydrogen atoms, and one
oxygen atom.
(c) These molecules have the same chemical composition (types and number of atoms) but different chemical structures. They are
structural isomers.
Use the Build a Molecule simulation to repeat Exercise, but build a molecule with three carbons, seven hydrogens, and one
chlorine.
a. Draw the structural formula of this molecule and state its name.
b. Can you arrange these atoms to make a different molecule? If so, draw its structural formula and state its name.
c. How are the molecules drawn in (a) and (b) the same? How do they differ? What are they called (the type of relationship
between these molecules, not their names)?

Using the periodic table, classify each of the following elements as a metal or a nonmetal, and then further classify each as a main-
group (representative) element, transition metal, or inner transition metal:
a. uranium
b. bromine
c. strontium
d. neon
e. gold
f. americium
g. rhodium
h. sulfur
i. carbon
j. potassium
(a) metal, inner transition metal; (b) nonmetal, representative element; (c) metal, representative element; (d) nonmetal,
representative element; (e) metal, transition metal; (f) metal, inner transition metal; (g) metal, transition metal; (h) nonmetal,
representative element; (i) nonmetal, representative element; (j) metal, representative element
Using the periodic table, classify each of the following elements as a metal or a nonmetal, and then further classify each as a main-
group (representative) element, transition metal, or inner transition metal:
1. (a) cobalt
2. (b) europium
3. (c) iodine

4. (d) indium
5. (e) lithium
6. (f) oxygen
7. (g) cadmium
8. (h) terbium
9. (i) rhenium
Using the periodic table, identify the lightest member of each of the following groups:
1. (a) noble gases
2. (b) alkaline earth metals
3. (c) alkali metals
4. (d) chalcogens
(a) He; (b) Be; (c) Li; (d) O
Using the periodic table, identify the heaviest member of each of the following groups:
1. (a) alkali metals
2. (b) chalcogens
3. (c) noble gases
4. (d) alkaline earth metals
1. Use the periodic table to give the name and symbol for each of the following elements:
2. (a) the noble gas in the same period as germanium
3. (b) the alkaline earth metal in the same period as selenium
4. (c) the halogen in the same period as lithium
5. (d) the chalcogen in the same period as cadmium
(a) krypton, Kr; (b) calcium, Ca; (c) fluorine, F; (d) tellurium, Te
Use the periodic table to give the name and symbol for each of the following elements:
1. (a) the halogen in the same period as the alkali metal with 11 protons
2. (b) the alkaline earth metal in the same period with the neutral noble gas with 18 electrons
3. (c) the noble gas in the same row as an isotope with 30 neutrons and 25 protons
4. (d) the noble gas in the same period as gold
Write a symbol for each of the following neutral isotopes. Include the atomic number and mass number for each.
1. (a) the alkali metal with 11 protons and a mass number of 23
2. (b) the noble gas element with and 75 neutrons in its nucleus and 54 electrons in the neutral atom
3. (c) the isotope with 33 protons and 40 neutrons in its nucleus
4. (d) the alkaline earth metal with 88 electrons and 138 neutrons
(a) 23
11
Na ; (b) 129
54
Xe ; (c) 73
33
As ; (d) 226
88
Ra
Write a symbol for each of the following neutral isotopes. Include the atomic number and mass number for each.
1. (a) the chalcogen with a mass number of 125
2. (b) the halogen whose longest-lived isotope is radioactive
3. (c) the noble gas, used in lighting, with 10 electrons and 10 neutrons
4. (d) the lightest alkali metal with three neutrons

Using the periodic table, predict whether the following chlorides are ionic or covalent: KCl, NCl3, ICl, MgCl2, PCl5, and CCl4.
Ionic: KCl, MgCl2; Covalent: NCl3, ICl, PCl5, CCl4
Using the periodic table, predict whether the following chlorides are ionic or covalent: SiCl4, PCl3, CaCl2, CsCl, CuCl2, and CrCl3.
For each of the following compounds, state whether it is ionic or covalent. If it is ionic, write the symbols for the ions involved:

1. (a) NF3
2. (b) BaO,
3. (c) (NH4)2CO3
4. (d) Sr(H2PO4)2
5. (e) IBr
6. (f) Na2O
(a) covalent; (b) ionic, Ba2+, O2−; (c) ionic, NH , CO ; (d) ionic, Sr2+, H
+
4
2−
3 2
PO
−
4
; (e) covalent; (f) ionic, Na+, O2−
For each of the following compounds, state whether it is ionic or covalent, and if it is ionic, write the symbols for the ions involved:
1. (a) KClO4
2. (b) MgC2H3O2
3. (c) H2S
4. (d) Ag2S
5. (e) N2Cl4
6. (f) Co(NO3)2
For each of the following pairs of ions, write the symbol for the formula of the compound they will form:
1. (a) Ca2+, S2−
2. (b) NH , SO
+
4
2−
4
3. (c) Al3+, Br−

4. (d) Na+, HPO 2−
5. (e) Mg2+, PO 3−
(a) CaS; (b) (NH4)2CO3; (c) AlBr3; (d) Na2HPO4; (e) Mg3 (PO4)2
For each of the following pairs of ions, write the symbol for the formula of the compound they will form:
1. (a) K+, O2−
2. (b) NH , PO
+
4
3−
3. (c) Al3+, O2−

4. (d) Na+, CO 2−
3
5. (e) Ba2+, PO 3−
4

Name the following compounds:
1. (a) CsCl
2. (b) BaO
3. (c) K2S
4. (d) BeCl2
5. (e) HBr
6. (f) AlF3
(a) cesium chloride; (b) barium oxide; (c) potassium sulfide; (d) beryllium chloride; (e) hydrogen bromide; (f) aluminum fluoride
Name the following compounds:
1. (a) NaF
2. (b) Rb2O
3. (c) BCl3
4. (d) H2Se
5. (e) P4O6
6. (f) ICl3
Write the formulas of the following compounds:
1. (a) rubidium bromide
2. (b) magnesium selenide

3. (c) sodium oxide
4. (d) calcium chloride
5. (e) hydrogen fluoride
6. (f) gallium phosphide
7. (g) aluminum bromide
8. (h) ammonium sulfate
(a) RbBr; (b) MgSe; (c) Na2O; (d) CaCl2; (e) HF; (f) GaP; (g) AlBr3; (h) (NH4)2SO4
1. (a) lithium carbonate
2. (b) sodium perchlorate
3. (c) barium hydroxide
4. (d) ammonium carbonate
5. (e) sulfuric acid
6. (f) calcium acetate
7. (g) magnesium phosphate
8. (h) sodium sulfite
1. (a) chlorine dioxide
2. (b) dinitrogen tetraoxide
3. (c) potassium phosphide
4. (d) silver(I) sulfide
5. (e) aluminum nitride
6. (f) silicon dioxide
(a) ClO2; (b) N2O4; (c) K3P; (d) Ag2S; (e) AlN; (f) SiO2
1. (a) barium chloride
2. (b) magnesium nitride
3. (c) sulfur dioxide
4. (d) nitrogen trichloride
5. (e) dinitrogen trioxide
6. (f) tin(IV) chloride
Each of the following compounds contains a metal that can exhibit more than one ionic charge. Name these compounds:
1. (a) Cr2O3
2. (b) FeCl2
3. (c) CrO3
4. (d) TiCl4
5. (e) CoO
6. (f) MoS2
(a) chromium(III) oxide; (b) iron(II) chloride; (c) chromium(VI) oxide; (d) titanium(IV) chloride; (e) cobalt(II) oxide; (f)
molybdenum(IV) sulfide
Each of the following compounds contains a metal that can exhibit more than one ionic charge. Name these compounds:
1. (a) NiCO3
2. (b) MoO3
3. (c) Co(NO3)2
4. (d) V2O5
5. (e) MnO2
6. (f) Fe2O3

The following ionic compounds are found in common household products. Write the formulas for each compound:
1. (a) potassium phosphate
2. (b) copper(II) sulfate
3. (c) calcium chloride
4. (d) titanium dioxide
5. (e) ammonium nitrate
6. (f) sodium bisulfate (the common name for sodium hydrogen sulfate)
(a) K3PO4; (b) CuSO4; (c) CaCl2; (d) TiO2; (e) NH4NO3; (f) NaHSO4
The following ionic compounds are found in common household products. Name each of the compounds:
1. (a) Ca(H2PO4)2
2. (b) FeSO4
3. (c) CaCO3
4. (d) MgO
5. (e) NaNO2
6. (f) KI
What are the IUPAC names of the following compounds?
1. (a) manganese dioxide
2. (b) mercurous chloride (Hg2Cl2)
3. (c) ferric nitrate [Fe(NO3)3]
4. (d) titanium tetrachloride
5. (e) cupric bromide (CuBr2)
(a) manganese(IV) oxide; (b) mercury(I) chloride; (c) iron(III) nitrate; (d) titanium(IV) chloride; (e) copper(II) bromide
This page titled 2.E: Atoms, Molecules, and Ions (Exercises) is shared under a CC BY license and was authored, remixed, and/or curated by
OpenStax.

CHAPTER OVERVIEW
3: Electronic Structure and Periodic Properties

General Chemistry
The study of chemistry must at some point extend to the molecular level, for the physical and chemical properties of a substance
are ultimately explained in terms of the structure and bonding of molecules. This module introduces some basic facts and principles
that are needed for a discussion of organic molecules.
3.2: The Bohr Model
Contributors
[email protected]).
This page titled 3: Electronic Structure and Periodic Properties is shared under a CC BY license and was authored, remixed, and/or curated by
OpenStax.
1
Explain the basic behavior of waves, including traveling waves and standing waves
Describe the wave nature of light
Use appropriate equations to calculate related light-wave properties such as period, frequency, wavelength, and energy
Distinguish between line and continuous emission spectra
Describe the particle nature of light
The nature of light has been a subject of inquiry since antiquity. In the seventeenth century, Isaac Newton performed experiments
with lenses and prisms and was able to demonstrate that white light consists of the individual colors of the rainbow combined
together. Newton explained his optics findings in terms of a "corpuscular" view of light, in which light was composed of streams of
extremely tiny particles travelling at high speeds according to Newton's laws of motion. Others in the seventeenth century, such as
Christiaan Huygens, had shown that optical phenomena such as reflection and refraction could be equally well explained in terms
of light as waves travelling at high speed through a medium called "luminiferous aether" that was thought to permeate all space.
Early in the nineteenth century, Thomas Young demonstrated that light passing through narrow, closely spaced slits produced
interference patterns that could not be explained in terms of Newtonian particles but could be easily explained in terms of waves.
Later in the nineteenth century, after James Clerk Maxwell developed his theory of electromagnetic radiation and showed that light
was the visible part of a vast spectrum of electromagnetic waves, the particle view of light became thoroughly discredited. By the
end of the nineteenth century, scientists viewed the physical universe as roughly comprising two separate domains: matter
composed of particles moving according to Newton's laws of motion, and electromagnetic radiation consisting of waves governed
by Maxwell's equations. Today, these domains are referred to as classical mechanics and classical electrodynamics (or classical
electromagnetism). Although there were a few physical phenomena that could not be explained within this framework, scientists at
that time were so confident of the overall soundness of this framework that they viewed these aberrations as puzzling paradoxes
that would ultimately be resolved somehow within this framework. As we shall see, these paradoxes led to a contemporary
framework that intimately connects particles and waves at a fundamental level called wave-particle duality, which has superseded
the classical view.
Visible light and other forms of electromagnetic radiation play important roles in chemistry, since they can be used to infer the
energies of electrons within atoms and molecules. Much of modern technology is based on electromagnetic radiation. For example,
radio waves from a mobile phone, X-rays used by dentists, the energy used to cook food in your microwave, the radiant heat from
red-hot objects, and the light from your television screen are forms of electromagnetic radiation that all exhibit wavelike behavior.
Waves
A wave is an oscillation or periodic movement that can transport energy from one point in space to another. Common examples of
waves are all around us. Shaking the end of a rope transfers energy from your hand to the other end of the rope, dropping a pebble
into a pond causes waves to ripple outward along the water's surface, and the expansion of air that accompanies a lightning strike
generates sound waves (thunder) that can travel outward for several miles. In each of these cases, kinetic energy is transferred
through matter (the rope, water, or air) while the matter remains essentially in place. An insightful example of a wave occurs in
sports stadiums when fans in a narrow region of seats rise simultaneously and stand with their arms raised up for a few seconds
before sitting down again while the fans in neighboring sections likewise stand up and sit down in sequence. While this wave can
quickly encircle a large stadium in a few seconds, none of the fans actually travel with the wave-they all stay in or above their
seats.
Waves need not be restricted to travel through matter. As Maxwell showed, electromagnetic waves consist of an electric field
oscillating in step with a perpendicular magnetic field, both of which are perpendicular to the direction of travel. These waves can
travel through a vacuum at a constant speed of 2.998 × 108 m/s, the speed of light (denoted by c).
All waves, including forms of electromagnetic radiation, are characterized by, a wavelength (denoted by λ, the lowercase Greek
letter lambda), a frequency (denoted by ν, the lowercase Greek letter nu), and an amplitude. As can be seen in Figure 3.1.1, the
wavelength is the distance between two consecutive peaks or troughs in a wave (measured in meters in the SI system).
Electromagnetic waves have wavelengths that fall within an enormous range-wavelengths of kilometers (103 m) to picometers
(10−12 m) have been observed. The frequency is the number of wave cycles that pass a specified point in space in a specified

amount of time (in the SI system, this is measured in seconds). A cycle corresponds to one complete wavelength. The unit for
frequency, expressed as cycles per second [s−1], is the hertz (Hz). Common multiples of this unit are megahertz, (1 MHz = 1 × 106
Hz) and gigahertz (1 GHz = 1 × 109 Hz). The amplitude corresponds to the magnitude of the wave's displacement and so, in Figure,
this corresponds to one-half the height between the peaks and troughs. The amplitude is related to the intensity of the wave, which
for light is the brightness, and for sound is the loudness.
Figure 3.1.1 : One-dimensional sinusoidal waves show the relationship among wavelength, frequency, and speed. The wave with
the shortest wavelength has the highest frequency. Amplitude is one-half the height of the wave from peak to trough. (CC by 4.0;
OpenStax)
This figure includes 5 one-dimensional sinusoidal waves in two columns. The column on the left includes three waves, and the
column on the right includes two waves. In each column, dashed vertical line segments extend down the left and right sides of the
column. A right pointing arrow extends from the left dashed line to the right dashed line in both columns and is labeled, “Distance
traveled in 1 second.” The waves all begin on the left side at a crest. The wave at the upper left shows 3 peaks to the right of the
starting point. A bracket labeled, “lambda subscript 1,” extends upward from the second and third peaks. Beneath this wave is the
label, “nu subscript 1 equals 4 cycles per second equals 3 hertz.” The wave below has six peaks to the right of the starting point
with a bracket similarly connecting the third and fourth peaks which is labeled, “lambda subscript 2.” Beneath this wave is the
label, “nu subscript 2 equals 8 cycles per second equals 6 hertz” The third wave in the column has twelve peaks to the right of the
starting point with a bracket similarly connecting the seventh and eighth peaks which is labeled, “lambda subscript 3.” Beneath this
wave is the label, “nu subscript 3 equals 12 cycles per second equals 12 hertz.” All waves in this column appear to have the same
vertical distance from peak to trough. In the second column, the two waves are similarly shown, but lack the lambda labels. The top
wave in this column has a greater vertical distance between the peaks and troughs and is labeled, “Higher amplitude.” The wave
beneath it has a lesser distance between the peaks and troughs and is labeled, “Lower amplitude.”
The product of a wave's wavelength (λ) and its frequency (ν), λν, is the speed of the wave. Thus, for electromagnetic radiation in a
vacuum:
8 −1
c = 2.998 × 10 ms = λν (3.1.1)
Wavelength and frequency are inversely proportional: As the wavelength increases, the frequency decreases. The inverse
proportionality is illustrated in Figure 3.1.2. This figure also shows the electromagnetic spectrum, the range of all types of
electromagnetic radiation. Each of the various colors of visible light has specific frequencies and wavelengths associated with
them, and you can see that visible light makes up only a small portion of the electromagnetic spectrum. Because the technologies
developed to work in various parts of the electromagnetic spectrum are different, for reasons of convenience and historical legacies,
different units are typically used for different parts of the spectrum. For example, radio waves are usually specified as frequencies
(typically in units of MHz), while the visible region is usually specified in wavelengths (typically in units of nm or angstroms).

Figure 3.1.2 : Portions of the electromagnetic spectrum are shown in order of decreasing frequency and increasing wavelength.
Examples of some applications for various wavelengths include positron emission tomography (PET) scans, X-ray imaging, remote
controls, wireless Internet, cellular telephones, and radios. (credit “Cosmic ray": modification of work by NASA; credit “PET
scan": modification of work by the National Institute of Health; credit “X-ray": modification of work by Dr. Jochen Lengerke;
credit “Dental curing": modification of work by the Department of the Navy; credit “Night vision": modification of work by the
Department of the Army; credit “Remote": modification of work by Emilian Robert Vicol; credit “Cell phone": modification of
work by Brett Jordan; credit “Microwave oven": modification of work by Billy Mabray; credit “Ultrasound": modification of work
by Jane Whitney; credit “AM radio": modification of work by Dave Clausen)
 Example 3.1.1: Determining the Frequency and Wavelength of Radiation
A sodium streetlight gives off yellow light that has a wavelength of 589 nm (1 nm = 1 × 10−9 m). What is the frequency of this
light?
Solution
We can rearrange the Equation 3.1.1 to solve for the frequency:
c
ν =
λ
Since c is expressed in meters per second, we must also convert 589 nm to meters.
8 −1 9
2.998 × 10 m s 1 × 10 nm
14 −1
ν =( )( ) = 5.09 × 10 s
589 nm 1 m
 Exercise 3.1.1
One of the frequencies used to transmit and receive cellular telephone signals in the United States is 850 MHz. What is the
wavelength in meters of these radio waves?
Answer
0.353 m = 35.3 cm
Wireless Communication
Many valuable technologies operate in the radio (3 kHz-300 GHz) frequency region of the electromagnetic spectrum. At the low
frequency (low energy, long wavelength) end of this region are AM (amplitude modulation) radio signals (540-2830 kHz) that can
travel long distances. FM (frequency modulation) radio signals are used at higher frequencies (87.5-108.0 MHz). In AM radio, the
information is transmitted by varying the amplitude of the wave (Figure 3.1.5). In FM radio, by contrast, the amplitude is constant
and the instantaneous frequency varies.

Figure 3.1.3 : Radio and cell towers are typically used to transmit long-wavelength electromagnetic radiation. Increasingly, cell
towers are designed to blend in with the landscape, as with the Tucson, Arizona, cell tower (right) disguised as a palm tree. (credit
left: modification of work by Sir Mildred Pierce; credit middle: modification of work by M.O. Stevens)
Other technologies also operate in the radio-wave portion of the electromagnetic spectrum. For example, 4G cellular telephone
signals are approximately 880 MHz, while Global Positioning System (GPS) signals operate at 1.228 and 1.575 GHz, local area
wireless technology (Wi-Fi) networks operate at 2.4 to 5 GHz, and highway toll sensors operate at 5.8 GHz. The frequencies
associated with these applications are convenient because such waves tend not to be absorbed much by common building materials.
Figure 3.1.4 : This schematic depicts how amplitude modulation (AM) and frequency modulation (FM) can be used to transmit a
radio wave.
One particularly characteristic phenomenon of waves results when two or more waves come into contact: They interfere with each
other. Figure 3.1.5 shows the interference patterns that arise when light passes through narrow slits closely spaced about a
wavelength apart. The fringe patterns produced depend on the wavelength, with the fringes being more closely spaced for shorter
wavelength light passing through a given set of slits. When the light passes through the two slits, each slit effectively acts as a new
source, resulting in two closely spaced waves coming into contact at the detector (the camera in this case). The dark regions in
Figure 3.1.5 correspond to regions where the peaks for the wave from one slit happen to coincide with the troughs for the wave
from the other slit (destructive interference), while the brightest regions correspond to the regions where the peaks for the two
waves (or their two troughs) happen to coincide (constructive interference). Likewise, when two stones are tossed close together
into a pond, interference patterns are visible in the interactions between the waves produced by the stones. Such interference
patterns cannot be explained by particles moving according to the laws of classical mechanics.

Figure 3.1.5 : Interference fringe patterns are shown for light passing through two closely spaced, narrow slits. The spacing of the
fringes depends on the wavelength, with the fringes being more closely spaced for the shorter-wavelength blue light. (credit:
PASCO)
 Dorothy Hodgkin
Because the wavelengths of X-rays (10-10,000 picometers [pm]) are comparable to the size of atoms, X-rays can be used to
determine the structure of molecules. When a beam of X-rays is passed through molecules packed together in a crystal, the X-
rays collide with the electrons and scatter. Constructive and destructive interference of these scattered X-rays creates a specific
diffraction pattern. Calculating backward from this pattern, the positions of each of the atoms in the molecule can be
determined very precisely. One of the pioneers who helped create this technology was Dorothy Crowfoot Hodgkin.
She was born in Cairo, Egypt, in 1910, where her British parents were studying archeology. Even as a young girl, she was
fascinated with minerals and crystals. When she was a student at Oxford University, she began researching how X-ray
crystallography could be used to determine the structure of biomolecules. She invented new techniques that allowed her and
her students to determine the structures of vitamin B12, penicillin, and many other important molecules. Diabetes, a disease that
affects 382 million people worldwide, involves the hormone insulin. Hodgkin began studying the structure of insulin in 1934,
but it required several decades of advances in the field before she finally reported the structure in 1969. Understanding the
structure has led to better understanding of the disease and treatment options.
Not all waves are travelling waves. Standing waves (also known as stationary waves) remain constrained within some region of
space. As we shall see, standing waves play an important role in our understanding of the electronic structure of atoms and
molecules. The simplest example of a standing wave is a one-dimensional wave associated with a vibrating string that is held fixed
at its two end points. Figure 3.1.6 shows the four lowest-energy standing waves (the fundamental wave and the lowest three
harmonics) for a vibrating string at a particular amplitude. Although the string's motion lies mostly within a plane, the wave itself is
considered to be one dimensional, since it lies along the length of the string. The motion of string segments in a direction
perpendicular to the string length generates the waves and so the amplitude of the waves is visible as the maximum displacement of
the curves seen in Figure 3.1.6. The key observation from the figure is that only those waves having an integer number, n, of half-
wavelengths between the end points can form. A system with fixed end points such as this restricts the number and type of the
possible waveforms. This is an example of quantization, in which only discrete values from a more general set of continuous values
of some property are observed. Another important observation is that the harmonic waves (those waves displaying more than one-
half wavelength) all have one or more points between the two end points that are not in motion. These special points are nodes. The
energies of the standing waves with a given amplitude in a vibrating string increase with the number of half-wavelengths n. Since
the number of nodes is n – 1, the energy can also be said to depend on the number of nodes, generally increasing as the number of
nodes increases.
Figure 3.1.6 : A vibrating string shows some one-dimensional standing waves. Since the two end points of the string are held fixed,
only waves having an integer number of half-wavelengths can form. The points on the string between the end points that are not
moving are called the nodes.

An example of two-dimensional standing waves is shown in Figure 3.1.7 which shows the vibrational patterns on a flat surface.
Although the vibrational amplitudes cannot be seen like they could in the vibrating string, the nodes have been made visible by
sprinkling the drum surface with a powder that collects on the areas of the surface that have minimal displacement. For one-
dimensional standing waves, the nodes were points on the line, but for two-dimensional standing waves, the nodes are lines on the
surface (for three-dimensional standing waves, the nodes are two-dimensional surfaces within the three-dimensional volume).
Because of the circular symmetry of the drum surface, its boundary conditions (the drum surface being tightly constrained to the
circumference of the drum) result in two types of nodes: radial nodes that sweep out all angles at constant radii and, thus, are seen
as circles about the center, and angular nodes that sweep out all radii at constant angles and, thus, are seen as lines passing through
the center. The upper left image in Figure 3.1.7 shows two radial nodes, while the image in the lower right shows the vibrational
pattern associated with three radial nodes and two angular nodes.
Figure 3.1.7 : Two-dimensional standing waves can be visualized on a vibrating surface. The surface has been sprinkled with a
powder that collects near the nodal lines. There are two types of nodes visible: radial nodes (circles) and angular nodes (radii).
For a more animated video, check this link out.
Blackbody Radiation and the Ultraviolet Catastrophe

The last few decades of the nineteenth century witnessed intense research activity in commercializing newly discovered electric
lighting. This required obtaining a better understanding of the distributions of light emitted from various sources being considered.
Artificial lighting is usually designed to mimic natural sunlight within the limitations of the underlying technology. Such lighting
consists of a range of broadly distributed frequencies that form a continuous spectrum. Figure 3.1.8 shows the wavelength
distribution for sunlight. The most intense radiation is in the visible region, with the intensity dropping off rapidly for shorter
wavelength ultraviolet (UV) light, and more slowly for longer wavelength infrared (IR) light.

Figure 3.1.8 : The spectral distribution (light intensity vs. wavelength) of sunlight reaches the Earth's atmosphere as UV light,
visible light, and IR light. The unabsorbed sunlight at the top of the atmosphere has a distribution that approximately matches the
theoretical distribution of a blackbody at 5250 °C, represented by the blue curve. (credit: modification of work by American
Society for Testing and Materials (ASTM) Terrestrial Reference Spectra for Photovoltaic Performance Evaluation)
In Figure 3.1.8, the solar distribution is compared to a representative distribution, called a blackbody spectrum, that corresponds to
a temperature of 5250 °C. The blackbody spectrum matches the solar spectrum quite well. A blackbody is a convenient, ideal
emitter that approximates the behavior of many materials when heated. It is “ideal” in the same sense that an ideal gas is a
convenient, simple representation of real gases that works well, provided that the pressure is not too high nor the temperature too
low. A good approximation of a blackbody that can be used to observe blackbody radiation is a metal oven that can be heated to
very high temperatures. The oven has a small hole allowing for the light being emitted within the oven to be observed with a
spectrometer so that the wavelengths and their intensities can be measured. Figure 3.1.8 shows the resulting curves for some
representative temperatures. Each distribution depends only on a single parameter: the temperature. The maxima in the blackbody
curves, λmax, shift to shorter wavelengths as the temperature increases, reflecting the observation that metals being heated to high
temperatures begin to glow a darker red that becomes brighter as the temperature increases, eventually becoming white hot at very
high temperatures as the intensities of all of the visible wavelengths become appreciable. This common observation was at the heart
of the first paradox that showed the fundamental limitations of classical physics that we will examine.
Physicists derived mathematical expressions for the blackbody curves using well-accepted concepts from the theories of classical
mechanics and classical electromagnetism. The theoretical expressions as functions of temperature fit the observed experimental
blackbody curves well at longer wavelengths, but showed significant discrepancies at shorter wavelengths. Not only did the
theoretical curves not show a peak, they absurdly showed the intensity becoming infinitely large as the wavelength became smaller,
which would imply that everyday objects at room temperature should be emitting large amounts of UV light. This became known
as the “ultraviolet catastrophe” because no one could find any problems with the theoretical treatment that could lead to such
unrealistic short-wavelength behavior. Finally, around 1900, Max Planck derived a theoretical expression for blackbody radiation
that fit the experimental observations exactly (within experimental error). Planck developed his theoretical treatment by extending
the earlier work that had been based on the premise that the atoms composing the oven vibrated at increasing frequencies (or
decreasing wavelengths) as the temperature increased, with these vibrations being the source of the emitted electromagnetic
radiation. But where the earlier treatments had allowed the vibrating atoms to have any energy values obtained from a continuous
set of energies (perfectly reasonable, according to classical physics), Planck found that by restricting the vibrational energies to
discrete values for each frequency, he could derive an expression for blackbody radiation that correctly had the intensity dropping
rapidly for the short wavelengths in the UV region.
E = nhν, n = 1, 2, 3, . . .
The quantity h is a constant now known as Planck's constant, in his honor. Although Planck was pleased he had resolved the
blackbody radiation paradox, he was disturbed that to do so, he needed to assume the vibrating atoms required quantized energies,

which he was unable to explain. The value of Planck's constant is very small, 6.626 × 10−34 joule seconds (J s), which helps explain
why energy quantization had not been observed previously in macroscopic phenomena.
Figure 3.1.9 : Blackbody spectral distribution curves are shown for some representative temperatures.
A graph is shown with a horizontal axis labeled, “Wavelength lambda (micrometers)” and a vertical axis labeled, “Intensity I (a r b.
units).” The horizontal axis begins at 0 and extends to 3.0 with markings provided every 0.1 micrometer. Similarly, the vertical axis
begins at 0 and extends to 10 with markings every 1 unit. Two vertical dashed lines are drawn. The first appears at about 0.39
micrometers and the second at about 0.72 micrometers. To the left of the first of these lines, the label, “Ultraviolet,” appears at the
top of the graph. Between these lines, the label, “Visible,” appears at the top of the graph. To the right of the second of these lines,
the label, “Infrared,” appears at the top of the graph. To the far right of the graph in open space a purple dot is placed which is
labeled, “lambda maximum.” A “Temperature” label is located in a central region of the graph. A blue curve begins on the
horizontal axis at about 0.05 micrometers. This curve increases steeply to a maximum value between the two vertical line segments
of approximately 9.5 at about 0.55 micrometers. This curve decreases rapidly at first, then tapers off to reach a value of about 1.5 at
the far right end of the graph. This blue curve is labeled 6000 K beneath the “Temperature” label. Curves are similarly drawn in
green for 5000 K, orange for 4000 K, and red for 3000 K. As the temperature decreases, the height of the peak is lower and shifted
right on the graph. The maximum value for the green curve is around 4.5 at 7.2 micrometers. This curve tapers at the right end of
the graph to a value around 0.6. The maximum for the orange curve is around 2 at about 0.9 micrometers. This curve tapers at the
right end of the graph to a value around 0.2. The maximum for the red curve is around 0.7 at about 1.2 micrometers. This curve
tapers at the right end of the graph to a value around 0.1. The entire region under the blue curve that is between the two dashed
lines, indicating the visible region, is shaded with vertical bands of color. The colors extending left to right across this region are
violet, indigo, blue, green, yellow, orange, and red. A purple dot is placed at the peak of each of the four colored curves. These
peaks are connected with a dashed curve.
The Photoelectric Effect

The next paradox in the classical theory to be resolved concerned the photoelectric effect (Figure 3.1.10). It had been observed that
electrons could be ejected from the clean surface of a metal when light having a frequency greater than some threshold frequency
was shone on it. Surprisingly, the kinetic energy of the ejected electrons did not depend on the brightness of the light, but increased
with increasing frequency of the light. Since the electrons in the metal had a certain amount of binding energy keeping them there,
the incident light needed to have more energy to free the electrons. According to classical wave theory, a wave's energy depends on
its intensity (which depends on its amplitude), not its frequency. One part of these observations was that the number of electrons
ejected within in a given time period was seen to increase as the brightness increased. In 1905, Albert Einstein was able to resolve
the paradox by incorporating Planck's quantization findings into the discredited particle view of light (Einstein actually won his
Nobel prize for this work, and not for his theories of relativity for which he is most famous).
Einstein argued that the quantized energies that Planck had postulated in his treatment of blackbody radiation could be applied to
the light in the photoelectric effect so that the light striking the metal surface should not be viewed as a wave, but instead as a
stream of particles (later called photons) whose energy depended on their frequency, according to Planck's formula, E = hν (or, in
hc
terms of wavelength using c = νλ, E = ). Electrons were ejected when hit by photons having sufficient energy (a frequency
λ
greater than the threshold). The greater the frequency, the greater the kinetic energy imparted to the escaping electrons by the
collisions. Einstein also argued that the light intensity did not depend on the amplitude of the incoming wave, but instead

corresponded to the number of photons striking the surface within a given time period. This explains why the number of ejected
electrons increased with increasing brightness, since the greater the number of incoming photons, the greater the likelihood that
they would collide with some of the electrons.
With Einstein's findings, the nature of light took on a new air of mystery. Although many light phenomena could be explained
either in terms of waves or particles, certain phenomena, such as the interference patterns obtained when light passed through a
double slit, were completely contrary to a particle view of light, while other phenomena, such as the photoelectric effect, were
completely contrary to a wave view of light. Somehow, at a deep fundamental level still not fully understood, light is both wavelike
and particle-like. This is known as wave-particle duality.
Figure 3.1.10 : Photons with low frequencies do not have enough energy to cause electrons to be ejected via the photoelectric
effect. For any frequency of light above the threshold frequency, the kinetic energy of an ejected electron will increase linearly with
the energy of the incoming photon.
The figure includes three diagrams of waves approaching a flat, horizontal surface that is labeled, “Metal,” from an angle around
45 degrees above and to the left relative to the surface. At the top of the diagram at the center is the label, “E equals h nu.” At the
left, a sinusoidal wave reaches the surface and stops. The portion of the diagram near the flat metal surface is labeled, “No
electrons ejected,” and the wave is labeled, “700 n m.” To the right, a second similar, more compressed wave, which is labeled,
“550 n m,” reaches the flat surface. This time, an arrow extends up and to the right at an angle of approximately 45 degrees. A tiny
yellow circle with a negative sign in it is at the center of the arrow shaft. Above this arrow is the equation, “v subscript max equals
2.96 times 10 superscript 5 m per s.” To the far right, a third similar, even more compressed wave, which is labeled “400 n m”
reaches the flat surface. This time, an arrow extends up and to the right at an angle of approximately 45 degrees. A tiny yellow
circle with a negative sign in it is at the center of the arrow shaft. Above this arrow is the equation “v subscript max equals 6.22
times 10 superscript 5 m per s.”
 Example 3.1.2: Calculating the Energy of Radiation
When we see light from a neon sign, we are observing radiation from excited neon atoms. If this radiation has a wavelength of
640 nm, what is the energy of the photon being emitted?
Solution
We use the part of Planck's equation that includes the wavelength, λ, and convert units of nanometers to meters so that the units
of λ and c are the same.
hc
E =
λ
−34 8 −1
(6.626 × 10 J s )(2.998 × 10 m s )
=
1 m
(640 nm ) ( )
9
10 nm
−19
= 3.10 × 10 J
 Exercise 3.1.2
The microwaves in an oven are of a specific frequency that will heat the water molecules contained in food. (This is why most
plastics and glass do not become hot in a microwave oven-they do not contain water molecules.) This frequency is about 3 ×
109 Hz. What is the energy of one photon in these microwaves?

Answer
2 × 10−24 J
 Example 3.1.3: Photoelectric Effect
Identify which of the following statements are false and, where necessary, change the italicized word or phrase to make them
true, consistent with Einstein's explanation of the photoelectric effect.
a. Increasing the brightness of incoming light increases the kinetic energy of the ejected electrons.
b. Increasing the wavelength of incoming light increases the kinetic energy of the ejected electrons.
c. Increasing the brightness of incoming light increases the number of ejected electrons.
d. Increasing the frequency of incoming light can increase the number of ejected electrons.
Solution
a. False. Increasing the brightness of incoming light has no effect on the kinetic energy of the ejected electrons. Only energy,
not the number or amplitude, of the photons influences the kinetic energy of the electrons.
b. False. Increasing the frequency of incoming light increases the kinetic energy of the ejected electrons. Frequency is
proportional to energy and inversely proportional to wavelength. Frequencies above the threshold value transfer the excess
energy into the kinetic energy of the electrons.
c. True. Because the number of collisions with photons increases with brighter light, the number of ejected electrons
increases.
d. True with regard to the threshold energy binding the electrons to the metal. Below this threshold, electrons are not emitted
and above it they are. Once over the threshold value, further increasing the frequency does not increase the number of
ejected electrons
 Exercise 3.1.3
Calculate the threshold energy in kJ/mol of electrons in aluminum, given that the lowest frequency photon for which the
photoelectric effect is observed is 9.87 × 10 H z .
14
Answer
3.94 kJ/mol
Line Spectra
Another paradox within the classical electromagnetic theory that scientists in the late nineteenth century struggled with concerned
the light emitted from atoms and molecules. When solids, liquids, or condensed gases are heated sufficiently, they radiate some of
the excess energy as light. Photons produced in this manner have a range of energies, and thereby produce a continuous spectrum in
which an unbroken series of wavelengths is present. Most of the light generated from stars (including our sun) is produced in this
fashion. You can see all the visible wavelengths of light present in sunlight by using a prism to separate them. As can be seen in
Figure 3.1.8, sunlight also contains UV light (shorter wavelengths) and IR light (longer wavelengths) that can be detected using
instruments but that are invisible to the human eye. Incandescent (glowing) solids such as tungsten filaments in incandescent lights
also give off light that contains all wavelengths of visible light. These continuous spectra can often be approximated by blackbody
radiation curves at some appropriate temperature, such as those shown in Figure 3.1.9.
In contrast to continuous spectra, light can also occur as discrete or line spectra having very narrow line widths interspersed
throughout the spectral regions such as those shown in Figure 3.1.5. Exciting a gas at low partial pressure using an electrical
current, or heating it, will produce line spectra. Fluorescent light bulbs and neon signs operate in this way (Figure 3.1.11). Each
element displays its own characteristic set of lines, as do molecules, although their spectra are generally much more complicated.

Figure 3.1.11 : Neon signs operate by exciting a gas at low partial pressure using an electrical current. This sign shows the elaborate
artistic effects that can be achieved. (credit: Dave Shaver)
Each emission line consists of a single wavelength of light, which implies that the light emitted by a gas consists of a set of discrete
energies. For example, when an electric discharge passes through a tube containing hydrogen gas at low pressure, the H2 molecules
are broken apart into separate H atoms, and we see a blue-pink color. Passing the light through a prism produces a line spectrum,
indicating that this light is composed of photons of four visible wavelengths, as shown in Figure 3.1.12.
Figure 3.1.12 : Line spectra of select gas. Compare the two types of emission spectra: continuous spectrum of white light (top) and
the line spectra of the light from excited sodium, hydrogen, calcium, and mercury atoms.
An image is shown with 5 rows. Across the top and bottom of the image is a scale that begins at 4000 angstroms at the left and
extends to 740 angstroms at the far right. The top row is a continuous band of the visible spectrum, showing the colors from violet
at the far left through indigo, blue, green, yellow, orange, and red at the far right. The second row, labeled, “N a,” shows the
emission spectrum for the element sodium, which includes two narrow vertical bands in the blue range, two narrow bands in the
yellow-green range, two narrow bands in the yellow range, and one narrow band in the orange range. The third row, labeled, “H,”
shows the emission spectrum for hydrogen. This spectrum shows single bands in the violet, indigo, blue, and orange regions. The
fourth row, labeled, “C a,” shows the emission spectrum for calcium. This spectrum shows bands in the following colors and
frequencies; one violet, five indigo, one blue, two green, two yellow-green, one yellow, two yellow-orange, one orange, and one
red. The fifth row, labeled, “H g,” shows the emission spectrum for mercury. This spectrum shows bands in the following colors
and frequencies; two violet, one indigo, two blue, one green, two yellow, two orange, and one orange-red. It is important to note
that each of the color bands for the emission spectra of the elements matches to a specific wavelength of light. Extending a vertical
line from the bands to the scale above or below the diagram will match the band to a specific measurement on the scale.
The origin of discrete spectra in atoms and molecules was extremely puzzling to scientists in the late nineteenth century, since
according to classical electromagnetic theory, only continuous spectra should be observed. Even more puzzling, in 1885, Johann

Balmer was able to derive an empirical equation that related the four visible wavelengths of light emitted by hydrogen atoms to
whole integers. That equation is the following one, in which k is a constant:
1 1 1
=k( − ) , n = 3, 4, 5, 6
2
λ 4 n
Other discrete lines for the hydrogen atom were found in the UV and IR regions. Johannes Rydberg generalized Balmer's work and
developed an empirical formula that predicted all of hydrogen's emission lines, not just those restricted to the visible range, where,
n1 and n2 are integers, n1 < n2, and R is the Rydberg constant (1.097 × 107 m−1).
∞
1 1 1
= R∞ ( − )
2 2
λ n n
1 2
Even in the late nineteenth century, spectroscopy was a very precise science, and so the wavelengths of hydrogen were measured to
very high accuracy, which implied that the Rydberg constant could be determined very precisely as well. That such a simple
formula as the Rydberg formula could account for such precise measurements seemed astounding at the time, but it was the
eventual explanation for emission spectra by Neils Bohr in 1913 that ultimately convinced scientists to abandon classical physics
and spurred the development of modern quantum mechanics.
Summary
Light and other forms of electromagnetic radiation move through a vacuum with a constant speed, c, of 2.998 × 108 m s−1. This
radiation shows wavelike behavior, which can be characterized by a frequency, ν, and a wavelength, λ, such that c = λν. Light is an
example of a travelling wave. Other important wave phenomena include standing waves, periodic oscillations, and vibrations.
Standing waves exhibit quantization, since their wavelengths are limited to discrete integer multiples of some characteristic lengths.
Electromagnetic radiation that passes through two closely spaced narrow slits having dimensions roughly similar to the wavelength
will show an interference pattern that is a result of constructive and destructive interference of the waves. Electromagnetic radiation
also demonstrates properties of particles called photons. The energy of a photon is related to the frequency (or alternatively, the
hc
wavelength) of the radiation as E = hν (or E = ), where h is Planck's constant. That light demonstrates both wavelike and
λ
particle-like behavior is known as wave-particle duality. All forms of electromagnetic radiation share these properties, although
various forms including X-rays, visible light, microwaves, and radio waves interact differently with matter and have very different
practical applications. Electromagnetic radiation can be generated by exciting matter to higher energies, such as by heating it. The
emitted light can be either continuous (incandescent sources like the sun) or discrete (from specific types of excited atoms).
Continuous spectra often have distributions that can be approximated as blackbody radiation at some appropriate temperature. The
line spectrum of hydrogen can be obtained by passing the light from an electrified tube of hydrogen gas through a prism. This line
spectrum was simple enough that an empirical formula called the Rydberg formula could be derived from the spectrum. Three
historically important paradoxes from the late 19th and early 20th centuries that could not be explained within the existing
framework of classical mechanics and classical electromagnetism were the blackbody problem, the photoelectric effect, and the
discrete spectra of atoms. The resolution of these paradoxes ultimately led to quantum theories that superseded the classical
theories.
Key Equations
c = λν
hc
E = hν = , where h = 6.626 × 10−34 J s
λ
1 1 1
= R∞ ( − )
2 2
λ n n
1 2
Glossary
amplitude
extent of the displacement caused by a wave (for sinusoidal waves, it is one-half the difference from the peak height to the
trough depth, and the intensity is proportional to the square of the amplitude)
blackbody

idealized perfect absorber of all incident electromagnetic radiation; such bodies emit electromagnetic radiation in characteristic
continuous spectra called blackbody radiation
continuous spectrum
electromagnetic radiation given off in an unbroken series of wavelengths (e.g., white light from the sun)
electromagnetic radiation
energy transmitted by waves that have an electric-field component and a magnetic-field component
electromagnetic spectrum
range of energies that electromagnetic radiation can comprise, including radio, microwaves, infrared, visible, ultraviolet, X-
rays, and gamma rays; since electromagnetic radiation energy is proportional to the frequency and inversely proportional to the
wavelength, the spectrum can also be specified by ranges of frequencies or wavelengths
frequency (ν )
number of wave cycles (peaks or troughs) that pass a specified point in space per unit time
hertz (Hz)
the unit of frequency, which is the number of cycles per second, s−1
intensity
property of wave-propagated energy related to the amplitude of the wave, such as brightness of light or loudness of sound
interference pattern
pattern typically consisting of alternating bright and dark fringes; it results from constructive and destructive interference of
waves
line spectrum
electromagnetic radiation emitted at discrete wavelengths by a specific atom (or atoms) in an excited state
node
any point of a standing wave with zero amplitude
photon
smallest possible packet of electromagnetic radiation, a particle of light
quantization
occurring only in specific discrete values, not continuous
standing wave
(also, stationary wave) localized wave phenomenon characterized by discrete wavelengths determined by the boundary
conditions used to generate the waves; standing waves are inherently quantized
wave
oscillation that can transport energy from one point to another in space
wavelength (λ)
distance between two consecutive peaks or troughs in a wave
wave-particle duality
term used to describe the fact that elementary particles including matter exhibit properties of both particles (including localized
position, momentum) and waves (including nonlocalization, wavelength, frequency)
This page titled 3.1: Electromagnetic Energy is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
6.1: Electromagnetic Energy is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

3.2: The Bohr Model
Describe the Bohr model of the hydrogen atom
Use the Rydberg equation to calculate energies of light emitted or absorbed by hydrogen atoms
Following the work of Ernest Rutherford and his colleagues in the early twentieth century, the picture of atoms consisting of tiny
dense nuclei surrounded by lighter and even tinier electrons continually moving about the nucleus was well established. This
picture was called the planetary model, since it pictured the atom as a miniature “solar system” with the electrons orbiting the
nucleus like planets orbiting the sun. The simplest atom is hydrogen, consisting of a single proton as the nucleus about which a
single electron moves. The electrostatic force attracting the electron to the proton depends only on the distance between the two
particles.
m1 m2
Fgravity = G
2
r
with
G is a gravitational constant
m1 and m are the masses of particle 1 and 2, respectively
2
r is the distance between the two particles
The electrostatic force has the same form as the gravitational force between two mass particles except that the electrostatic force
depends on the magnitudes of the charges on the particles (+1 for the proton and −1 for the electron) instead of the magnitudes of
the particle masses that govern the gravitational force.
m1 m2
Felectrostatic = k
2
r
with
k is a constant
m1 and m are the masses of particle 1 and 2, respectively
2
r is the distance between the two particles
Since forces can be derived from potentials, it is convenient to work with potentials instead, since they are forms of energy. The
electrostatic potential is also called the Coulomb potential. Because the electrostatic potential has the same form as the gravitational
potential, according to classical mechanics, the equations of motion should be similar, with the electron moving around the nucleus
in circular or elliptical orbits (hence the label “planetary” model of the atom). Potentials of the form V(r) that depend only on the
radial distance r are known as central potentials. Central potentials have spherical symmetry, and so rather than specifying the
position of the electron in the usual Cartesian coordinates (x, y, z), it is more convenient to use polar spherical coordinates centered
at the nucleus, consisting of a linear coordinate r and two angular coordinates, usually specified by the Greek letters theta (θ) and
phi (Φ). These coordinates are similar to the ones used in GPS devices and most smart phones that track positions on our (nearly)
spherical earth, with the two angular coordinates specified by the latitude and longitude, and the linear coordinate specified by sea-
level elevation. Because of the spherical symmetry of central potentials, the energy and angular momentum of the classical
hydrogen atom are constants, and the orbits are constrained to lie in a plane like the planets orbiting the sun. This classical
mechanics description of the atom is incomplete, however, since an electron moving in an elliptical orbit would be accelerating (by
changing direction) and, according to classical electromagnetism, it should continuously emit electromagnetic radiation. This loss
in orbital energy should result in the electron’s orbit getting continually smaller until it spirals into the nucleus, implying that atoms
are inherently unstable.
In 1913, Niels Bohr attempted to resolve the atomic paradox by ignoring classical electromagnetism’s prediction that the orbiting
electron in hydrogen would continuously emit light. Instead, he incorporated into the classical mechanics description of the atom
Planck’s ideas of quantization and Einstein’s finding that light consists of photons whose energy is proportional to their frequency.
Bohr assumed that the electron orbiting the nucleus would not normally emit any radiation (the stationary state hypothesis), but it
would emit or absorb a photon if it moved to a different orbit. The energy absorbed or emitted would reflect differences in the
orbital energies according to this equation:

hc
|ΔE| = | Ef − Ei | = hu = (3.2.1)
λ
In this equation, h is Planck’s constant and Ei and Ef are the initial and final orbital energies, respectively. The absolute value of the
energy difference is used, since frequencies and wavelengths are always positive. Instead of allowing for continuous values for the
angular momentum, energy, and orbit radius, Bohr assumed that only discrete values for these could occur (actually, quantizing any
one of these would imply that the other two are also quantized). Bohr’s expression for the quantized energies is:
k
En = − (3.2.2)
2
n
with n = 1, 2, 3, . . .
In this expression, k is a constant comprising fundamental constants such as the electron mass and charge and Planck’s constant.
Inserting the expression for the orbit energies into the equation for ΔE gives
1 1 hc
ΔE = k ( − ) = (3.2.3)
2 2
n n λ
1 2
or
1 k 1 1
= ( − ) (3.2.4)
2 2
λ hc n n
1 2
The lowest few energy levels are shown in Figure 3.2.1. One of the fundamental laws of physics is that matter is most stable with
the lowest possible energy. Thus, the electron in a hydrogen atom usually moves in the n = 1 orbit, the orbit in which it has the
lowest energy. When the electron is in this lowest energy orbit, the atom is said to be in its ground electronic state (or simply
ground state). If the atom receives energy from an outside source, it is possible for the electron to move to an orbit with a higher n
value and the atom is now in an excited electronic state (or simply an excited state) with a higher energy. When an electron
transitions from an excited state (higher energy orbit) to a less excited state, or ground state, the difference in energy is emitted as a
photon. Similarly, if a photon is absorbed by an atom, the energy of the photon moves an electron from a lower energy orbit up to a
more excited one.
Figure 3.2.1 : Quantum numbers and energy levels in a hydrogen atom. The more negative the calculated value, the lower the
energy.
We can relate the energy of electrons in atoms to what we learned previously about energy. The law of conservation of energy says
that we can neither create nor destroy energy. Thus, if a certain amount of external energy is required to excite an electron from one
energy level to another, that same amount of energy will be liberated when the electron returns to its initial state (Figure 3.2.2). In
effect, an atom can “store” energy by using it to promote an electron to a state with a higher energy and release it when the electron
returns to a lower state. The energy can be released as one quantum of energy, as the electron returns to its ground state (say, from

n =5 to n = 1 ), or it can be released as two or more smaller quanta as the electron falls to an intermediate state, then to the
ground state (say, from n = 5 to n = 4 , emitting one quantum, then to n = 1 , emitting a second quantum).
Figure 3.2.2 : The horizontal lines show the relative energy of orbits in the Bohr model of the hydrogen atom, and the vertical
arrows depict the energy of photons absorbed (left) or emitted (right) as electrons move between these orbits.
The figure includes a diagram representing the relative energy levels of the quantum numbers of the hydrogen atom. An upward
pointing arrow at the left of the diagram is labeled, “E.” A grey shaded vertically oriented rectangle is placed just right of the arrow.
The rectangle height matches the arrow length. Colored, horizontal line segments are placed inside the rectangle and labels are
placed to the right of the box, arranged in a column with the heading, “Energy, n.” At the very base of the rectangle, a purple
horizontal line segment is drawn. A black line extends to the right to the label, “1.” At a level approximately three-quarters of the
distance to the top of the rectangle, a blue horizontal line segment is drawn. A black line extends to the right to the label, “2.” At a
level approximately seven-eighths the distance from the base of the rectangle, a green horizontal line segment is drawn. A black
line extends to the right to the label, “3.” Just a short distance above this segment, an orange horizontal line segment is drawn. A
black line segment extends to the right to the label, “4.” Just above this segment, a red horizontal line segment is drawn. A black
line extends to the right to the label, “5.” Just a short distance above this segment, a brown horizontal line segment is drawn. A
black line extends to the right to the label, “infinity.” Arrows are drawn to depict energies of photons absorbed, as shown by
upward pointing arrows on the left, or released as shown by downward pointing arrows on the right side of the diagram between
the colored line segments. The label, “Electron moves to higher energy as light is absorbed,” is placed beneath the upward pointing
arrows. Similarly, the label, “Electron moves to lower energy as light is emitted,” appears beneath the downward pointing arrows.
Moving left to right across the diagram, arrows extend from one colored line segment to the next in the following order: purple to
blue, purple to green, purple to orange, purple to red, purple to brown, blue to green, blue to orange, and blue to red. The arrows
originating from the same colored segment are grouped together by close placement of the arrows. Similarly, the downward arrows
follow in this sequence; brown to purple, red to purple, orange to purple, green to purple, blue to purple, red to blue, orange to blue,
and green to blue. Arrows are again grouped by close placement according to the color at which the arrows end.
Since Bohr’s model involved only a single electron, it could also be applied to the single electron ions He+, Li2+, Be3+, and so
forth, which differ from hydrogen only in their nuclear charges, and so one-electron atoms and ions are collectively referred to as
hydrogen-like or hydrogenic atoms. The energy expression for hydrogen-like atoms is a generalization of the hydrogen atom
energy, in which Z is the nuclear charge (+1 for hydrogen, +2 for He, +3 for Li, and so on) and k has a value of 2.179 × 10 J . –18
2
kZ
En = − (3.2.5)
2
n
The sizes of the circular orbits for hydrogen-like atoms are given in terms of their radii by the following expression, in which a is o
a constant called the Bohr radius, with a value of 5.292 × 10 m:

−11
2
n
r = a0 (3.2.6)
Z
The equation also shows us that as the electron’s energy increases (as n increases), the electron is found at greater distances from
the nucleus. This is implied by the inverse dependence on r in the Coulomb potential, since, as the electron moves away from the
nucleus, the electrostatic attraction between it and the nucleus decreases, and it is held less tightly in the atom. Note that as n gets
larger and the orbits get larger, their energies get closer to zero, and so the limits n ⟶ ∞ and r ⟶ ∞ imply that E = 0

corresponds to the ionization limit where the electron is completely removed from the nucleus. Thus, for hydrogen in the ground
state n = 1 , the ionization energy would be:
ΔE = En⟶∞ − E1 = 0 + k = k (3.2.7)
With three extremely puzzling paradoxes now solved (blackbody radiation, the photoelectric effect, and the hydrogen atom), and all
involving Planck’s constant in a fundamental manner, it became clear to most physicists at that time that the classical theories that
worked so well in the macroscopic world were fundamentally flawed and could not be extended down into the microscopic domain
of atoms and molecules. Unfortunately, despite Bohr’s remarkable achievement in deriving a theoretical expression for the Rydberg
constant, he was unable to extend his theory to the next simplest atom, He, which only has two electrons. Bohr’s model was
severely flawed, since it was still based on the classical mechanics notion of precise orbits, a concept that was later found to be
untenable in the microscopic domain, when a proper model of quantum mechanics was developed to supersede classical
mechanics.
 Example 3.2.1: Calculating the Energy of an Electron in a Bohr Orbit
Early researchers were very excited when they were able to predict the energy of an electron at a particular distance from the
nucleus in a hydrogen atom. If a spark promotes the electron in a hydrogen atom into an orbit with n = 3 , what is the
calculated energy, in joules, of the electron?
Solution
The energy of the electron is given by Equation 3.2.5:
2
−kZ
E =
2
n
The atomic number, Z , of hydrogen is 1; k = 2.179 × 10 –18

J ; and the electron is characterized by an n value of 3. Thus,
−18 2
−(2.179 × 10 J) × (1 )
−19
E = = −2.421 × 10 J
2
(3)
 Exercise 3.2.1
The electron in Example 3.2.1 in the n = 3 state is promoted even further to an orbit with n = 6 . What is its new energy?
Answer
TBD
 Example 3.2.2: Calculating Electron Transitions in a One–electron System
What is the energy (in joules) and the wavelength (in meters) of the line in the spectrum of hydrogen that represents the
movement of an electron from Bohr orbit with n = 4 to the orbit with n = 6? In what part of the electromagnetic spectrum do
we find this radiation?
Solution
In this case, the electron starts out with n = 4 , so n = 4 . It comes to rest in the
1 n =6 orbit, so n2 = 6 . The difference in
energy between the two states is given by this expression:
1 1
−18
ΔE = E1 − E2 = 2.179 × 10 ( − )
2 2
n n
1 2
1 1
−18
ΔE = 2.179 × 10 ( − ) J
2 2
4 6

1 1
−18
ΔE = 2.179 × 10 ( − ) J
16 36
−20
ΔE = 7.566 × 10 J
This energy difference is positive, indicating a photon enters the system (is absorbed) to excite the electron from the n = 4 orbit
up to the n = 6 orbit. The wavelength of a photon with this energy is found by the expression E = hcλ . Rearrangement gives:
hc
λ =
E
From the figure of electromagnetic radiation, we can see that this wavelength is found in the infrared portion of the
electromagnetic spectrum.
 Exercise 3.2.2
What is the energy in joules and the wavelength in meters of the photon produced when an electron falls from the n = 5 to the
n = 3 level in a H e ion (Z = 2 for H e )?
+ +
Answer
6.198 × 10
–19
J and 3.205 × 10−7
m
Bohr’s model of the hydrogen atom provides insight into the behavior of matter at the microscopic level, but it is does not account
for electron–electron interactions in atoms with more than one electron. It does introduce several important features of all models
used to describe the distribution of electrons in an atom. These features include the following:
The energies of electrons (energy levels) in an atom are quantized, described by quantum numbers: integer numbers having only
specific allowed value and used to characterize the arrangement of electrons in an atom.
An electron’s energy increases with increasing distance from the nucleus.
The discrete energies (lines) in the spectra of the elements result from quantized electronic energies.
Of these features, the most important is the postulate of quantized energy levels for an electron in an atom. As a consequence, the
model laid the foundation for the quantum mechanical model of the atom. Bohr won a Nobel Prize in Physics for his contributions
to our understanding of the structure of atoms and how that is related to line spectra emissions.
Summary
Bohr incorporated Planck’s and Einstein’s quantization ideas into a model of the hydrogen atom that resolved the paradox of atom
stability and discrete spectra. The Bohr model of the hydrogen atom explains the connection between the quantization of photons
and the quantized emission from atoms. Bohr described the hydrogen atom in terms of an electron moving in a circular orbit about
a nucleus. He postulated that the electron was restricted to certain orbits characterized by discrete energies. Transitions between
these allowed orbits result in the absorption or emission of photons. When an electron moves from a higher-energy orbit to a more
stable one, energy is emitted in the form of a photon. To move an electron from a stable orbit to a more excited one, a photon of
energy must be absorbed. Using the Bohr model, we can calculate the energy of an electron and the radius of its orbit in any one-
electron system.
Glossary
Bohr’s model of the hydrogen atom
structural model in which an electron moves around the nucleus only in circular orbits, each with a specific allowed radius; the
orbiting electron does not normally emit electromagnetic radiation, but does so when changing from one orbit to another.
excited state
state having an energy greater than the ground-state energy

ground state
state in which the electrons in an atom, ion, or molecule have the lowest energy possible
quantum number
integer number having only specific allowed values and used to characterize the arrangement of electrons in an atom
This page titled 3.2: The Bohr Model is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
6.2: The Bohr Model is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

Extend the concept of wave–particle duality that was observed in electromagnetic radiation to matter as well
Understand the general idea of the quantum mechanical description of electrons in an atom, and that it uses the notion of
three-dimensional wave functions, or orbitals, that define the distribution of probability to find an electron in a particular
part of space
List and describe traits of the four quantum numbers that form the basis for completely specifying the state of an electron in
an atom
Bohr’s model explained the experimental data for the hydrogen atom and was widely accepted, but it also raised many questions.
Why did electrons orbit at only fixed distances defined by a single quantum number n = 1, 2, 3, and so on, but never in between?
Why did the model work so well describing hydrogen and one-electron ions, but could not correctly predict the emission spectrum
for helium or any larger atoms? To answer these questions, scientists needed to completely revise the way they thought about
matter.
Behavior in the Microscopic World

We know how matter behaves in the macroscopic world—objects that are large enough to be seen by the naked eye follow the rules
of classical physics. A billiard ball moving on a table will behave like a particle: It will continue in a straight line unless it collides
with another ball or the table cushion, or is acted on by some other force (such as friction). The ball has a well-defined position and
velocity (or a well-defined momentum, p = mv , defined by mass m and velocity v ) at any given moment. In other words, the ball
is moving in a classical trajectory. This is the typical behavior of a classical object.
When waves interact with each other, they show interference patterns that are not displayed by macroscopic particles such as the
billiard ball. For example, interacting waves on the surface of water can produce interference patters similar to those shown on
Figure 3.3.1. This is a case of wave behavior on the macroscopic scale, and it is clear that particles and waves are very different
phenomena in the macroscopic realm.
Figure 3.3.1 : An interference pattern on the water surface is formed by interacting waves. The waves are caused by reflection of
water from the rocks. (credit: modification of work by Sukanto Debnath)
A photograph is shown of ripples in water. The ripples display an interference pattern with each other.
As technological improvements allowed scientists to probe the microscopic world in greater detail, it became increasingly clear by
the 1920s that very small pieces of matter follow a different set of rules from those we observe for large objects. The
unquestionable separation of waves and particles was no longer the case for the microscopic world.
One of the first people to pay attention to the special behavior of the microscopic world was Louis de Broglie. He asked the
question: If electromagnetic radiation can have particle-like character, can electrons and other submicroscopic particles exhibit
wavelike character? In his 1925 doctoral dissertation, de Broglie extended the wave–particle duality of light that Einstein used to
resolve the photoelectric-effect paradox to material particles. He predicted that a particle with mass m and velocity v (that is, with
linear momentum p) should also exhibit the behavior of a wave with a wavelength value λ, given by this expression in which h is
the familiar Planck’s constant
h h
λ = = (3.3.1)
mv p

This is called the de Broglie wavelength. Unlike the other values of λ discussed in this chapter, the de Broglie wavelength is a
characteristic of particles and other bodies, not electromagnetic radiation (note that this equation involves velocity [v, m/s], not
frequency [ν, Hz]. Although these two symbols are identical, they mean very different things). Where Bohr had postulated the
electron as being a particle orbiting the nucleus in quantized orbits, de Broglie argued that Bohr’s assumption of quantization can
be explained if the electron is considered not as a particle, but rather as a circular standing wave such that only an integer number
of wavelengths could fit exactly within the orbit (Figure 3.3.2).
Figure 3.3.1 : If an electron is viewed as a wave circling around the nucleus, an integer number of wavelengths must fit into the
orbit for this standing wave behavior to be possible.
This figure includes a circle formed from a dashed line. A sinusoidal wave pattern indicated with a solid red line is wrapped around
the circle, centered about the edge of the circle. Line segments extend outward from the circle extending through 2 wave crests
along the circle. A double ended arrow is drawn between these segments and is labeled, “wavelength, lambda.” A dashed double
headed arrow is drawn from the center to the edge of the circle and is labeled, “radius r.”
For a circular orbit of radius r, the circumference is 2πr, and so de Broglie’s condition is:
2πr = nλ (3.3.2)
with n = 1, 2, 3, . . .
Since the de Broglie expression relates the wavelength to the momentum and, hence, velocity, this implies:
nh nh nhr nhr
2πr = nλ = = = = (3.3.3)
p mv mvr L
This expression can be rearranged to give Bohr’s formula for the quantization of the angular momentum:
nh
L = = nℏ (3.3.4)
2π
Classical angular momentum L for a circular motion is equal to the product of the radius of the circle and the momentum of the
moving particle p.
L = rp = rmv (for a circular motion) (3.3.5)
Figure 3.3.3 : The diagram shows angular momentum for a circular motion.
Shortly after de Broglie proposed the wave nature of matter, two scientists at Bell Laboratories, C. J. Davisson and L. H. Germer,
demonstrated experimentally that electrons can exhibit wavelike behavior by showing an interference pattern for electrons
travelling through a regular atomic pattern in a crystal. The regularly spaced atomic layers served as slits, as used in other
interference experiments. Since the spacing between the layers serving as slits needs to be similar in size to the wavelength of the
tested wave for an interference pattern to form, Davisson and Germer used a crystalline nickel target for their “slits,” since the
spacing of the atoms within the lattice was approximately the same as the de Broglie wavelengths of the electrons that they used.
Figure 3.3.4 shows an interference pattern.

Figure 3.3.4 : (a) The interference pattern for electrons passing through very closely spaced slits demonstrates that quantum
particles such as electrons can exhibit wavelike behavior. (b) The experimental results illustrated here demonstrate the wave–
particle duality in electrons. The electrons pass through very closely spaced slits, forming an interference pattern, with increasing
numbers of electrons being recorded from the left image to the right. With only a few electrons recorded, it is clear that the
electrons arrive as individual localized “particles,” but in a seemingly random pattern. As more electrons arrive, a wavelike
interference pattern begins to emerge. Note that the probability of the final electron location is still governed by the wave-type
distribution, even for a single electron, but it can be observed more easily if many electron collisions have been recorded.
The wave–particle duality of matter can be seen by observing what happens if electron collisions are recorded over a long period of
time. Initially, when only a few electrons have been recorded, they show clear particle-like behavior, having arrived in small
localized packets that appear to be random. As more and more electrons arrived and were recorded, a clear interference pattern that
is the hallmark of wavelike behavior emerged. Thus, it appears that while electrons are small localized particles, their motion does
not follow the equations of motion implied by classical mechanics, but instead it is governed by some type of a wave equation that
governs a probability distribution even for a single electron’s motion. Thus the wave–particle duality first observed with photons is
actually a fundamental behavior intrinsic to all quantum particles.
DR. QUANTUM - DOUBLE SLIT EXPERI…

EXPERI…
Video 3.3.1 : View the Dr. Quantum – Double Slit Experiment cartoon for an easy-to-understand description of wave–particle
duality and the associated experiments.
 Example 3.3.1: Calculating the Wavelength of a Particle
If an electron travels at a velocity of 1.000 × 107 m s–1 and has a mass of 9.109 × 10–28 g, what is its wavelength?
Solution

We can use de Broglie’s equation to solve this problem, but we first must do a unit conversion of Planck’s constant. You
learned earlier that 1 J = 1 kg m2/s2. Thus, we can write h = 6.626 × 10–34 J s as 6.626 × 10–34 kg m2/s.
h
λ =
mv
−34 2
6.626 × 10 kg m /s
=
−31 7
(9.109 × 10 kg)(1.000 × 10 m/s)
−11
= 7.274 × 10 m
This is a small value, but it is significantly larger than the size of an electron in the classical (particle) view. This size is the
same order of magnitude as the size of an atom. This means that electron wavelike behavior is going to be noticeable in an
atom.
 Exercise 3.3.1
Calculate the wavelength of a softball with a mass of 100 g traveling at a velocity of 35 m s–1, assuming that it can be modeled
as a single particle.
Answer
1.9 × 10–34 m.
We never think of a thrown softball having a wavelength, since this wavelength is so small it is impossible for our senses or any
known instrument to detect (strictly speaking, the wavelength of a real baseball would correspond to the wavelengths of its
constituent atoms and molecules, which, while much larger than this value, would still be microscopically tiny). The de Broglie
wavelength is only appreciable for matter that has a very small mass and/or a very high velocity.
Werner Heisenberg considered the limits of how accurately we can measure properties of an electron or other microscopic particles.
He determined that there is a fundamental limit to how accurately one can measure both a particle’s position and its momentum
simultaneously. The more accurately we measure the momentum of a particle, the less accurately we can determine its position at
that time, and vice versa. This is summed up in what we now call the Heisenberg uncertainty principle: It is fundamentally
impossible to determine simultaneously and exactly both the momentum and the position of a particle. For a particle of mass m
moving with velocity vx in the x direction (or equivalently with momentum px), the product of the uncertainty in the position, Δx,
ℏ h
and the uncertainty in the momentum, Δpx , must be greater than or equal to (recall that ℏ = , the value of Planck’s constant
2 2π
divided by 2π).
ℏ
Δx × Δpx = (Δx)(mΔv) ≥
2
This equation allows us to calculate the limit to how precisely we can know both the simultaneous position of an object and its
momentum. For example, if we improve our measurement of an electron’s position so that the uncertainty in the position (Δx) has a
value of, say, 1 pm (10–12 m, about 1% of the diameter of a hydrogen atom), then our determination of its momentum must have an
uncertainty with a value of at least
−34 2
h (1.055 × 10 kg m /s)
−23
[Δp = mΔv = ] = = 5 × 10 kg m/s.
−12
(2Δx) (2 × 1 × 10 m)
The value of ħ is not large, so the uncertainty in the position or momentum of a macroscopic object like a baseball is too
insignificant to observe. However, the mass of a microscopic object such as an electron is small enough that the uncertainty can be
large and significant.
It should be noted that Heisenberg’s uncertainty principle is not just limited to uncertainties in position and momentum, but it also
links other dynamical variables. For example, when an atom absorbs a photon and makes a transition from one energy state to
ℏ
another, the uncertainty in the energy and the uncertainty in the time required for the transition are similarly related, as ΔE Δt ≥ .
2
As will be discussed later, even the vector components of angular momentum cannot all be specified exactly simultaneously.

Heisenberg’s principle imposes ultimate limits on what is knowable in science. The uncertainty principle can be shown to be a
consequence of wave–particle duality, which lies at the heart of what distinguishes modern quantum theory from classical
mechanics. Recall that the equations of motion obtained from classical mechanics are trajectories where, at any given instant in
time, both the position and the momentum of a particle can be determined exactly. Heisenberg’s uncertainty principle implies that
such a view is untenable in the microscopic domain and that there are fundamental limitations governing the motion of quantum
particles. This does not mean that microscopic particles do not move in trajectories, it is just that measurements of trajectories are
limited in their precision. In the realm of quantum mechanics, measurements introduce changes into the system that is being
observed.
The Quantum–Mechanical Model of an Atom

Shortly after de Broglie published his ideas that the electron in a hydrogen atom could be better thought of as being a circular
standing wave instead of a particle moving in quantized circular orbits, as Bohr had argued, Erwin Schrödinger extended de
Broglie’s work by incorporating the de Broglie relation into a wave equation, deriving what is today known as the Schrödinger
equation. When Schrödinger applied his equation to hydrogen-like atoms, he was able to reproduce Bohr’s expression for the
energy and, thus, the Rydberg formula governing hydrogen spectra, and he did so without having to invoke Bohr’s assumptions of
stationary states and quantized orbits, angular momenta, and energies; quantization in Schrödinger’s theory was a natural
consequence of the underlying mathematics of the wave equation. Like de Broglie, Schrödinger initially viewed the electron in
hydrogen as being a physical wave instead of a particle, but where de Broglie thought of the electron in terms of circular stationary
waves, Schrödinger properly thought in terms of three-dimensional stationary waves, or wavefunctions, represented by the Greek
letter psi, ψ. A few years later, Max Born proposed an interpretation of the wavefunction ψ that is still accepted today: Electrons
are still particles, and so the waves represented by ψ are not physical waves but, instead, are complex probability amplitudes. The
square of the magnitude of a wavefunction ∣ψ∣ describes the probability of the quantum particle being present near a certain
2
location in space. This means that wavefunctions can be used to determine the distribution of the electron’s density with respect to
the nucleus in an atom. In the most general form, the Schrödinger equation can be written as:
^
H ψ = Eψ
^
H is the Hamiltonian operator, a set of mathematical operations representing the total energy of the quantum particle (such as an
electron in an atom), ψ is the wavefunction of this particle that can be used to find the special distribution of the probability of
finding the particle, and E is the actual value of the total energy of the particle.
Schrödinger’s work, as well as that of Heisenberg and many other scientists following in their footsteps, is generally referred to as
quantum mechanics.
Schrödinger's Cat
Video 3.3.2 : You may also have heard of Schrödinger because of his famous thought experiment. This story explains the concepts
of superposition and entanglement as related to a cat in a box with poison (Schrödinger's Cat [www.youtube.com]).

Understanding Quantum Theory of Electrons in Atoms
The goal of this section is to understand the electron orbitals (location of electrons in atoms), their different energies, and other
properties. The use of quantum theory provides the best understanding to these topics. This knowledge is a precursor to chemical
bonding.
As was described previously, electrons in atoms can exist only on discrete energy levels but not between them. It is said that the
energy of an electron in an atom is quantized, that is, it can be equal only to certain specific values and can jump from one energy
level to another but not transition smoothly or stay between these levels.
The energy levels are labeled with an n value, where n = 1, 2, 3, …. Generally speaking, the energy of an electron in an atom is
greater for greater values of n. This number, n, is referred to as the principal quantum number. The principal quantum number
defines the location of the energy level. It is essentially the same concept as the n in the Bohr atom description. Another name for
the principal quantum number is the shell number. The shells of an atom can be thought of concentric circles radiating out from the
nucleus. The electrons that belong to a specific shell are most likely to be found within the corresponding circular area. The further
we proceed from the nucleus, the higher the shell number, and so the higher the energy level (Figure 3.3.5). The positively charged
protons in the nucleus stabilize the electronic orbitals by electrostatic attraction between the positive charges of the protons and the
negative charges of the electrons. So the further away the electron is from the nucleus, the greater the energy it has.
Figure 3.3.5 : Different shells are numbered by principal quantum numbers.

This quantum mechanical model for where electrons reside in an atom can be used to look at electronic transitions, the events when
an electron moves from one energy level to another. If the transition is to a higher energy level, energy is absorbed, and the energy
change has a positive value. To obtain the amount of energy necessary for the transition to a higher energy level, a photon is
absorbed by the atom. A transition to a lower energy level involves a release of energy, and the energy change is negative. This
process is accompanied by emission of a photon by the atom. The following equation summarizes these relationships and is based
on the hydrogen atom:
ΔE = Efinal − Einitial
−18
1 1
= −2.18 × 10 ( − ) J
2 2
n n
f i
The values nf and ni are the final and initial energy states of the electron.
The principal quantum number is one of three quantum numbers used to characterize an orbital. An atomic orbital, which is distinct
from an orbit, is a general region in an atom within which an electron is most probable to reside. The quantum mechanical model
specifies the probability of finding an electron in the three-dimensional space around the nucleus and is based on solutions of the
Schrödinger equation. In addition, the principal quantum number defines the energy of an electron in a hydrogen or hydrogen-like
atom or an ion (an atom or an ion with only one electron) and the general region in which discrete energy levels of electrons in a
multi-electron atoms and ions are located.
Another quantum number is l, the angular momentum quantum number. It is an integer that defines the shape of the orbital, and
takes on the values, l = 0, 1, 2, …, n – 1. This means that an orbital with n = 1 can have only one value of l, l = 0, whereas n = 2
permits l = 0 and l = 1, and so on. The principal quantum number defines the general size and energy of the orbital. The l value
specifies the shape of the orbital. Orbitals with the same value of l form a subshell. In addition, the greater the angular momentum
quantum number, the greater is the angular momentum of an electron at this orbital.

Orbitals with l = 0 are called s orbitals (or the s subshells). The value l = 1 corresponds to the p orbitals. For a given n, p orbitals
constitute a p subshell (e.g., 3p if n = 3). The orbitals with l = 2 are called the d orbitals, followed by the f-, g-, and h-orbitals for l =
3, 4, 5, and there are higher values we will not consider.
There are certain distances from the nucleus at which the probability density of finding an electron located at a particular orbital is
zero. In other words, the value of the wavefunction ψ is zero at this distance for this orbital. Such a value of radius r is called a
radial node. The number of radial nodes in an orbital is n – l – 1.
Figure 3.3.6 : The graphs show the probability (y axis) of finding an electron for the 1s, 2s, 3s orbitals as a function of distance
from the nucleus.
Consider the examples in Figure 3.3.7. The orbitals depicted are of the s type, thus l = 0 for all of them. It can be seen from the
graphs of the probability densities that there are 1 – 0 – 1 = 0 places where the density is zero (nodes) for 1s (n = 1), 2 – 0 – 1 = 1
node for 2s, and 3 – 0 – 1 = 2 nodes for the 3s orbitals.
The s subshell electron density distribution is spherical and the p subshell has a dumbbell shape. The d and f orbitals are more
complex. These shapes represent the three-dimensional regions within which the electron is likely to be found.

Figure 3.3.7 : Shapes of s, p, d, and f orbitals.
If an electron has an angular momentum (l ≠ 0), then this vector can point in different directions. In addition, the z component of
the angular momentum can have more than one value. This means that if a magnetic field is applied in the z direction, orbitals with
different values of the z component of the angular momentum will have different energies resulting from interacting with the field.
The magnetic quantum number, called ml, specifies the z component of the angular momentum for a particular orbital. For
example, for an s orbital, l = 0, and the only value of ml is zero. For p orbitals, l = 1, and ml can be equal to –1, 0, or +1. Generally
speaking, ml can be equal to –l, –(l – 1), …, –1, 0, +1, …, (l – 1), l. The total number of possible orbitals with the same value of l (a
subshell) is 2l + 1. Thus, there is one s-orbital for ml = 0, there are three p-orbitals for ml = 1, five d-orbitals for ml = 2, seven f-
orbitals for ml = 3, and so forth. The principal quantum number defines the general value of the electronic energy. The angular
momentum quantum number determines the shape of the orbital. And the magnetic quantum number specifies orientation of the
orbital in space, as can be seen in Figure 3.3.7.

Figure 3.3.8 : The chart shows the energies of electron orbitals in a multi-electron atom.
Figure 3.3.8 illustrates the energy levels for various orbitals. The number before the orbital name (such as 2s, 3p, and so forth)
stands for the principal quantum number, n. The letter in the orbital name defines the subshell with a specific angular momentum
quantum number l = 0 for s orbitals, 1 for p orbitals, 2 for d orbitals. Finally, there are more than one possible orbitals for l ≥ 1,
each corresponding to a specific value of ml. In the case of a hydrogen atom or a one-electron ion (such as He+, Li2+, and so on),
energies of all the orbitals with the same n are the same. This is called a degeneracy, and the energy levels for the same principal
quantum number, n, are called degenerate energy levels. However, in atoms with more than one electron, this degeneracy is
eliminated by the electron–electron interactions, and orbitals that belong to different subshells have different energies. Orbitals
within the same subshell (for example ns, np, nd, nf, such as 2p, 3s) are still degenerate and have the same energy.
While the three quantum numbers discussed in the previous paragraphs work well for describing electron orbitals, some
experiments showed that they were not sufficient to explain all observed results. It was demonstrated in the 1920s that when
hydrogen-line spectra are examined at extremely high resolution, some lines are actually not single peaks but, rather, pairs of
closely spaced lines. This is the so-called fine structure of the spectrum, and it implies that there are additional small differences in
energies of electrons even when they are located in the same orbital. These observations led Samuel Goudsmit and George
Uhlenbeck to propose that electrons have a fourth quantum number. They called this the spin quantum number, or ms.
The other three quantum numbers, n, l, and ml, are properties of specific atomic orbitals that also define in what part of the space an
electron is most likely to be located. Orbitals are a result of solving the Schrödinger equation for electrons in atoms. The electron
spin is a different kind of property. It is a completely quantum phenomenon with no analogues in the classical realm. In addition, it
cannot be derived from solving the Schrödinger equation and is not related to the normal spatial coordinates (such as the Cartesian
x, y, and z). Electron spin describes an intrinsic electron “rotation” or “spinning.” Each electron acts as a tiny magnet or a tiny
rotating object with an angular momentum, even though this rotation cannot be observed in terms of the spatial coordinates.
The magnitude of the overall electron spin can only have one value, and an electron can only “spin” in one of two quantized states.
One is termed the α state, with the z component of the spin being in the positive direction of the z axis. This corresponds to the spin
1 1
quantum number ms = . The other is called the β state, with the z component of the spin being negative and ms = − . Any
2 2
electron, regardless of the atomic orbital it is located in, can only have one of those two values of the spin quantum number. The
1 1
energies of electrons having m s =− and m s = are different if an external magnetic field is applied.
2 2
Figure 3.3.9 : Electrons with spin values $±\ce{1/2}$ in an external magnetic field.

Figure 3.3.9 illustrates this phenomenon. An electron acts like a tiny magnet. Its moment is directed up (in the positive direction of
1
the z axis) for the spin quantum number and down (in the negative z direction) for the spin quantum number of − . A magnet 1
2
2
has a lower energy if its magnetic moment is aligned with the external magnetic field (the left electron) and a higher energy for the
1
magnetic moment being opposite to the applied field. This is why an electron with ms = has a slightly lower energy in an
2
1
external field in the positive z direction, and an electron with m s =− has a slightly higher energy in the same field. This is true
2
even for an electron occupying the same orbital in an atom. A spectral line corresponding to a transition for electrons from the
same orbital but with different spin quantum numbers has two possible values of energy; thus, the line in the spectrum will show a
fine structure splitting.
The Pauli Exclusion Principle

An electron in an atom is completely described by four quantum numbers: n, l, ml, and ms. The first three quantum numbers define
the orbital and the fourth quantum number describes the intrinsic electron property called spin. An Austrian physicist Wolfgang
Pauli formulated a general principle that gives the last piece of information that we need to understand the general behavior of
electrons in atoms. The Pauli exclusion principle can be formulated as follows: No two electrons in the same atom can have exactly
the same set of all the four quantum numbers. What this means is that electrons can share the same orbital (the same set of the
quantum numbers n, l, and ml), but only if their spin quantum numbers ms have different values. Since the spin quantum number
1
can only have two values (± ) , no more than two electrons can occupy the same orbital (and if two electrons are located in the
2
same orbital, they must have opposite spins). Therefore, any atomic orbital can be populated by only zero, one, or two electrons.
The properties and meaning of the quantum numbers of electrons in atoms are briefly summarized in Table 3.3.1.
Table 3.3.1 : Quantum Numbers, Their Properties, and Significance
Name Symbol Allowed values Physical meaning
shell, the general region for the

principal quantum number n 1, 2, 3, 4, …. value of energy for an electron on
the orbital
angular momentum or azimuthal

l 0≤l≤n–1 subshell, the shape of the orbital
quantum number
magnetic quantum number ml – l ≤ ml ≤ l orientation of the orbital
1 1 direction of the intrinsic quantum

spin quantum number ms , −
2 2 “spinning” of the electron
 Example 3.3.2: Working with Shells and Subshells
Indicate the number of subshells, the number of orbitals in each subshell, and the values of l and ml for the orbitals in the n = 4
shell of an atom.
Solution
For n = 4, l can have values of 0, 1, 2, and 3. Thus, s, p, d, and f subshells are found in the n = 4 shell of an atom. For l = 0 (the
s subshell), ml can only be 0. Thus, there is only one 4s orbital. For l = 1 (p-type orbitals), m can have values of –1, 0, +1, so
we find three 4p orbitals. For l = 2 (d-type orbitals), ml can have values of –2, –1, 0, +1, +2, so we have five 4d orbitals. When
l = 3 (f-type orbitals), ml can have values of –3, –2, –1, 0, +1, +2, +3, and we can have seven 4f orbitals. Thus, we find a total
of 16 orbitals in the n = 4 shell of an atom.

 Exercise 3.3.2
Identify the subshell in which electrons with the following quantum numbers are found:
a. n = 3, l = 1;
b. n = 5, l = 3;
c. n = 2, l = 0.
Answer a
3p
Answer b
5f
Answer c
2s
 Example 3.3.3: Maximum Number of Electrons
Calculate the maximum number of electrons that can occupy a shell with (a) n = 2, (b) n = 5, and (c) n as a variable. Note you
are only looking at the orbitals with the specified n value, not those at lower energies.
Solution
(a) When n = 2, there are four orbitals (a single 2s orbital, and three orbitals labeled 2p). These four orbitals can contain eight
electrons.
(b) When n = 5, there are five subshells of orbitals that we need to sum:
1 orbital labeled 5s
3 orbitals labeled 5p
5 orbitals labeled 5d
7 orbitals labeled 5f
+9 orbitals labeled 5g
–––––––––––––––––––––
25 orbitals total
Again, each orbital holds two electrons, so 50 electrons can fit in this shell.
(c) The number of orbitals in any shell n will equal n2. There can be up to two electrons in each orbital, so the maximum number of
electrons will be 2 × n2
 Exercise 3.3.3
If a shell contains a maximum of 32 electrons, what is the principal quantum number, n?
Answer
n=4
 Example 3.3.4: Working with Quantum Numbers

Complete the following table for atomic orbitals:
Table for Atomic Orbitals
Orbital n l ml degeneracy Radial nodes (no.)
4f

4 1
7 7 3
5d
Solution
The table can be completed using the following rules:
The orbital designation is nl, where l = 0, 1, 2, 3, 4, 5, … is mapped to the letter sequence s, p, d, f, g, h, …,
The ml degeneracy is the number of orbitals within an l subshell, and so is 2l + 1 (there is one s orbital, three p orbitals, five
d orbitals, seven f orbitals, and so forth).
The number of radial nodes is equal to n – l – 1.
Solution to Example 6.3.4
4f 4 3 7 0
4p 4 1 3 2
7f 7 3 7 3
5d 5 2 5 2
 Exercise 3.3.4
How many orbitals have l = 2 and n = 3?
Answer
The five degenerate 3d orbitals
Summary
Macroscopic objects act as particles. Microscopic objects (such as electrons) have properties of both a particle and a wave. Their
exact trajectories cannot be determined. The quantum mechanical model of atoms describes the three-dimensional position of the
electron in a probabilistic manner according to a mathematical function called a wavefunction, often denoted as ψ. Atomic
wavefunctions are also called orbitals. The squared magnitude of the wavefunction describes the distribution of the probability of
finding the electron in a particular region in space. Therefore, atomic orbitals describe the areas in an atom where electrons are
most likely to be found.
An atomic orbital is characterized by three quantum numbers. The principal quantum number, n, can be any positive integer. The
general region for value of energy of the orbital and the average distance of an electron from the nucleus are related to n. Orbitals
having the same value of n are said to be in the same shell. The angular momentum quantum number, l, can have any integer value
from 0 to n – 1. This quantum number describes the shape or type of the orbital. Orbitals with the same principal quantum number
and the same l value belong to the same subshell. The magnetic quantum number, ml, with 2l + 1 values ranging from –l to +l,
1
describes the orientation of the orbital in space. In addition, each electron has a spin quantum number, ms, that can be equal to ± .
2
No two electrons in the same atom can have the same set of values for all the four quantum numbers.
Glossary
angular momentum quantum number (l)
quantum number distinguishing the different shapes of orbitals; it is also a measure of the orbital angular momentum

atomic orbital
mathematical function that describes the behavior of an electron in an atom (also called the wavefunction), it can be used to find
the probability of locating an electron in a specific region around the nucleus, as well as other dynamical variables
d orbital
region of space with high electron density that is either four lobed or contains a dumbbell and torus shape; describes orbitals
with l = 2. An electron in this orbital is called a d electron
electron density
a measure of the probability of locating an electron in a particular region of space, it is equal to the squared absolute value of
the wave function ψ
f orbital
multilobed region of space with high electron density, describes orbitals with l = 3. An electron in this orbital is called an f
electron
Heisenberg uncertainty principle

rule stating that it is impossible to exactly determine both certain conjugate dynamical properties such as the momentum and the
position of a particle at the same time. The uncertainty principle is a consequence of quantum particles exhibiting wave–particle
duality
magnetic quantum number (ml)

quantum number signifying the orientation of an atomic orbital around the nucleus; orbitals having different values of ml but the
same subshell value of l have the same energy (are degenerate), but this degeneracy can be removed by application of an
external magnetic field
p orbital
dumbbell-shaped region of space with high electron density, describes orbitals with l = 1. An electron in this orbital is called a p
electron
Pauli exclusion principle

specifies that no two electrons in an atom can have the same value for all four quantum numbers
principal quantum number (n)

quantum number specifying the shell an electron occupies in an atom
quantum mechanics
field of study that includes quantization of energy, wave-particle duality, and the Heisenberg uncertainty principle to describe
matter
s orbital
spherical region of space with high electron density, describes orbitals with l = 0. An electron in this orbital is called an s
electron
shell
set of orbitals with the same principal quantum number, n
spin quantum number (ms)

1 1
number specifying the electron spin direction, either + or −
2 2
subshell
set of orbitals in an atom with the same values of n and l
wavefunction (ψ)

mathematical description of an atomic orbital that describes the shape of the orbital; it can be used to calculate the probability of
finding the electron at any given location in the orbital, as well as dynamical variables such as the energy and the angular
momentum
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Derive the predicted ground-state electron configurations of atoms
Identify and explain exceptions to predicted electron configurations for atoms and ions
Relate electron configurations to element classifications in the periodic table
Having introduced the basics of atomic structure and quantum mechanics, we can use our understanding of quantum numbers to
determine how atomic orbitals relate to one another. This allows us to determine which orbitals are occupied by electrons in each
atom. The specific arrangement of electrons in orbitals of an atom determines many of the chemical properties of that atom.
Orbital Energies and Atomic Structure

The energy of atomic orbitals increases as the principal quantum number, n , increases. In any atom with two or more electrons, the
repulsion between the electrons makes energies of subshells with different values of l differ so that the energy of the orbitals
increases within a shell in the order s < p < d < f. Figure 3.4.1 depicts how these two trends in increasing energy relate. The 1s
orbital at the bottom of the diagram is the orbital with electrons of lowest energy. The energy increases as we move up to the 2s and
then 2p, 3s, and 3p orbitals, showing that the increasing n value has more influence on energy than the increasing l value for small
atoms. However, this pattern does not hold for larger atoms. The 3d orbital is higher in energy than the 4s orbital. Such overlaps
continue to occur frequently as we move up the chart.
Figure 3.4.1 : Generalized energy-level diagram for atomic orbitals in an atom with two or more electrons (not to scale).
Electrons in successive atoms on the periodic table tend to fill low-energy orbitals first. Thus, many students find it confusing that,
for example, the 5p orbitals fill immediately after the 4d, and immediately before the 6s. The filling order is based on observed
experimental results, and has been confirmed by theoretical calculations. As the principal quantum number, n, increases, the size of
the orbital increases and the electrons spend more time farther from the nucleus. Thus, the attraction to the nucleus is weaker and
the energy associated with the orbital is higher (less stabilized). But this is not the only effect we have to take into account. Within
each shell, as the value of l increases, the electrons are less penetrating (meaning there is less electron density found close to the
nucleus), in the order s > p > d > f. Electrons that are closer to the nucleus slightly repel electrons that are farther out, offsetting the
more dominant electron–nucleus attractions slightly (recall that all electrons have −1 charges, but nuclei have +Z charges). This
phenomenon is called shielding and will be discussed in more detail in the next section. Electrons in orbitals that experience more
shielding are less stabilized and thus higher in energy. For small orbitals (1s through 3p), the increase in energy due to n is more
significant than the increase due to l; however, for larger orbitals the two trends are comparable and cannot be simply predicted. We
will discuss methods for remembering the observed order.
The arrangement of electrons in the orbitals of an atom is called the electron configuration of the atom. We describe an electron
configuration with a symbol that contains three pieces of information ( Figure 3.4.2):
1. The number of the principal quantum shell, n,

2. The letter that designates the orbital type (the subshell, l), and
3. A superscript number that designates the number of electrons in that particular subshell.
For example, the notation 2p4 (read "two–p–four") indicates four electrons in a p subshell (l = 1) with a principal quantum number
(n) of 2. The notation 3d8 (read "three–d–eight") indicates eight electrons in the d subshell (i.e., l = 2) of the principal shell for
which n = 3.
Figure 3.4.2 : The diagram of an electron configuration specifies the subshell (n and l value, with letter symbol) and superscript
number of electrons.
The Aufbau Principle

To determine the electron configuration for any particular atom, we can “build” the structures in the order of atomic numbers.
Beginning with hydrogen, and continuing across the periods of the periodic table, we add one proton at a time to the nucleus and
one electron to the proper subshell until we have described the electron configurations of all the elements. This procedure is called
the Aufbau principle, from the German word Aufbau (“to build up”). Each added electron occupies the subshell of lowest energy
available (in the order shown in Figure 3.4.3), subject to the limitations imposed by the allowed quantum numbers according to the
Pauli exclusion principle. Electrons enter higher-energy subshells only after lower-energy subshells have been filled to capacity.
Figure 3.4.3 illustrates the traditional way to remember the filling order for atomic orbitals.
Figure 3.4.3 : The arrow leads through each subshell in the appropriate filling order for electron configurations. This chart is
straightforward to construct. Simply make a column for all the s orbitals with each n shell on a separate row. Repeat for p, d, and f.
Be sure to only include orbitals allowed by the quantum numbers (no 1p or 2d, and so forth). Finally, draw diagonal lines from top
to bottom as shown.
Since the arrangement of the periodic table is based on the electron configurations, Figure 3.4.4 provides an alternative method for
determining the electron configuration. The filling order simply begins at hydrogen and includes each subshell as you proceed in
increasing Z order. For example, after filling the 3p block up to Ar, we see the orbital will be 4s (K, Ca), followed by the 3d
orbitals.

Figure 3.4.4 : This periodic table shows the electron configuration for each subshell. By “building up” from hydrogen, this table
can be used to determine the electron configuration for any atom on the periodic table.
We will now construct the ground-state electron configuration and orbital diagram for a selection of atoms in the first and second
periods of the periodic table. Orbital diagrams are pictorial representations of the electron configuration, showing the individual
orbitals and the pairing arrangement of electrons. We start with a single hydrogen atom (atomic number 1), which consists of one
proton and one electron. Referring to either Figure 3.4.3 or 3.4.4, we would expect to find the electron in the 1s orbital. By
1
convention, the m s =+ value is usually filled first. The electron configuration and the orbital diagram are:
2
Following hydrogen is the noble gas helium, which has an atomic number of 2. The helium atom contains two protons and two
1
electrons. The first electron has the same four quantum numbers as the hydrogen atom electron (n = 1, l = 0, ml = 0, ms = + ).
2
The second electron also goes into the 1s orbital and fills that orbital. The second electron has the same n, l, and ml quantum
1
numbers, but must have the opposite spin quantum number, ms = − . This is in accord with the Pauli exclusion principle: No
2
two electrons in the same atom can have the same set of four quantum numbers. For orbital diagrams, this means two arrows go in
each box (representing two electrons in each orbital) and the arrows must point in opposite directions (representing paired spins).
The electron configuration and orbital diagram of helium are:
The n = 1 shell is completely filled in a helium atom.

The next atom is the alkali metal lithium with an atomic number of 3. The first two electrons in lithium fill the 1s orbital and have
the same sets of four quantum numbers as the two electrons in helium. The remaining electron must occupy the orbital of next
lowest energy, the 2s orbital (Figure 3.4.3 or 3.4.4). Thus, the electron configuration and orbital diagram of lithium are:
An atom of the alkaline earth metal beryllium, with an atomic number of 4, contains four protons in the nucleus and four electrons
surrounding the nucleus. The fourth electron fills the remaining space in the 2s orbital.
An atom of boron (atomic number 5) contains five electrons. The n = 1 shell is filled with two electrons and three electrons will
occupy the n = 2 shell. Because any s subshell can contain only two electrons, the fifth electron must occupy the next energy level,
which will be a 2p orbital. There are three degenerate 2p orbitals (ml = −1, 0, +1) and the electron can occupy any one of these p
orbitals. When drawing orbital diagrams, we include empty boxes to depict any empty orbitals in the same subshell that we are
filling.
Carbon (atomic number 6) has six electrons. Four of them fill the 1s and 2s orbitals. The remaining two electrons occupy the 2p
subshell. We now have a choice of filling one of the 2p orbitals and pairing the electrons or of leaving the electrons unpaired in two
different, but degenerate, p orbitals. The orbitals are filled as described by Hund’s rule: the lowest-energy configuration for an atom
with electrons within a set of degenerate orbitals is that having the maximum number of unpaired electrons. Thus, the two electrons
in the carbon 2p orbitals have identical n, l, and ms quantum numbers and differ in their ml quantum number (in accord with the
Pauli exclusion principle). The electron configuration and orbital diagram for carbon are:
Nitrogen (atomic number 7) fills the 1s and 2s subshells and has one electron in each of the three 2p orbitals, in accordance with
Hund’s rule. These three electrons have unpaired spins. Oxygen (atomic number 8) has a pair of electrons in any one of the 2p
orbitals (the electrons have opposite spins) and a single electron in each of the other two. Fluorine (atomic number 9) has only one
2p orbital containing an unpaired electron. All of the electrons in the noble gas neon (atomic number 10) are paired, and all of the
orbitals in the n = 1 and the n = 2 shells are filled. The electron configurations and orbital diagrams of these four elements are:

Figure 3.4.5 : Since the core electron shells correspond to noble gas electron configurations, we can abbreviate electron
configurations by writing the noble gas that matches the core electron configuration, along with the valence electrons in a
condensed format. For our sodium example, the symbol [Ne] represents core electrons, (1s22s22p6) and our abbreviated or
condensed configuration is [Ne]3s1.
The alkali metal sodium (atomic number 11) has one more electron than the neon atom. This electron must go into the lowest-
energy subshell available, the 3s orbital, giving a 1s22s22p63s1 configuration. The electrons occupying the outermost shell orbital(s)
(highest value of n) are called valence electrons, and those occupying the inner shell orbitals are called core electrons ( Figure
\PageIndex5\PageIndex5). Since the core electron shells correspond to noble gas electron configurations, we can abbreviate
electron configurations by writing the noble gas that matches the core electron configuration, along with the valence electrons in a
condensed format. For our sodium example, the symbol [Ne] represents core electrons, (1s22s22p6) and our abbreviated or
condensed configuration is [Ne]3s1.
Figure 3.4.5 : A core-abbreviated electron configuration (right) replaces the core electrons with the noble gas symbol whose
configuration matches the core electron configuration of the other element.
Similarly, the abbreviated configuration of lithium can be represented as [He]2s1, where [He] represents the configuration of the
helium atom, which is identical to that of the filled inner shell of lithium. Writing the configurations in this way emphasizes the
similarity of the configurations of lithium and sodium. Both atoms, which are in the alkali metal family, have only one electron in a
valence s subshell outside a filled set of inner shells.
1
Li : [He] 2s
1
Na : [Ne] 3s
The alkaline earth metal magnesium (atomic number 12), with its 12 electrons in a [Ne]3s2 configuration, is analogous to its family
member beryllium, [He]2s2. Both atoms have a filled s subshell outside their filled inner shells. Aluminum (atomic number 13),
with 13 electrons and the electron configuration [Ne]3s23p1, is analogous to its family member boron, [He]2s22p1.

The electron configurations of silicon (14 electrons), phosphorus (15 electrons), sulfur (16 electrons), chlorine (17 electrons), and
argon (18 electrons) are analogous in the electron configurations of their outer shells to their corresponding family members
carbon, nitrogen, oxygen, fluorine, and neon, respectively, except that the principal quantum number of the outer shell of the
heavier elements has increased by one to n = 3. Figure 3.4.6 shows the lowest energy, or ground-state, electron configuration for
these elements as well as that for atoms of each of the known elements.
Figure 3.4.6 : This version of the periodic table shows the outer-shell electron configuration of each element. Note that down each
group, the configuration is often similar.
When we come to the next element in the periodic table, the alkali metal potassium (atomic number 19), we might expect that we
would begin to add electrons to the 3d subshell. However, all available chemical and physical evidence indicates that potassium is
like lithium and sodium, and that the next electron is not added to the 3d level but is, instead, added to the 4s level (Figure 3.4.3 or
3.4.4). As discussed previously, the 3d orbital with no radial nodes is higher in energy because it is less penetrating and more
shielded from the nucleus than the 4s, which has three radial nodes. Thus, potassium has an electron configuration of [Ar]4s1.
Hence, potassium corresponds to Li and Na in its valence shell configuration. The next electron is added to complete the 4s
subshell and calcium has an electron configuration of [Ar]4s2. This gives calcium an outer-shell electron configuration
corresponding to that of beryllium and magnesium.
Beginning with the transition metal scandium (atomic number 21), additional electrons are added successively to the 3d subshell.
This subshell is filled to its capacity with 10 electrons (remember that for l = 2 [d orbitals], there are 2l + 1 = 5 values of ml,
meaning that there are five d orbitals that have a combined capacity of 10 electrons). The 4p subshell fills next. Note that for three
series of elements, scandium (Sc) through copper (Cu), yttrium (Y) through silver (Ag), and lutetium (Lu) through gold (Au), a
total of 10 d electrons are successively added to the (n – 1) shell next to the n shell to bring that (n – 1) shell from 8 to 18 electrons.
For two series, lanthanum (La) through lutetium (Lu) and actinium (Ac) through lawrencium (Lr), 14 f electrons (l = 3, 2l + 1 = 7
ml values; thus, seven orbitals with a combined capacity of 14 electrons) are successively added to the (n – 2) shell to bring that
shell from 18 electrons to a total of 32 electrons.

 Example 3.4.1: Quantum Numbers and Electron Configurations
What is the electron configuration and orbital diagram for a phosphorus atom? What are the four quantum numbers for the last
electron added?
Solution
The atomic number of phosphorus is 15. Thus, a phosphorus atom contains 15 electrons. The order of filling of the energy
levels is 1s, 2s, 2p, 3s, 3p, 4s, . . . The 15 electrons of the phosphorus atom will fill up to the 3p orbital, which will contain
three electrons:
The last electron added is a 3p electron. Therefore, n = 3 and, for a p-type orbital, l = 1. The ml value could be –1, 0, or +1. The
1
three p orbitals are degenerate, so any of these ml values is correct. For unpaired electrons, convention assigns the value of +
2
1
for the spin quantum number; thus, m s =+ .
2
 Exercise 3.4.1
Identify the atoms from the electron configurations given:

a. [Ar]4s23d5
b. [Kr]5s24d105p6
Answer a
Mn
Answer b
Xe
The periodic table can be a powerful tool in predicting the electron configuration of an element. However, we do find exceptions to
the order of filling of orbitals that are shown in Figure 3.4.3 or 3.4.4. For instance, the electron configurations of the transition
metals chromium (Cr; atomic number 24) and copper (Cu; atomic number 29), among others, are not those we would expect. In
general, such exceptions involve subshells with very similar energy, and small effects can lead to changes in the order of filling.
In the case of Cr and Cu, we find that half-filled and completely filled subshells apparently represent conditions of preferred
stability. This stability is such that an electron shifts from the 4s into the 3d orbital to gain the extra stability of a half-filled 3d
subshell (in Cr) or a filled 3d subshell (in Cu). Other exceptions also occur. For example, niobium (Nb, atomic number 41) is
predicted to have the electron configuration [Kr]5s24d3. Experimentally, we observe that its ground-state electron configuration is
actually [Kr]5s14d4. We can rationalize this observation by saying that the electron–electron repulsions experienced by pairing the
electrons in the 5s orbital are larger than the gap in energy between the 5s and 4d orbitals. There is no simple method to predict the
exceptions for atoms where the magnitude of the repulsions between electrons is greater than the small differences in energy
between subshells.
Electron Configurations and the Periodic Table

As described earlier, the periodic table arranges atoms based on increasing atomic number so that elements with the same chemical
properties recur periodically. When their electron configurations are added to the table (Figure 3.4.6), we also see a periodic
recurrence of similar electron configurations in the outer shells of these elements. Because they are in the outer shells of an atom,
valence electrons play the most important role in chemical reactions. The outer electrons have the highest energy of the electrons in

an atom and are more easily lost or shared than the core electrons. Valence electrons are also the determining factor in some
physical properties of the elements.
Elements in any one group (or column) have the same number of valence electrons; the alkali metals lithium and sodium each have
only one valence electron, the alkaline earth metals beryllium and magnesium each have two, and the halogens fluorine and
chlorine each have seven valence electrons. The similarity in chemical properties among elements of the same group occurs
because they have the same number of valence electrons. It is the loss, gain, or sharing of valence electrons that defines how
elements react.
It is important to remember that the periodic table was developed on the basis of the chemical behavior of the elements, well before
any idea of their atomic structure was available. Now we can understand why the periodic table has the arrangement it has—the
arrangement puts elements whose atoms have the same number of valence electrons in the same group. This arrangement is
emphasized in Figure 3.4.6, which shows in periodic-table form the electron configuration of the last subshell to be filled by the
Aufbau principle. The colored sections of Figure 3.4.6 show the three categories of elements classified by the orbitals being filled:
main group, transition, and inner transition elements. These classifications determine which orbitals are counted in the valence
shell, or highest energy level orbitals of an atom.
1. Main group elements (sometimes called representative elements) are those in which the last electron added enters an s or a p
orbital in the outermost shell, shown in blue and red in Figure 3.4.6. This category includes all the nonmetallic elements, as
well as many metals and the intermediate semimetallic elements. The valence electrons for main group elements are those with
the highest n level. For example, gallium (Ga, atomic number 31) has the electron configuration [Ar]4s23d104p1, which contains
three valence electrons (underlined). The completely filled d orbitals count as core, not valence, electrons.
2. Transition elements or transition metals. These are metallic elements in which the last electron added enters a d orbital. The
valence electrons (those added after the last noble gas configuration) in these elements include the ns and (n – 1) d electrons.
The official IUPAC definition of transition elements specifies those with partially filled d orbitals. Thus, the elements with
completely filled orbitals (Zn, Cd, Hg, as well as Cu, Ag, and Au in Figure 3.4.6) are not technically transition elements.
However, the term is frequently used to refer to the entire d block (colored yellow in Figure 3.4.6), and we will adopt this usage
in this textbook.
3. Inner transition elements are metallic elements in which the last electron added occupies an f orbital. They are shown in green
in Figure 3.4.6. The valence shells of the inner transition elements consist of the (n – 2)f, the (n – 1)d, and the ns subshells.
There are two inner transition series:
1. The lanthanide series: lanthanide (La) through lutetium (Lu)
2. The actinide series: actinide (Ac) through lawrencium (Lr)
Lanthanum and actinium, because of their similarities to the other members of the series, are included and used to name the series,
even though they are transition metals with no f electrons.
Electron Configurations of Ions

We have seen that ions are formed when atoms gain or lose electrons. A cation (positively charged ion) forms when one or more
electrons are removed from a parent atom. For main group elements, the electrons that were added last are the first electrons
removed. For transition metals and inner transition metals, however, electrons in the s orbital are easier to remove than the d or f
electrons, and so the highest ns electrons are lost, and then the (n – 1)d or (n – 2)f electrons are removed. An anion (negatively
charged ion) forms when one or more electrons are added to a parent atom. The added electrons fill in the order predicted by the
Aufbau principle.
 Example 3.4.2: Predicting Electron Configurations of Ions
What is the electron configuration and orbital diagram of:

a. Na+
b. P3–
c. Al2+
d. Fe2+
e. Sm3+
Solution

First, write out the electron configuration for each parent atom. We have chosen to show the full, unabbreviated configurations
to provide more practice for students who want it, but listing the core-abbreviated electron configurations is also acceptable.
Next, determine whether an electron is gained or lost. Remember electrons are negatively charged, so ions with a positive
charge have lost an electron. For main group elements, the last orbital gains or loses the electron. For transition metals, the last
s orbital loses an electron before the d orbitals.
a. Na: 1s22s22p63s1. Sodium cation loses one electron, so Na+: 1s22s22p63s1 = Na+: 1s22s22p6.
b. P: 1s22s22p63s23p3. Phosphorus trianion gains three electrons, so P3−: 1s22s22p63s23p6.
c. Al: 1s22s22p63s23p1. Aluminum dication loses two electrons Al2+: 1s22s22p63s23p1 = Al2+: 1s22s22p63s1.
d. Fe: 1s22s22p63s23p64s23d6. Iron(II) loses two electrons and, since it is a transition metal, they are removed from the 4s
orbital Fe2+: 1s22s22p63s23p64s23d6 = 1s22s22p63s23p63d6.
e. Sm: 1s22s22p63s23p64s23d104p65s24d105p66s24f6. Samarium trication loses three electrons. The first two will be lost from
the 6s orbital, and the final one is removed from the 4f orbital. Sm3+: 1s22s22p63s23p64s23d104p65s24d105p66s24f6 =
1s22s22p63s23p64s23d104p65s24d105p64f5.
 Exercise 3.4.2
a. Which ion with a +2 charge has the electron configuration 1s22s22p63s23p63d104s24p64d5?
b. Which ion with a +3 charge has this configuration?
Answer a
Tc2+
Answer b
Ru3+
Summary
The relative energy of the subshells determine the order in which atomic orbitals are filled (1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, and so on).
Electron configurations and orbital diagrams can be determined by applying the Pauli exclusion principle (no two electrons can
have the same set of four quantum numbers) and Hund’s rule (whenever possible, electrons retain unpaired spins in degenerate
orbitals).
Electrons in the outermost orbitals, called valence electrons, are responsible for most of the chemical behavior of elements. In the
periodic table, elements with analogous valence electron configurations usually occur within the same group. There are some
exceptions to the predicted filling order, particularly when half-filled or completely filled orbitals can be formed. The periodic table
can be divided into three categories based on the orbital in which the last electron to be added is placed: main group elements (s
and p orbitals), transition elements (d orbitals), and inner transition elements (f orbitals).
Glossary
Aufbau principle
procedure in which the electron configuration of the elements is determined by “building” them in order of atomic numbers,
adding one proton to the nucleus and one electron to the proper subshell at a time
core electron
electron in an atom that occupies the orbitals of the inner shells
electron configuration
electronic structure of an atom in its ground state given as a listing of the orbitals occupied by the electrons
Hund’s rule

every orbital in a subshell is singly occupied with one electron before any one orbital is doubly occupied, and all electrons in
singly occupied orbitals have the same spin
orbital diagram
pictorial representation of the electron configuration showing each orbital as a box and each electron as an arrow
valence electrons
electrons in the outermost or valence shell (highest value of n) of a ground-state atom; determine how an element reacts
valence shell
outermost shell of electrons in a ground-state atom; for main group elements, the orbitals with the highest n level (s and p
subshells) are in the valence shell, while for transition metals, the highest energy s and d subshells make up the valence shell
and for inner transition elements, the highest s, d, and f subshells are included
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Describe and explain the observed trends in atomic size, ionization energy, and electron affinity of the elements
The elements in groups (vertical columns) of the periodic table exhibit similar chemical behavior. This similarity occurs because
the members of a group have the same number and distribution of electrons in their valence shells. However, there are also other
patterns in chemical properties on the periodic table. For example, as we move down a group, the metallic character of the atoms
increases. Oxygen, at the top of Group 16 (6A), is a colorless gas; in the middle of the group, selenium is a semiconducting solid;
and, toward the bottom, polonium is a silver-grey solid that conducts electricity.
As we go across a period from left to right, we add a proton to the nucleus and an electron to the valence shell with each successive
element. As we go down the elements in a group, the number of electrons in the valence shell remains constant, but the principal
quantum number increases by one each time. An understanding of the electronic structure of the elements allows us to examine
some of the properties that govern their chemical behavior. These properties vary periodically as the electronic structure of the
elements changes. They are (1) size (radius) of atoms and ions, (2) ionization energies, and (3) electron affinities.
Variation in Covalent Radius

The quantum mechanical picture makes it difficult to establish a definite size of an atom. However, there are several practical ways
to define the radius of atoms and, thus, to determine their relative sizes that give roughly similar values. We will use the covalent
radius (Figure 3.5.1), which is defined as one-half the distance between the nuclei of two identical atoms when they are joined by a
covalent bond (this measurement is possible because atoms within molecules still retain much of their atomic identity).

Figure 3.5.1 : (a) The radius of an atom is defined as one-half the distance between the nuclei in a molecule consisting of two
identical atoms joined by a covalent bond. The atomic radius for the halogens increases down the group as n increases. (b)
Covalent radii of the elements are shown to scale. The general trend is that radii increase down a group and decrease across a
period.
This figure has two parts: a and b. In figure a, 4 diatomic molecules are shown to illustrate the method of determining the atomic
radius of an atom. The first model, in light green, is used to find the F atom radius. Two spheres are pushed very tightly together.
The distance between the centers of the two atoms is indicated above the diagram with a double headed arrow labeled, “128 p m.”
The endpoints of this arrow connect to line segments that extend to the atomic radii below. Beneath the molecule is the label, “F
radius equals 128 p m divided by 2 equals 64 p m.” The next three models are similarly used to show the atomic radii of additional
atoms. The second diatomic molecule is in a darker shade of green. The distance between the radii is 198 p m. Beneath the
molecule is the label, “C l radius equals 198 p m divided by 2 equals 99 pm.” The third diatomic molecule is in red. The distance
between the radii is 228 p m. Beneath the molecule is the label, “B r radius equals 228 p m divided by 2 equals 114 pm.” The
fourth diatomic molecule is in purple. The distance between the radii is 266 p m. Beneath the molecule is the label, “I radius equals
266 p m divided by 2 equals 133 p m.” In figure b, a periodic table layout is used to compare relative sizes of atoms using green
spheres. No spheres are provided for the noble or inert gas, group 18 elements. General trends noted are increasing circle size
moving from top to bottom in a group, with a general tendency toward increasing atomic radii toward the lower left corner of the
periodic table.
We know that as we scan down a group, the principal quantum number, n, increases by one for each element. Thus, the electrons
are being added to a region of space that is increasingly distant from the nucleus. Consequently, the size of the atom (and its
covalent radius) must increase as we increase the distance of the outermost electrons from the nucleus. This trend is illustrated for
the covalent radii of the halogens in Table 3.5.1 and Figure 3.5.1. The trends for the entire periodic table can be seen in Figure
3.5.2.
Table 3.5.1 : Covalent Radii of the Halogen Group Elements

Atom Covalent radius (pm) Nuclear charge
F 64 +9
Cl 99 +17
Br 114 +35
I 133 +53
At 148 +85

As shown in Figure 3.5.2, as we move across a period from left to right, we generally find that each element has a smaller covalent
radius than the element preceding it. This might seem counterintuitive because it implies that atoms with more electrons have a
smaller atomic radius. This can be explained with the concept of effective nuclear charge, Z . This is the pull exerted on a
ef f
specific electron by the nucleus, taking into account any electron–electron repulsions. For hydrogen, there is only one electron and
so the nuclear charge (Z) and the effective nuclear charge (Zeff) are equal. For all other atoms, the inner electrons partially shield the
outer electrons from the pull of the nucleus, and thus:
Zeff = Z − shielding
Shielding is determined by the probability of another electron being between the electron of interest and the nucleus, as well as by
the electron–electron repulsions the electron of interest encounters. Core electrons are adept at shielding, while electrons in the
same valence shell do not block the nuclear attraction experienced by each other as efficiently. Thus, each time we move from one
element to the next across a period, Z increases by one, but the shielding increases only slightly. Thus, Zeff increases as we move
from left to right across a period. The stronger pull (higher effective nuclear charge) experienced by electrons on the right side of
the periodic table draws them closer to the nucleus, making the covalent radii smaller.
Figure 3.5.2 : Within each period, the trend in atomic radius decreases as Z increases; for example, from K to Kr. Within each group
(e.g., the alkali metals shown in purple), the trend is that atomic radius increases as Z increases.
This graph is labeled Atomic Number on the horizontal axis and Radius (p m) on the vertical axis. A black jagged line connects the
radii values for elements with atomic numbers 1 through 60 on the graph. Peaks are evident at the locations of the alkali metals: L i,
N a, K, R b, and C s. Similarly, minima exist at the locations of noble or inert gases: H e, N e, A r, K r, X e, and R n. The locations
of period 4 and period 5 transition elements are provided with green dots.
Thus, as we would expect, the outermost or valence electrons are easiest to remove because they have the highest energies, are
shielded more, and are farthest from the nucleus. As a general rule, when the representative elements form cations, they do so by
the loss of the ns or np electrons that were added last in the Aufbau process. The transition elements, on the other hand, lose the ns
electrons before they begin to lose the (n – 1)d electrons, even though the ns electrons are added first, according to the Aufbau
principle.
 Example 3.5.1: Sorting Atomic Radii
Predict the order of increasing covalent radius for Ge, Fl, Br, Kr.
Solution

Radius increases as we move down a group, so Ge < Fl (Note: Fl is the symbol for flerovium, element 114, NOT fluorine).
Radius decreases as we move across a period, so Kr < Br < Ge. Putting the trends together, we obtain Kr < Br < Ge < Fl.
 Exercise 3.5.1
Give an example of an atom whose size is smaller than fluorine.
Answer
Ne or He
Variation in Ionic Radii

Ionic radius is the measure used to describe the size of an ion. A cation always has fewer electrons and the same number of protons
as the parent atom; it is smaller than the atom from which it is derived (Figure 3.5.3). For example, the covalent radius of an
aluminum atom (1s22s22p63s23p1) is 118 pm, whereas the ionic radius of an Al3+ (1s22s22p6) is 68 pm. As electrons are removed
from the outer valence shell, the remaining core electrons occupying smaller shells experience a greater effective nuclear charge
Zeff (as discussed) and are drawn even closer to the nucleus.
Figure 3.5.3 : The radius for a cation is smaller than the parent atom (Al), due to the lost electrons; the radius for an anion is larger
than the parent (S), due to the gained electrons.
The figure includes spheres in green to represent the relative sizes of A l and S atoms. Beneath each of these spheres is a red
sphere. The red sphere represents the ionic states of aluminum and sulfur respectively. While radius for the aluminum cation is
smaller than aluminum, the sulfur anion has a greater radius than sulfur.
Cations with larger charges are smaller than cations with smaller charges (e.g., V2+ has an ionic radius of 79 pm, while that of V3+
is 64 pm). Proceeding down the groups of the periodic table, we find that cations of successive elements with the same charge
generally have larger radii, corresponding to an increase in the principal quantum number, n.
An anion (negative ion) is formed by the addition of one or more electrons to the valence shell of an atom. This results in a greater
repulsion among the electrons and a decrease in Z per electron. Both effects (the increased number of electrons and the
ef f
decreased Zeff) cause the radius of an anion to be larger than that of the parent atom ( Figure 3.5.3). For example, a sulfur atom
([Ne]3s23p4) has a covalent radius of 104 pm, whereas the ionic radius of the sulfide anion ([Ne]3s23p6) is 170 pm. For consecutive
elements proceeding down any group, anions have larger principal quantum numbers and, thus, larger radii.
Atoms and ions that have the same electron configuration are said to be isoelectronic. Examples of isoelectronic species are N3–,
O2–, F–, Ne, Na+, Mg2+, and Al3+ (1s22s22p6). Another isoelectronic series is P3–, S2–, Cl–, Ar, K+, Ca2+, and Sc3+ ([Ne]3s23p6). For
atoms or ions that are isoelectronic, the number of protons determines the size. The greater the nuclear charge, the smaller the
radius in a series of isoelectronic ions and atoms.
Variation in Ionization Energies

The amount of energy required to remove the most loosely bound electron from a gaseous atom in its ground state is called its first
ionization energy (IE1). The first ionization energy for an element, X, is the energy required to form a cation with +1 charge:
+ −
X(g) ⟶ X (g) + e IE
1
The energy required to remove the second most loosely bound electron is called the second ionization energy (IE2).
+ 2+ −
X (g) ⟶ X (g) + e IE
2
The energy required to remove the third electron is the third ionization energy, and so on. Energy is always required to remove
electrons from atoms or ions, so ionization processes are endothermic and IE values are always positive. For larger atoms, the most
loosely bound electron is located farther from the nucleus and so is easier to remove. Thus, as size (atomic radius) increases, the

ionization energy should decrease. Relating this logic to what we have just learned about radii, we would expect first ionization
energies to decrease down a group and to increase across a period.
Figure 3.5.4 : The first ionization energy of the elements in the first five periods are plotted against their atomic number.
This figure includes Atomic Number on the horizontal axis and, Ionization Energy (k J divided by mol) on the vertical axis. A red
jagged line connects the ionization energies for elements with atomic numbers 1 through 86 on the graph. Peaks are evident at the
locations of the noble or inert gases: H e, N e, A r, K r, X e, and R n. Similarly, minima exist at the locations of the alkali metals: L
i, N a, K, R b, and C s.
Figure 3.5.4 graphs the relationship between the first ionization energy and the atomic number of several elements. Within a
period, the values of first ionization energy for the elements (IE1) generally increases with increasing Z. Down a group, the IE1
value generally decreases with increasing Z. There are some systematic deviations from this trend, however. Note that the
ionization energy of boron (atomic number 5) is less than that of beryllium (atomic number 4) even though the nuclear charge of
boron is greater by one proton. This can be explained because the energy of the subshells increases as l increases, due to
penetration and shielding (as discussed previously in this chapter). Within any one shell, the s electrons are lower in energy than the
p electrons. This means that an s electron is harder to remove from an atom than a p electron in the same shell. The electron
removed during the ionization of beryllium ([He]2s2) is an s electron, whereas the electron removed during the ionization of boron
([He]2s22p1) is a p electron; this results in a lower first ionization energy for boron, even though its nuclear charge is greater by one
proton. Thus, we see a small deviation from the predicted trend occurring each time a new subshell begins.
Figure 3.5.5 : This version of the periodic table shows the first ionization energy of (IE: 1), in kJ/mol, of selected elements.
The trends for first ionization energies across periods and down groups are shown in this version of the periodic table.
Another deviation occurs as orbitals become more than one-half filled. The first ionization energy for oxygen is slightly less than
that for nitrogen, despite the trend in increasing IE1 values across a period. Looking at the orbital diagram of oxygen, we can see

that removing one electron will eliminate the electron–electron repulsion caused by pairing the electrons in the 2p orbital and will
result in a half-filled orbital (which is energetically favorable). Analogous changes occur in succeeding periods (note the dip for
sulfur after phosphorus in Figure 3.5.4.
The electronic configuration for oxygen is 1s superscript 2, 2s superscript, 2p superscript 4. An orbital diagram shows 2 squares
each filled with a pair of opposite pointing arrows to represent the 1s ans 2s orbitals. Each of the three connected square which
represents the 2p orbitals are filled with one arrow respectively with the addition of 1 red arrow in the first of the three squares.
Removing an electron from a cation is more difficult than removing an electron from a neutral atom because of the greater
electrostatic attraction to the cation. Likewise, removing an electron from a cation with a higher positive charge is more difficult
than removing an electron from an ion with a lower charge. Thus, successive ionization energies for one element always increase.
As seen in Table 3.5.2, there is a large increase in the ionization energies (color change) for each element. This jump corresponds
to removal of the core electrons, which are harder to remove than the valence electrons. For example, Sc and Ga both have three
valence electrons, so the rapid increase in ionization energy occurs after the third ionization.
Table 3.5.2: Successive Ionization Energies for Selected Elements (kJ/mol)
Element IE1 IE2 IE3 IE4 IE5 IE6 IE7
K 418.8 3051.8 4419.6 5876.9 7975.5 9590.6 11343
Ca 589.8 1145.4 4912.4 6490.6 8153.0 10495.7 12272.9
Sc 633.1 1235.0 2388.7 7090.6 8842.9 10679.0 13315.0
Ga 578.8 1979.4 2964.6 6180 8298.7 10873.9 13594.8
Ge 762.2 1537.5 3302.1 4410.6 9021.4 Not available Not available
As 944.5 1793.6 2735.5 4836.8 6042.9 12311.5 Not available
 Example 3.5.2: Ranking Ionization Energies

Predict the order of increasing energy for the following processes: IE1 for Al, IE1 for Tl, IE2 for Na, IE3 for Al.
Solution
Removing the 6p1 electron from Tl is easier than removing the 3p1 electron from Al because the higher n orbital is farther from
the nucleus, so IE1(Tl) < IE1(Al). Ionizing the third electron from
2+ 3+ −
Al (Al ⟶ Al +e )
requires more energy because the cation Al2+ exerts a stronger pull on the electron than the neutral Al atom, so IE1(Al) <
IE3(Al). The second ionization energy for sodium removes a core electron, which is a much higher energy process than
removing valence electrons. Putting this all together, we obtain:
IE1(Tl) < IE1(Al) < IE3(Al) < IE2(Na).
 Exercise 3.5.2
Which has the lowest value for IE1: O, Po, Pb, or Ba?
Answer
Ba

Variation in Electron Affinities
The electron affinity [EA] is the energy change for the process of adding an electron to a gaseous atom to form an anion (negative
ion).
− −
X(g) + e ⟶ X (g) EA
1
This process can be either endothermic or exothermic, depending on the element. The EA of some of the elements is given in
Figure 3.5.6. You can see that many of these elements have negative values of EA, which means that energy is released when the
gaseous atom accepts an electron. However, for some elements, energy is required for the atom to become negatively charged and
the value of their EA is positive. Just as with ionization energy, subsequent EA values are associated with forming ions with more
charge. The second EA is the energy associated with adding an electron to an anion to form a –2 ion, and so on.
Figure 3.5.6 : This version of the periodic table displays the electron affinity values (in kJ/mol) for selected elements.:
The trend for electron affinity values across periods and down groups is shown in this version of the periodic table. Values are not
shown for groups 3 to 12 as well as period 7.
As we might predict, it becomes easier to add an electron across a series of atoms as the effective nuclear charge of the atoms
increases. We find, as we go from left to right across a period, EAs tend to become more negative. The exceptions found among the
elements of group 2 (2A), group 15 (5A), and group 18 (8A) can be understood based on the electronic structure of these groups.
The noble gases, group 18 (8A), have a completely filled shell and the incoming electron must be added to a higher n level, which
is more difficult to do. Group 2 (2A) has a filled ns subshell, and so the next electron added goes into the higher energy np, so,
again, the observed EA value is not as the trend would predict. Finally, group 15 (5A) has a half-filled np subshell and the next
electron must be paired with an existing np electron. In all of these cases, the initial relative stability of the electron configuration
disrupts the trend in EA.
We also might expect the atom at the top of each group to have the largest EA; their first ionization potentials suggest that these
atoms have the largest effective nuclear charges. However, as we move down a group, we see that the second element in the group
most often has the greatest EA. The reduction of the EA of the first member can be attributed to the small size of the n = 2 shell and
the resulting large electron–electron repulsions. For example, chlorine, with an EA value of –348 kJ/mol, has the highest value of
any element in the periodic table. The EA of fluorine is –322 kJ/mol. When we add an electron to a fluorine atom to form a fluoride
anion (F–), we add an electron to the n = 2 shell. The electron is attracted to the nucleus, but there is also significant repulsion from
the other electrons already present in this small valence shell. The chlorine atom has the same electron configuration in the valence
shell, but because the entering electron is going into the n = 3 shell, it occupies a considerably larger region of space and the
electron–electron repulsions are reduced. The entering electron does not experience as much repulsion and the chlorine atom
accepts an additional electron more readily.
The properties discussed in this section (size of atoms and ions, effective nuclear charge, ionization energies, and electron
affinities) are central to understanding chemical reactivity. For example, because fluorine has an energetically favorable EA and a
large energy barrier to ionization (IE), it is much easier to form fluorine anions than cations. Metallic properties including

conductivity and malleability (the ability to be formed into sheets) depend on having electrons that can be removed easily. Thus,
metallic character increases as we move down a group and decreases across a period in the same trend observed for atomic size
because it is easier to remove an electron that is farther away from the nucleus.
Summary
Electron configurations allow us to understand many periodic trends. Covalent radius increases as we move down a group because
the n level (orbital size) increases. Covalent radius mostly decreases as we move left to right across a period because the effective
nuclear charge experienced by the electrons increases, and the electrons are pulled in tighter to the nucleus. Anionic radii are larger
than the parent atom, while cationic radii are smaller, because the number of valence electrons has changed while the nuclear
charge has remained constant. Ionization energy (the energy associated with forming a cation) decreases down a group and mostly
increases across a period because it is easier to remove an electron from a larger, higher energy orbital. Electron affinity (the energy
associated with forming an anion) is more favorable (exothermic) when electrons are placed into lower energy orbitals, closer to
the nucleus. Therefore, electron affinity becomes increasingly negative as we move left to right across the periodic table and
decreases as we move down a group. For both IE and electron affinity data, there are exceptions to the trends when dealing with
completely filled or half-filled subshells.
Glossary
covalent radius
one-half the distance between the nuclei of two identical atoms when they are joined by a covalent bond
effective nuclear charge

charge that leads to the Coulomb force exerted by the nucleus on an electron, calculated as the nuclear charge minus shielding
electron affinity
energy required to add an electron to a gaseous atom to form an anion
ionization energy
energy required to remove an electron from a gaseous atom or ion. The associated number (e.g., second ionization energy)
corresponds to the charge of the ion produced (X2+)
isoelectronic
group of ions or atoms that have identical electron configurations
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Q6.1.1
The light produced by a red neon sign is due to the emission of light by excited neon atoms. Qualitatively describe the spectrum
produced by passing light from a neon lamp through a prism.
S6.1.1
The spectrum consists of colored lines, at least one of which (probably the brightest) is red.
Q6.1.2
An FM radio station found at 103.1 on the FM dial broadcasts at a frequency of 1.031 × 108 s−1 (103.1 MHz). What is the
wavelength of these radio waves in meters?
S6.1.2
c
λ =
ν
m
8
2.998 × 10
s
λ = = 2.908 m
1
8
1.031 × 10
s
Q6.1.3
FM-95, an FM radio station, broadcasts at a frequency of 9.51 × 107 s−1 (95.1 MHz). What is the wavelength of these radio waves
in meters?
S6.1.3
c
λ =
ν
m
8
2.998 × 10
s
λ = = 3.15 m
1
7
9.51 × 10
s
Q6.1.4
A bright violet line occurs at 435.8 nm in the emission spectrum of mercury vapor. What amount of energy, in joules, must be
released by an electron in a mercury atom to produce a photon of this light?
S6.1.4
hc
E =
λ
8
m −34
(2.998 × 10 ) (6.6262 × 10 Js)
s
E =
−7
4.358 × 10 m
−19
= 4.56 × 10 J
Q6.1.5
Light with a wavelength of 614.5 nm looks orange. What is the energy, in joules, per photon of this orange light? What is the
energy in eV (1 eV = 1.602 × 10−19 J)?
S6.1.5
1.) First convert 614.5 nm into meters
6.145nm = 6.145 × 10 −7
m

2.) Then calculate the amount of energy this wavelength of light contains using the equations:
c hc
E = hν and ν = which can be manipulated algebraically into: E =
λ λ
h = Plancks constant → 6.6262 × 10 −34

Js
m
c = Speed of light → 2.998 × 10 8
s
λ = wavelength of photon → 6.145 × 10 −7
m
−34 8
m
(6.6262 × 10 Js) (2.998 × 10 )
s −19
= = 3.233 × 10 J (3.E.1)
−7
6.145 × 10 m
3.) Then convert Joules into eV:
−19
1eV
= (3.233 × 10 J) × (3.E.2)
−19
1.602 × 10 J
= 2.018eV (3.E.3)
Q6.1.6
Heated lithium atoms emit photons of light with an energy of 2.961 × 10−19 J. Calculate the frequency and wavelength of one of
these photons. What is the total energy in 1 mole of these photons? What is the color of the emitted light?
S6.1.6
E
1.) E = hν and ν =
h

Js
−19
2.961 × 10 J
Frequency: ν = −34
= 4.469 × 10
14
Hz
6.6262 × 10 Js
c
2.) λ =
ν
m
c = Speed of light → 2.998 × 10 8
m
8
2.998 × 10
s
Wavelength: λ = = 6.709 × 10
−7
m = Red Light
1
14
4.469 × 10
s
Total energy:
−19 23
2.961 × 10 J 6.022 × 10 photons
5
E = × = 1.783 × 10 J
1 photon 1 mole
Q6.1.7
A photon of light produced by a surgical laser has an energy of 3.027 × 10−19 J. Calculate the frequency and wavelength of the
photon. What is the total energy in 1 mole of photons? What is the color of the emitted light?
S6.1.7
ν = 4.568 × 1014 s; λ = 656.3 nm; Energy mol−1 = 1.823 × 105 J mol−1; red
Q6.1.8
When rubidium ions are heated to a high temperature, two lines are observed in its line spectrum at wavelengths (a) 7.9 × 10−7 m
and (b) 4.2 × 10−7 m. What are the frequencies of the two lines? What color do we see when we heat a rubidium compound?

Q6.1.9
The emission spectrum of cesium contains two lines whose frequencies are (a) 3.45 × 1014 Hz and (b) 6.53 × 1014 Hz. What are the
wavelengths and energies per photon of the two lines? What color are the lines?
S6.1.9
(a) λ = 8.69 × 10−7 m; E = 2.29 × 10−19 J; (b) λ = 4.59 × 10−7 m; E = 4.33 × 10−19 J; The color of (a) is red; (b) is blue.
Q6.1.10
Photons of infrared radiation are responsible for much of the warmth we feel when holding our hands before a fire. These photons
will also warm other objects. How many infrared photons with a wavelength of 1.5 × 10−6 m must be absorbed by the water to
warm a cup of water (175 g) from 25.0 °C to 40 °
S6.1.10
1.) First we must use the equation: q=mCΔT° to calculate the amount of Energy in Joules (J) to warm 175g of H2O a total of 15°
Celsius
m = mass in grams(g) → 175g
4.184J
C = Specific heat of H2O(l) →
g°C
ΔT° = Difference in temperature → 40 - 25 =15°

4.184J
q = 175g × × 15°C (3.E.4)
g°C
q= 11,000 J
2.) Now we need to calculate the amount of energy in Joules (J) that one Photon with a wavelength of 1.5x10-6 m contains. We will
use the equations:
c hc
E = hν and ν = which can be manipulated algebraically into: E =
λ λ

Js
m
c = Speed of light → 2.998 × 10 8
s
λ = wavelength of photon → 1.5 × 10 −6
m
m
−34 8
(6.6262 × 10 Js) (2.998 × 10 )
s −19
= = 1.3 × 10 J (3.E.5)
−6
1.5 × 10 m
This is the energy in one photon, so now we have to see how many times 1.3x10-19 J fits into the 11,000 J from our first calculation:
11, 000 J
22
= = 8.3 × 10 photons (3.E.6)
J
−19
1.3 × 10
photon
22
= 8.3 × 10 photons (3.E.7)
Q6.1.11
One of the radiographic devices used in a dentist's office emits an X-ray of wavelength 2.090 × 10−11 m. What is the energy, in
joules, and frequency of this X-ray?
S6.1.11
E = 9.502 × 10−15 J; ν = 1.434 × 1019 s−1
Q6.1.12
The eyes of certain reptiles pass a single visual signal to the brain when the visual receptors are struck by photons of a wavelength
of 850 nm. If a total energy of 3.15 × 10−14 J is required to trip the signal, what is the minimum number of photons that must strike

the receptor?
S6.1.12
1.) First we need to convert nanometers to meters
850nm = 8.5 x 10-7 m
2. Then calculate Energy in Joules a photon of this wavelength (λ) produces:
m
−34 8
(6.6262 × 10 Js) (2.998 × 10 )
hc s −19
J
(E = ) = = 2.3 × 10 (3.E.8)
−7
λ 8.5 × 10 m photon
3.) Then we need to find out how many of these photons it will take to trip the visual signal to the brain:
−14
3.15 × 10 J
= (3.E.9)
J
−19
2.3 × 10
photon
5
= 1.3 × 10 photons (3.E.10)
Q6.1.13
RGB color television and computer displays use cathode ray tubes that produce colors by mixing red, green, and blue light. If we
look at the screen with a magnifying glass, we can see individual dots turn on and off as the colors change. Using a spectrum of
visible light, determine the approximate wavelength of each of these colors. What is the frequency and energy of a photon of each
of these colors?
S6.1.13
Red: 660 nm; 4.54 × 1014 Hz; 3.01 × 10−19 J.
Green: 520 nm; 5.77 × 1014 Hz; 3.82 × 10−19 J.
Blue: 440 nm; 6.81 × 1014 Hz; 4.51 × 10−19 J.
Somewhat different numbers are also possible.
Q6.1.14
Answer the following questions about a Blu-ray laser:
a. The laser on a Blu-ray player has a wavelength of 405 nm. In what region of the electromagnetic spectrum is this radiation?
What is its frequency?
b. A Blu-ray laser has a power of 5 milliwatts (1 watt = 1 J s−1). How many photons of light are produced by the laser in 1 hour?
c. The ideal resolution of a player using a laser (such as a Blu-ray player), which determines how close together data can be stored
on a compact disk, is determined using the following formula: Resolution = 0.60(λ/NA), where λ is the wavelength of the laser
and NA is the numerical aperture. Numerical aperture is a measure of the size of the spot of light on the disk; the larger the NA,
the smaller the spot. In a typical Blu-ray system, NA = 0.95. If the 405-nm laser is used in a Blu-ray player, what is the closest
that information can be stored on a Blu-ray disk?
d. The data density of a Blu-ray disk using a 405-nm laser is 1.5 × 107 bits mm−2. Disks have an outside diameter of 120 mm and
a hole of 15-mm diameter. How many data bits can be contained on the disk? If a Blu-ray disk can hold 9,400,000 pages of text,
how many data bits are needed for a typed page? (Hint: Determine the area of the disk that is available to hold data. The area
inside a circle is given by A = πr2, where the radius r is one-half of the diameter.)
Q6.1.15
What is the threshold frequency for sodium metal if a photon with frequency 6.66 × 1014 s−1 ejects a photon with 7.74 × 10−20 J
kinetic energy? Will the photoelectric effect be observed if sodium is exposed to orange light?
S6.1.15
5.49 × 1014 s−1; no

6.2: The Bohr Model
Q6.2.1
Why is the electron in a Bohr hydrogen atom bound less tightly when it has a quantum number of 3 than when it has a quantum
number of 1?
Q6.2.2
What does it mean to say that the energy of the electrons in an atom is quantized?
S6.2.2
Quantized energy means that the electrons can possess only certain discrete energy values; values between those quantized
values are not permitted.
Q6.2.3
Using the Bohr model, determine the energy, in joules, necessary to ionize a ground-state hydrogen atom. Show your
calculations.
Q6.2.4
The electron volt (eV) is a convenient unit of energy for expressing atomic-scale energies. It is the amount of energy that an
electron gains when subjected to a potential of 1 volt; 1 eV = 1.602 × 10 J . Using the Bohr model, determine the energy,
−19
in electron volts, of the photon produced when an electron in a hydrogen atom moves from the orbit with n = 5 to the orbit
with n = 2 . Show your calculations.
S6.2.4
1 1
−18
E = E2 − E5 = 2.179 × 10 ( − ) J (3.E.11)
2 2
n n
2 5
1 1
−18 −19
= 2.179 × 10 ( − ) = 4.576 × 10 J (3.E.12)
2 2
2 5
−19
4.576 × 10 J
= = 2.856 eV (3.E.13)
−19 −1
1.602 × 10 J eV
Q6.2.5
Using the Bohr model, determine the lowest possible energy for the electron in the H e ion. +
Q6.2.6
Using the Bohr model, determine the energy of an electron with n = 6 in a hydrogen atom.
S6.2.6
−8.716 × 10−18 J
Q6.2.7
Using the Bohr model, determine the energy of an electron with n = 8 in a hydrogen atom.
Q6.2.8
How far from the nucleus in angstroms (1 angstrom = 1 × 10
–10
m ) is the electron in a hydrogen atom if it has an energy of
J?
−20
−8.72 × 10
S6.2.8
−20
−3.405 × 10 J

Q6.2.9
What is the radius, in angstroms, of the orbital of an electron with n = 8 in a hydrogen atom?
Q6.2.10
Using the Bohr model, determine the energy in joules of the photon produced when an electron in a He ion moves from the
+
orbit with n = 5 to the orbit with n = 2.
Q6.2.11
Using the Bohr model, determine the energy in joules of the photon produced when an electron in a Li2+ ion moves from the
orbit with n = 2 to the orbit with n = 1.
S6.2.11
1.471 × 10−17 J
Q6.2.12
Consider a large number of hydrogen atoms with electrons randomly distributed in the n = 1, 2, 3, and 4 orbits
a. How many different wavelengths of light are emitted by these atoms as the electrons fall into lower-energy orbitals?
b. Calculate the lowest and highest energies of light produced by the transitions described in part (a).
c. Calculate the frequencies and wavelengths of the light produced by the transitions described in part (b).
Q6.2.13
How are the Bohr model and the Rutherford model of the atom similar? How are they different?
Q6.2.14
The spectra of hydrogen and of calcium are shown in[link]. What causes the lines in these spectra? Why are the colors of the
lines different? Suggest a reason for the observation that the spectrum of calcium is more complicated than the spectrum of
hydrogen
S6.2.14
Both involve a relatively heavy nucleus with electrons moving around it, although strictly speaking, the Bohr model works only for
one-electron atoms or ions. According to classical mechanics, the Rutherford model predicts a miniature “solar system” with
electrons moving about the nucleus in circular or elliptical orbits that are confined to planes. If the requirements of classical
electromagnetic theory that electrons in such orbits would emit electromagnetic radiation are ignored, such atoms would be stable,
having constant energy and angular momentum, but would not emit any visible light (contrary to observation). If classical
electromagnetic theory is applied, then the Rutherford atom would emit electromagnetic radiation of continually increasing
frequency (contrary to the observed discrete spectra), thereby losing energy until the atom collapsed in an absurdly short time
(contrary to the observed long-term stability of atoms). The Bohr model retains the classical mechanics view of circular orbits
confined to planes having constant energy and angular momentum, but restricts these to quantized values dependent on a single
quantum number, n. The orbiting electron in Bohr’s model is assumed not to emit any electromagnetic radiation while moving
about the nucleus in its stationary orbits, but the atom can emit or absorb electromagnetic radiation when the electron changes from
one orbit to another. Because of the quantized orbits, such “quantum jumps” will produce discrete spectra, in agreement with
observations.

Q6.3.1
How are the Bohr model and the quantum mechanical model of the hydrogen atom similar? How are they different?
S6.3.1
Both models have a central positively charged nucleus with electrons moving about the nucleus in accordance with the Coulomb
electrostatic potential. The Bohr model assumes that the electrons move in circular orbits that have quantized energies, angular
momentum, and radii that are specified by a single quantum number, n = 1, 2, 3, …, but this quantization is an ad hoc assumption
made by Bohr to incorporate quantization into an essentially classical mechanics description of the atom. Bohr also assumed that

electrons orbiting the nucleus normally do not emit or absorb electromagnetic radiation, but do so when the electron switches to a
different orbit. In the quantum mechanical model, the electrons do not move in precise orbits (such orbits violate the Heisenberg
uncertainty principle) and, instead, a probabilistic interpretation of the electron’s position at any given instant is used, with a
mathematical function ψ called a wavefunction that can be used to determine the electron’s spatial probability distribution. These
wavefunctions, or orbitals, are three-dimensional stationary waves that can be specified by three quantum numbers that arise
naturally from their underlying mathematics (no ad hoc assumptions required): the principal quantum number, n (the same one used
by Bohr), which specifies shells such that orbitals having the same n all have the same energy and approximately the same spatial
extent; the angular momentum quantum number l, which is a measure of the orbital’s angular momentum and corresponds to the
orbitals’ general shapes, as well as specifying subshells such that orbitals having the same l (and n) all have the same energy; and
the orientation quantum number m, which is a measure of the z component of the angular momentum and corresponds to the
orientations of the orbitals. The Bohr model gives the same expression for the energy as the quantum mechanical expression and,
hence, both properly account for hydrogen’s discrete spectrum (an example of getting the right answers for the wrong reasons,
something that many chemistry students can sympathize with), but gives the wrong expression for the angular momentum (Bohr
orbits necessarily all have non-zero angular momentum, but some quantum orbitals [s orbitals] can have zero angular momentum).
Q6.3.2
What are the allowed values for each of the four quantum numbers: n, l, ml, and ms?
Q6.3.3
Describe the properties of an electron associated with each of the following four quantum numbers: n, l, ml, and ms.
S6.3.3
n determines the general range for the value of energy and the probable distances that the electron can be from the nucleus. l
determines the shape of the orbital. ml determines the orientation of the orbitals of the same l value with respect to one another. ms
determines the spin of an electron.
Q6.3.4
Answer the following questions:
a. Without using quantum numbers, describe the differences between the shells, subshells, and orbitals of an atom.
b. How do the quantum numbers of the shells, subshells, and orbitals of an atom differ?
Q6.3.5
a. n = 2, l = 1
b. n = 4, l = 2
c. n = 6, l = 0
S6.3.5
(a) 2p; (b) 4d; (c) 6s
Q6.3.6
Which of the subshells described in Question 5 contain degenerate orbitals? How many degenerate orbitals are in each?
Q6.3.7
a. n = 3, l = 2
b. n = 1, l = 0
c. n = 4, l = 3
S6.3.7
(a) 3d; (b) 1s; (c) 4f

Q6.3.8
Which of the subshells described in Question 7 contain degenerate orbitals? How many degenerate orbitals are in each?
Q6.3.9
Sketch the boundary surface of a d 2
x −y
2 and a py orbital. Be sure to show and label the axes.
Q6.3.10
Sketch the px and dxz orbitals. Be sure to show and label the coordinates.
Q6.3.11
Consider the orbitals shown here in outline.
a. What is the maximum number of electrons contained in an orbital of type (x)? Of type (y)? Of type (z)?
b. How many orbitals of type (x) are found in a shell with n = 2? How many of type (y)? How many of type (z)?
c. Write a set of quantum numbers for an electron in an orbital of type (x) in a shell with n = 4. Of an orbital of type (y) in a shell
with n = 2. Of an orbital of type (z) in a shell with n = 3.
d. What is the smallest possible n value for an orbital of type (x)? Of type (y)? Of type (z)?
e. What are the possible l and ml values for an orbital of type (x)? Of type (y)? Of type (z)?
S6.3.11
1 1 1
(a) x. 2, y. 2, z. 2; (b) x. 1, y. 3, z. 0; (c) x. 4 0 0 , y. 2 1 0 , z. 3 2 0 ; (d) x. 1, y. 2, z. 3; (e) x. l = 0, ml = 0, y. l = 1, ml = –1, 0,
2 2 2
or +1, z. l = 2, ml = –2, –1, 0, +1, +2
Q6.3.12
State the Heisenberg uncertainty principle. Describe briefly what the principle implies.
Q6.3.13
How many electrons could be held in the second shell of an atom if the spin quantum number ms could have three values instead of
just two? (Hint: Consider the Pauli exclusion principle.)
S6.3.13
12
Q6.3.14
Which of the following equations describe particle-like behavior? Which describe wavelike behavior? Do any involve both types of
behavior? Describe the reasons for your choices.

a. c = λν
2
mν
b. E =
2
2
n a0
c. r =
Z
d. E = hν
h
e. λ =
mν
Q6.3.15
Write a set of quantum numbers for each of the electrons with an n of 4 in a Se atom.
S6.3.15
n l ml s
1
4 0 0 +
2
1
4 0 0 −
2
1
4 1 −1 +
2
1
4 1 0 +
2
1
4 1 +1 +
2
1
4 1 −1 −
2

Q6.4.1
Read the labels of several commercial products and identify monatomic ions of at least four transition elements contained in the
products. Write the complete electron configurations of these cations.
Q6.4.2
Read the labels of several commercial products and identify monatomic ions of at least six main group elements contained in the
products. Write the complete electron configurations of these cations and anions.
S6.4.2
For example, Na+: 1s22s22p6; Ca2+: 1s22s22p6; Sn2+: 1s22s22p63s23p63d104s24p64d105s2; F–: 1s22s22p6; O2–: 1s22s22p6; Cl–:
1s22s22p63s23p6.
Q6.4.3
Using complete subshell notation (not abbreviations, 1s22s22p6, and so forth), predict the electron configuration of each of the
following atoms:
a. C
b. P
c. V
d. Sb
e. Sm
S6.4.3
a.) 1s22s22p2
b.) 1s22s22p63s23p3
c.) 1s22s22p63s23p63d34s2

d.) 1s22s22p63s23p63d104s24p64d105s25p3
e.) 1s22s22p63s23p63d104s24p64d104f65s25p66s2
Q6.4.4
Using complete subshell notation (1s22s22p6, and so forth), predict the electron configuration of each of the following atoms:
a. N
b. Si
c. Fe
d. Te
e. Tb
S6.4.4
a. 1s22s22p3;
b. 1s22s22p63s23p2;
c. 1s22s22p63s23p64s23d6;
d. 1s22s22p63s23p64s23d104p65s24d105p4;
e. 1s22s22p63s23p64s23d104p65s24d105p66s24f9
Q6.4.5
Is 1s22s22p6 the symbol for a macroscopic property or a microscopic property of an element? Explain your answer.
Q6.4.6
What additional information do we need to answer the question “Which ion has the electron configuration 1s22s22p63s23p6”?
S6.4.6
The charge on the ion.
Q6.4.7
Draw the orbital diagram for the valence shell of each of the following atoms:
a. C
b. P
c. V
d. Sb
e. Ru
Q6.4.8
Use an orbital diagram to describe the electron configuration of the valence shell of each of the following atoms:
a. N
b. Si
c. Fe
d. Te
e. Mo
S6.4.8
(a)
(b)

(c)
(d)
(e)
Q6.4.9
Using complete subshell notation (1s22s22p6, and so forth), predict the electron configurations of the following ions.
a. N3–
b. Ca2+
c. S–
d. Cs2+
e. Cr2+
f. Gd3+
Q6.4.10
Which atom has the electron configuration: 1s22s22p63s23p64s23d104p65s24d2?
S6.4.10
Zr
Q6.4.11
Which atom has the electron configuration: 1s22s22p63s23p63d74s2?
S6.4.11
Co ; Cobalt
Q6.4.12
Which ion with a +1 charge has the electron configuration 1s22s22p63s23p63d104s24p6? Which ion with a –2 charge has this
configuration?
S6.4.12
Rb+, Se2−

Q6.4.13
Which of the following atoms contains only three valence electrons: Li, B, N, F, Ne?
S6.4.13
B ; Boron
Q6.4.14
Which of the following has two unpaired electrons?
a. Mg
b. Si
c. S
d. Both Mg and S
e. Both Si and S.
S6.4.14
Although both (b) and (c) are correct, (e) encompasses both and is the best answer.
Q6.4.15
Which atom would be expected to have a half-filled 6p subshell?
S6.4.15
Bi ; Bismuth
Q6.4.16
Which atom would be expected to have a half-filled 4s subshell?
S6.4.16
K
Q6.4.17
In one area of Australia, the cattle did not thrive despite the presence of suitable forage. An investigation showed the cause to be
the absence of sufficient cobalt in the soil. Cobalt forms cations in two oxidation states, Co2+ and Co3+. Write the electron structure
of the two cations.
Q6.4.18
Thallium was used as a poison in the Agatha Christie mystery story “The Pale Horse.” Thallium has two possible cationic forms,
+1 and +3. The +1 compounds are the more stable. Write the electron structure of the +1 cation of thallium.
S6.4.18
1s22s22p63s23p63d104s24p64d105s25p66s24f145d10
Q6.4.19
Write the electron configurations for the following atoms or ions:
a. B3+
b. O–
c. Cl3+
d. Ca2+
e. Ti
Q6.4.20
Cobalt–60 and iodine–131 are radioactive isotopes commonly used in nuclear medicine. How many protons, neutrons, and
electrons are in atoms of these isotopes? Write the complete electron configuration for each isotope.

S6.4.20
Co has 27 protons, 27 electrons, and 33 neutrons: 1s22s22p63s23p64s23d7.
I has 53 protons, 53 electrons, and 78 neutrons: 1s22s22p63s23p63d104s24p64d105s25p5.
Q6.4.21
Write a set of quantum numbers for each of the electrons with an n of 3 in a Sc atom.

Q6.5.1
Based on their positions in the periodic table, predict which has the smallest atomic radius: Mg, Sr, Si, Cl, I.
S6.5.1
Cl
Q6.5.2
Based on their positions in the periodic table, predict which has the largest atomic radius: Li, Rb, N, F, I.
Q6.5.3
Based on their positions in the periodic table, predict which has the largest first ionization energy: Mg, Ba, B, O, Te.
S6.5.3
O
Q6.5.4
Based on their positions in the periodic table, predict which has the smallest first ionization energy: Li, Cs, N, F, I.
Q6.5.5
Based on their positions in the periodic table, rank the following atoms in order of increasing first ionization energy: F, Li, N, Rb
S6.5.5
Rb < Li < N < F
Q6.5.6
Based on their positions in the periodic table, rank the following atoms or compounds in order of increasing first ionization energy:
Mg, O, S, Si
Q6.5.7
Atoms of which group in the periodic table have a valence shell electron configuration of ns2np3?
S6.5.7
15 (5A)
Q6.5.8
Atoms of which group in the periodic table have a valence shell electron configuration of ns2?
Q6.5.9
Based on their positions in the periodic table, list the following atoms in order of increasing radius: Mg, Ca, Rb, Cs.
S6.5.9
Mg < Ca < Rb < Cs

Q6.5.10
Based on their positions in the periodic table, list the following atoms in order of increasing radius: Sr, Ca, Si, Cl.
Q6.5.11
Based on their positions in the periodic table, list the following ions in order of increasing radius: K+, Ca2+, Al3+, Si4+.
S6.5.11
Si4+ < Al3+ < Ca2+ < K+
Q6.5.12
List the following ions in order of increasing radius: Li+, Mg2+, Br–, Te2–.
Q6.5.13
Which atom and/or ion is (are) isoelectronic with Br+: Se2+, Se, As–, Kr, Ga3+, Cl–?
S6.5.13
Se, As−
Q6.5.14
Which of the following atoms and ions is (are) isoelectronic with S2+: Si4+, Cl3+, Ar, As3+, Si, Al3+?
Q6.5.15
Compare both the numbers of protons and electrons present in each to rank the following ions in order of increasing radius: As3–,
Br–, K+, Mg2+.
S6.5.15
Mg2+ < K+ < Br– < As3–
Q6.5.16
Of the five elements Al, Cl, I, Na, Rb, which has the most exothermic reaction? (E represents an atom.) What name is given to the
energy for the reaction? Hint: note the process depicted does not correspond to electron affinity
+ −
E (g) + e ⟶ E(g)
Q6.5.17
Of the five elements Sn, Si, Sb, O, Te, which has the most endothermic reaction? (E represents an atom.) What name is given to the
energy for the reaction?
+ −
E(g) ⟶ E (g) + e (3.E.14)
S6.5.17
O, IE1
Q6.5.18
The ionic radii of the ions S2–, Cl–, and K+ are 184, 181, 138 pm respectively. Explain why these ions have different sizes even
though they contain the same number of electrons.
Q6.5.19
Which main group atom would be expected to have the lowest second ionization energy?
S6.5.19
Ra

Q6.5.20
Explain why Al is a member of group 13 rather than group 3?
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CHAPTER OVERVIEW
4: Chemical Bonding and Molecular Geometry

General Chemistry
A chemical bond is an attraction between atoms that allows the formation of chemical substances that contain two or more atoms.
The bond is caused by the electrostatic force of attraction between opposite charges, either between electrons and nuclei, or as the
result of a dipole attraction. All bonds can be explained by quantum theory, but, in practice, simplification rules allow chemists to
predict the strength, directionality, and polarity of bonds. The octet rule and VSEPR theory are two examples. More sophisticated
theories are valence bond theory which includes orbital hybridization and resonance, and the linear combination of atomic orbitals
molecular orbital method. Electrostatics are used to describe bond polarities and the effects they have on chemical substances.
4.2: Ionic Bonding
Contributors
[email protected]).
This page titled 4: Chemical Bonding and Molecular Geometry is shared under a CC BY license and was authored, remixed, and/or curated by
OpenStax.
1
It has long been known that pure carbon occurs in different forms (allotropes) including graphite and diamonds. But it was not until
1985 that a new form of carbon was recognized: buckminsterfullerene, commonly known as a “buckyball.” This molecule was
named after the architect and inventor R. Buckminster Fuller (1895–1983), whose signature architectural design was the geodesic
dome, characterized by a lattice shell structure supporting a spherical surface. Experimental evidence revealed the formula, C60,
and then scientists determined how 60 carbon atoms could form one symmetric, stable molecule. They were guided by bonding
theory—the topic of this chapter—which explains how individual atoms connect to form more complex structures.
Figure 4.1.1 : Nicknamed “buckyballs,” buckminsterfullerene molecules (C60) contain only carbon atoms. Here they are shown in a
ball-and-stick model (left). These molecules have single and double carbon-carbon bonds arranged to form a geometric framework
of hexagons and pentagons, similar to the pattern on a soccer ball (center). This unconventional molecular structure is named after
architect R. Buckminster Fuller, whose innovative designs combined simple geometric shapes to create large, strong structures such
as this weather radar dome near Tucson, Arizona (right). (credit middle: modification of work by “Petey21”/Wikimedia Commons;
credit right: modification of work by Bill Morrow).
Three figures are shown. The left figure is a many-sides spherical ball composed of hexagonal rings which have carbon atoms at
each corner. The center picture shows a soccer ball. The right picture shown as water tower with sides shaped like hexagonal rings.
This page titled 4.1: Prelude to Chemical Bonding and Molecular Geometry is shared under a CC BY license and was authored, remixed, and/or
7.0: Prelude to Chemical Bonding and Molecular Geometry is licensed CC BY 4.0. Original source:

4.2: Ionic Bonding
Explain the formation of cations, anions, and ionic compounds
Predict the charge of common metallic and nonmetallic elements, and write their electron configurations
As you have learned, ions are atoms or molecules bearing an electrical charge. A cation (a positive ion) forms when a neutral atom
loses one or more electrons from its valence shell, and an anion (a negative ion) forms when a neutral atom gains one or more
electrons in its valence shell.
Compounds composed of ions are called ionic compounds (or salts), and their constituent ions are held together by ionic bonds:
electrostatic forces of attraction between oppositely charged cations and anions. The properties of ionic compounds shed some light
on the nature of ionic bonds. Ionic solids exhibit a crystalline structure and tend to be rigid and brittle; they also tend to have high
melting and boiling points, which suggests that ionic bonds are very strong. Ionic solids are also poor conductors of electricity for
the same reason—the strength of ionic bonds prevents ions from moving freely in the solid state. Most ionic solids, however,
dissolve readily in water. Once dissolved or melted, ionic compounds are excellent conductors of electricity and heat because the
ions can move about freely.
Neutral atoms and their associated ions have very different physical and chemical properties. Sodium atoms form sodium metal, a
soft, silvery-white metal that burns vigorously in air and reacts explosively with water. Chlorine atoms form chlorine gas, Cl2, a
yellow-green gas that is extremely corrosive to most metals and very poisonous to animals and plants. The vigorous reaction
between the elements sodium and chlorine forms the white, crystalline compound sodium chloride, common table salt, which
contains sodium cations and chloride anions (Figure Figure 4.2.1). The compound composed of these ions exhibits properties
entirely different from the properties of the elements sodium and chlorine. Chlorine is poisonous, but sodium chloride is essential
to life; sodium atoms react vigorously with water, but sodium chloride simply dissolves in water.
Figure 4.2.1 : (a) Sodium is a soft metal that must be stored in mineral oil to prevent reaction with air or water. (b) Chlorine is a
pale yellow-green gas. (c) When combined, they form white crystals of sodium chloride (table salt). (credit a: modification of work
by “Jurii”/Wikimedia Commons)
The Formation of Ionic Compounds

Binary ionic compounds are composed of just two elements: a metal (which forms the cations) and a nonmetal (which forms the
anions). For example, NaCl is a binary ionic compound. We can think about the formation of such compounds in terms of the
periodic properties of the elements. Many metallic elements have relatively low ionization potentials and lose electrons easily.
These elements lie to the left in a period or near the bottom of a group on the periodic table. Nonmetal atoms have relatively high
electron affinities and thus readily gain electrons lost by metal atoms, thereby filling their valence shells. Nonmetallic elements are
found in the upper-right corner of the periodic table.
As all substances must be electrically neutral, the total number of positive charges on the cations of an ionic compound must equal
the total number of negative charges on its anions. The formula of an ionic compound represents the simplest ratio of the numbers
of ions necessary to give identical numbers of positive and negative charges. For example, the formula for aluminum oxide, Al2O3,
indicates that this ionic compound contains two aluminum cations, Al3+, for every three oxide anions, O2− [thus, (2 × +3) + (3 × –
2) = 0].
It is important to note, however, that the formula for an ionic compound does not represent the physical arrangement of its ions. It
is incorrect to refer to a sodium chloride (NaCl) “molecule” because there is not a single ionic bond, per se, between any specific
pair of sodium and chloride ions. The attractive forces between ions are isotropic—the same in all directions—meaning that any

particular ion is equally attracted to all of the nearby ions of opposite charge. This results in the ions arranging themselves into a
tightly bound, three-dimensional lattice structure. Sodium chloride, for example, consists of a regular arrangement of equal
numbers of Na+ cations and Cl– anions (Figure Figure 4.2.2).
Figure 4.2.2 : The atoms in sodium chloride (common table salt) are arranged to (a) maximize opposite charges interacting. The
smaller spheres represent sodium ions, the larger ones represent chloride ions. In the expanded view (b), the geometry can be seen
more clearly. Note that each ion is “bonded” to all of the surrounding ions—six in this case.
Two diagrams are shown and labeled “a” and “b.” Diagram a shows a cube made up of twenty-seven alternating purple and green
spheres. The purple spheres are smaller than the green spheres. Diagram b shows the same spheres, but this time, they are spread
out and connected in three dimensions by white rods. The purple spheres are labeled “N superscript postive sign” while the green
are labeled “C l superscript negative sign.”
The strong electrostatic attraction between Na+ and Cl– ions holds them tightly together in solid NaCl. It requires 769 kJ of energy
to dissociate one mole of solid NaCl into separate gaseous Na+ and Cl– ions:
+ −
NaCl(s) ⟶ Na (g) + Cl (g) ΔH = 769 kJ
Electronic Structures of Cations

When forming a cation, an atom of a main group element tends to lose all of its valence electrons, thus assuming the electronic
structure of the noble gas that precedes it in the periodic table. For groups 1 (the alkali metals) and 2 (the alkaline earth metals), the
group numbers are equal to the numbers of valence shell electrons and, consequently, to the charges of the cations formed from
atoms of these elements when all valence shell electrons are removed. For example, calcium is a group 2 element whose neutral
atoms have 20 electrons and a ground state electron configuration of 1s22s22p63s23p64s2. When a Ca atom loses both of its valence
electrons, the result is a cation with 18 electrons, a 2+ charge, and an electron configuration of 1s22s22p63s23p6. The Ca2+ ion is
therefore isoelectronic with the noble gas Ar.
For groups 12–17, the group numbers exceed the number of valence electrons by 10 (accounting for the possibility of full d
subshells in atoms of elements in the fourth and greater periods). Thus, the charge of a cation formed by the loss of all valence
electrons is equal to the group number minus 10. For example, aluminum (in group 13) forms 3+ ions (Al3+).
Exceptions to the expected behavior involve elements toward the bottom of the groups. In addition to the expected ions Tl3+, Sn4+,
Pb4+, and Bi5+, a partial loss of these atoms’ valence shell electrons can also lead to the formation of Tl+, Sn2+, Pb2+, and Bi3+ ions.
The formation of these 1+, 2+, and 3+ cations is ascribed to the inert pair effect, which reflects the relatively low energy of the
valence s-electron pair for atoms of the heavy elements of groups 13, 14, and 15. Mercury (group 12) also exhibits an unexpected
behavior: it forms a diatomic ion, Hg (an ion formed from two mercury atoms, with an Hg-Hg bond), in addition to the expected
2+
monatomic ion Hg2+ (formed from only one mercury atom).

Transition and inner transition metal elements behave differently than main group elements. Most transition metal cations have 2+
or 3+ charges that result from the loss of their outermost s electron(s) first, sometimes followed by the loss of one or two d
electrons from the next-to-outermost shell. For example, iron (1s22s22p63s23p63d64s2) forms the ion Fe2+ (1s22s22p63s23p63d6) by
the loss of the 4s electrons and the ion Fe3+ (1s22s22p63s23p63d5) by the loss of the 4s electrons and one of the 3d electrons.
Although the d orbitals of the transition elements are—according to the Aufbau principle—the last to fill when building up electron
configurations, the outermost s electrons are the first to be lost when these atoms ionize. When the inner transition metals form
ions, they usually have a 3+ charge, resulting from the loss of their outermost s electrons and a d or f electron.
 Example 4.2.1: Determining the Electronic Structures of Cations
There are at least 14 elements categorized as “essential trace elements” for the human body. They are called “essential”
because they are required for healthy bodily functions, “trace” because they are required only in small amounts, and
“elements” in spite of the fact that they are really ions. Two of these essential trace elements, chromium and zinc, are required
as Cr3+ and Zn2+. Write the electron configurations of these cations.
Solution
First, write the electron configuration for the neutral atoms:
Zn: [Ar]3d104s2

Cr: [Ar]3d54s1
Next, remove electrons from the highest energy orbital. For the transition metals, electrons are removed from the s orbital first
and then from the d orbital. For the p-block elements, electrons are removed from the p orbitals and then from the s orbital.
Zinc is a member of group 12, so it should have a charge of 2+, and thus loses only the two electrons in its s orbital. Chromium
is a transition element and should lose its s electrons and then its d electrons when forming a cation. Thus, we find the
following electron configurations of the ions:
Zn2+: [Ar]3d10
Cr3+: [Ar]3d3
 Exercise 4.2.1
Potassium and magnesium are required in our diet. Write the electron configurations of the ions expected from these elements.
Answer
K+: [Ar], Mg2+: [Ne]
Electronic Structures of Anions

Most monatomic anions form when a neutral nonmetal atom gains enough electrons to completely fill its outer s and p orbitals,
thereby reaching the electron configuration of the next noble gas. Thus, it is simple to determine the charge on such a negative ion:
The charge is equal to the number of electrons that must be gained to fill the s and p orbitals of the parent atom. Oxygen, for
example, has the electron configuration 1s22s22p4, whereas the oxygen anion has the electron configuration of the noble gas neon
(Ne), 1s22s22p6. The two additional electrons required to fill the valence orbitals give the oxide ion the charge of 2– (O2–).
 Example 4.2.2: Determining the Electronic Structure of Anions
Selenium and iodine are two essential trace elements that form anions. Write the electron configurations of the anions.
Solution
Se2–: [Ar]3d104s24p6
I–: [Kr]4d105s25p6
 Exercise 4.2.2
Write the electron configurations of a phosphorus atom and its negative ion. Give the charge on the anion.
Answer
P: [Ne]3s23p3
P3–: [Ne]3s23p6
Summary
Atoms gain or lose electrons to form ions with particularly stable electron configurations. The charges of cations formed by the
representative metals may be determined readily because, with few exceptions, the electronic structures of these ions have either a
noble gas configuration or a completely filled electron shell. The charges of anions formed by the nonmetals may also be readily
determined because these ions form when nonmetal atoms gain enough electrons to fill their valence shells.

Glossary
inert pair effect
tendency of heavy atoms to form ions in which their valence s electrons are not lost
ionic bond
strong electrostatic force of attraction between cations and anions in an ionic compound
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Describe the formation of covalent bonds
Define electronegativity and assess the polarity of covalent bonds
In ionic compounds, electrons are transferred between atoms of different elements to form ions. But this is not the only way that
compounds can be formed. Atoms can also make chemical bonds by sharing electrons between each other. Such bonds are called
covalent bonds. Covalent bonds are formed between two atoms when both have similar tendencies to attract electrons to
themselves (i.e., when both atoms have identical or fairly similar ionization energies and electron affinities). For example, two
hydrogen atoms bond covalently to form an H2 molecule; each hydrogen atom in the H2 molecule has two electrons stabilizing it,
giving each atom the same number of valence electrons as the noble gas He.
Compounds that contain covalent bonds exhibit different physical properties than ionic compounds. Because the attraction between
molecules, which are electrically neutral, is weaker than that between electrically charged ions, covalent compounds generally have
much lower melting and boiling points than ionic compounds. In fact, many covalent compounds are liquids or gases at room
temperature, and, in their solid states, they are typically much softer than ionic solids. Furthermore, whereas ionic compounds are
good conductors of electricity when dissolved in water, most covalent compounds, being electrically neutral, are poor conductors
of electricity in any state.
Formation of Covalent Bonds

Nonmetal atoms frequently form covalent bonds with other nonmetal atoms. For example, the hydrogen molecule, H2, contains a
covalent bond between its two hydrogen atoms. Figure 4.3.1 illustrates why this bond is formed. Starting on the far right, we have
two separate hydrogen atoms with a particular potential energy, indicated by the red line. Along the x-axis is the distance between
the two atoms. As the two atoms approach each other (moving left along the x-axis), their valence orbitals (1s) begin to overlap.
The single electrons on each hydrogen atom then interact with both atomic nuclei, occupying the space around both atoms. The
strong attraction of each shared electron to both nuclei stabilizes the system, and the potential energy decreases as the bond
distance decreases. If the atoms continue to approach each other, the positive charges in the two nuclei begin to repel each other,
and the potential energy increases. The bond length is determined by the distance at which the lowest potential energy is achieved.

Figure 4.3.1 : The potential energy of two separate hydrogen atoms (right) decreases as they approach each other, and the single
electrons on each atom are shared to form a covalent bond. The bond length is the internuclear distance at which the lowest
potential energy is achieved.
It is essential to remember that energy must be added to break chemical bonds (an endothermic process), whereas forming chemical
bonds releases energy (an exothermic process). In the case of H2, the covalent bond is very strong; a large amount of energy, 436
kJ, must be added to break the bonds in one mole of hydrogen molecules and cause the atoms to separate:
H (g) ⟶ 2 H(g) ΔH = 436 kJ

2
Conversely, the same amount of energy is released when one mole of H2 molecules forms from two moles of H atoms:
2 H(g) ⟶ H (g) ΔH = −436 kJ

2
Pure vs. Polar Covalent Bonds

If the atoms that form a covalent bond are identical, as in H2, Cl2, and other diatomic molecules, then the electrons in the bond
must be shared equally. We refer to this as a pure covalent bond. Electrons shared in pure covalent bonds have an equal probability
of being near each nucleus. In the case of Cl2, each atom starts off with seven valence electrons, and each Cl shares one electron
with the other, forming one covalent bond:
Cl + Cl ⟶ Cl
2
The total number of electrons around each individual atom consists of six nonbonding electrons and two shared (i.e., bonding)
electrons for eight total electrons, matching the number of valence electrons in the noble gas argon. Since the bonding atoms are
identical, Cl2 also features a pure covalent bond.
When the atoms linked by a covalent bond are different, the bonding electrons are shared, but no longer equally. Instead, the
bonding electrons are more attracted to one atom than the other, giving rise to a shift of electron density toward that atom. This
unequal distribution of electrons is known as a polar covalent bond, characterized by a partial positive charge on one atom and a
partial negative charge on the other. The atom that attracts the electrons more strongly acquires the partial negative charge and vice
versa. For example, the electrons in the H–Cl bond of a hydrogen chloride molecule spend more time near the chlorine atom than
near the hydrogen atom. Thus, in an HCl molecule, the chlorine atom carries a partial negative charge and the hydrogen atom has a
partial positive charge. Figure 4.3.2 shows the distribution of electrons in the H–Cl bond. Note that the shaded area around Cl is
much larger than it is around H. Compare this to Figure 4.3.1, which shows the even distribution of electrons in the H2 nonpolar
bond.

Figure 4.3.2 : (a) The distribution of electron density in the HCl molecule is uneven. The electron density is greater around the
chlorine nucleus. The small, black dots indicate the location of the hydrogen and chlorine nuclei in the molecule. (b) Symbols δ+
and δ– indicate the polarity of the H–Cl bond.
We sometimes designate the positive and negative atoms in a polar covalent bond using a lowercase Greek letter “delta,” δ, with a
plus sign or minus sign to indicate whether the atom has a partial positive charge (δ+) or a partial negative charge (δ–). This
symbolism is shown for the H–Cl molecule in Figure 4.3.2b.
Electronegativity
Whether a bond is nonpolar or polar covalent is determined by a property of the bonding atoms called electronegativity.
Electronegativity is a measure of the tendency of an atom to attract electrons (or electron density) towards itself. It determines how
the shared electrons are distributed between the two atoms in a bond. The more strongly an atom attracts the electrons in its bonds,
the larger its electronegativity. Electrons in a polar covalent bond are shifted toward the more electronegative atom; thus, the more
electronegative atom is the one with the partial negative charge. The greater the difference in electronegativity, the more polarized
the electron distribution and the larger the partial charges of the atoms.
Figure 4.3.3 shows the electronegativity values of the elements as proposed by one of the most famous chemists of the twentieth
century: Linus Pauling. In general, electronegativity increases from left to right across a period in the periodic table and decreases
down a group. Thus, the nonmetals, which lie in the upper right, tend to have the highest electronegativities, with fluorine the most
electronegative element of all (EN = 4.0). Metals tend to be less electronegative elements, and the group 1 metals have the lowest
electronegativities. Note that noble gases are excluded from this figure because these atoms usually do not share electrons with
others atoms since they have a full valence shell. (While noble gas compounds such as XeO2 do exist, they can only be formed
under extreme conditions, and thus they do not fit neatly into the general model of electronegativity.)
Figure 4.3.3 : The electronegativity values derived by Pauling follow predictable periodic trends with the higher electronegativities
toward the upper right of the periodic table.
 Linus Pauling
Linus Pauling is the only person to have received two unshared (individual) Nobel Prizes: one for chemistry in 1954 for his
work on the nature of chemical bonds and one for peace in 1962 for his opposition to weapons of mass destruction. He
developed many of the theories and concepts that are foundational to our current understanding of chemistry, including
electronegativity and resonance structures.

Linus Pauling (1901–1994) made many important contributions to the field of chemistry. He was also a prominent activist,
publicizing issues related to health and nuclear weapons.
Pauling also contributed to many other fields besides chemistry. His research on sickle cell anemia revealed the cause of the
disease—the presence of a genetically inherited abnormal protein in the blood—and paved the way for the field of molecular
genetics. His work was also pivotal in curbing the testing of nuclear weapons; he proved that radioactive fallout from nuclear
testing posed a public health risk.
Electronegativity versus Electron Affinity

We must be careful not to confuse electronegativity and electron affinity. The electron affinity of an element is a measurable
physical quantity, namely, the energy released or absorbed when an isolated gas-phase atom acquires an electron, measured in
kJ/mol. Electronegativity, on the other hand, describes how tightly an atom attracts electrons in a bond. It is a dimensionless
quantity that is calculated, not measured. Pauling derived the first electronegativity values by comparing the amounts of energy
required to break different types of bonds. He chose an arbitrary relative scale ranging from 0 to 4.
Electronegativity and Bond Type

The absolute value of the difference in electronegativity (ΔEN) of two bonded atoms provides a rough measure of the polarity to be
expected in the bond and, thus, the bond type. When the difference is very small or zero, the bond is covalent and nonpolar. When
it is large, the bond is polar covalent or ionic. The absolute values of the electronegativity differences between the atoms in the
bonds H–H, H–Cl, and Na–Cl are 0 (nonpolar), 0.9 (polar covalent), and 2.1 (ionic), respectively. The degree to which electrons are
shared between atoms varies from completely equal (pure covalent bonding) to not at all (ionic bonding). Figure 4.3.4 shows the
relationship between electronegativity difference and bond type.
Figure 4.3.4 : As the electronegativity difference increases between two atoms, the bond becomes more ionic.
A rough approximation of the electronegativity differences associated with covalent, polar covalent, and ionic bonds is shown in
Figure 4.3.4. This table is just a general guide, however, with many exceptions. For example, the H and F atoms in HF have an
electronegativity difference of 1.9, and the N and H atoms in NH3 a difference of 0.9, yet both of these compounds form bonds that
are considered polar covalent. Likewise, the Na and Cl atoms in NaCl have an electronegativity difference of 2.1, and the Mn and I
atoms in MnI2 have a difference of 1.0, yet both of these substances form ionic compounds.
The best guide to the covalent or ionic character of a bond is to consider the types of atoms involved and their relative positions in
the periodic table. Bonds between two nonmetals are generally covalent; bonding between a metal and a nonmetal is often ionic.
Some compounds contain both covalent and ionic bonds. The atoms in polyatomic ions, such as OH–, NO , and NH , are held
−
3
+
4
together by polar covalent bonds. However, these polyatomic ions form ionic compounds by combining with ions of opposite

charge. For example, potassium nitrate, KNO3, contains the K+ cation and the polyatomic NO anion. Thus, bonding in potassium
−
nitrate is ionic, resulting from the electrostatic attraction between the ions K+ and NO , as well as covalent between the nitrogen
−
and oxygen atoms in NO . −
 Example 4.3.1: Electronegativity and Bond Polarity
Bond polarities play an important role in determining the structure of proteins. Using the electronegativity values in Table A2,
arrange the following covalent bonds—all commonly found in amino acids—in order of increasing polarity. Then designate the
positive and negative atoms using the symbols δ+ and δ–:
C–H, C–N, C–O, N–H, O–H, S–H
Solution
The polarity of these bonds increases as the absolute value of the electronegativity difference increases. The atom with the δ–
designation is the more electronegative of the two. Table 4.3.1 shows these bonds in order of increasing polarity.
Table 4.3.1 : Bond Polarity and Electronegativity Difference
Bond ΔEN Polarity
δ− δ+
C–H 0.4 C − H
δ− δ+
S–H 0.4 S − H
δ+ δ−
C–N 0.5 C − N
δ− δ+
N–H 0.9 N − H
δ+ δ−
C–O 1.0 C − O
δ− δ+
O–H 1.4 O − H
 Exercise 4.3.1
Silicones are polymeric compounds containing, among others, the following types of covalent bonds: Si–O, Si–C, C–H, and
C–C. Using the electronegativity values in Figure 4.3.3, arrange the bonds in order of increasing polarity and designate the
positive and negative atoms using the symbols δ+ and δ–.
Answer
Answer to Exercise 7.2.1
Bond Electronegativity Difference Polarity
C–C 0.0 nonpolar

δ− δ+
C–H 0.4 C − H
δ+ δ−
Si–C 0.7 Si − C
δ+ δ−
Si–O 1.7 Si − O
Summary
Covalent bonds form when electrons are shared between atoms and are attracted by the nuclei of both atoms. In pure covalent
bonds, the electrons are shared equally. In polar covalent bonds, the electrons are shared unequally, as one atom exerts a stronger
force of attraction on the electrons than the other. The ability of an atom to attract a pair of electrons in a chemical bond is called its
electronegativity. The difference in electronegativity between two atoms determines how polar a bond will be. In a diatomic

molecule with two identical atoms, there is no difference in electronegativity, so the bond is nonpolar or pure covalent. When the
electronegativity difference is very large, as is the case between metals and nonmetals, the bonding is characterized as ionic.
Glossary
bond length
distance between the nuclei of two bonded atoms at which the lowest potential energy is achieved
covalent bond
bond formed when electrons are shared between atoms
electronegativity
tendency of an atom to attract electrons in a bond to itself
polar covalent bond

covalent bond between atoms of different electronegativities; a covalent bond with a positive end and a negative end
pure covalent bond
(also, nonpolar covalent bond) covalent bond between atoms of identical electronegativities
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Write Lewis symbols for neutral atoms and ions
Draw Lewis structures depicting the bonding in simple molecules
Thus far, we have discussed the various types of bonds that form between atoms and/or ions. In all cases, these bonds involve the
sharing or transfer of valence shell electrons between atoms. In this section, we will explore the typical method for depicting
valence shell electrons and chemical bonds, namely Lewis symbols and Lewis structures.
Lewis Symbols
We use Lewis symbols to describe valence electron configurations of atoms and monatomic ions. A Lewis symbol consists of an
elemental symbol surrounded by one dot for each of its valence electrons:
Figure 4.4.1 shows the Lewis symbols for the elements of the third period of the periodic table. Electron dots are typically arranged
in four pairs located on the four "sides" of the atomic symbol.
Figure 4.4.1 : Lewis symbols illustrating the number of valence electrons for each element in the third period of the periodic table.
Lewis symbols can be used to illustrate the formation of cations from atoms, as shown here for sodium and calcium:
Likewise, they can be used to show the formation of anions from atoms, as shown here for chlorine and sulfur:
Figure 4.4.2 demonstrates the use of Lewis symbols to show the transfer of electrons during the formation of ionic compounds.

Figure 4.4.2 : Cations are formed when atoms lose electrons, represented by fewer Lewis dots, whereas anions are formed by atoms
gaining electrons. The total number of electrons does not change.
Lewis Structures
We also use Lewis symbols to indicate the formation of covalent bonds, which are shown in Lewis structures, drawings that
describe the bonding in molecules and polyatomic ions. For example, when two chlorine atoms form a chlorine molecule, they
share one pair of electrons:
The Lewis structure indicates that each Cl atom has three pairs of electrons that are not used in bonding (called lone pairs) and one
shared pair of electrons (written between the atoms). A dash (or line) is usually used to indicate a shared pair of electrons:
In the Lewis model, a single shared pair of electrons is a single bond. Each Cl atom interacts with eight valence electrons total: the
six in the lone pairs and the two in the single bond.
The Octet Rule

The other halogen molecules (F2, Br2, I2, and At2) form bonds like those in the chlorine molecule: one single bond between atoms
and three lone pairs of electrons per atom. This allows each halogen atom to have a noble gas electron configuration. The tendency
of main group atoms to form enough bonds to obtain eight valence electrons is known as the octet rule.
The number of bonds that an atom can form can often be predicted from the number of electrons needed to reach an octet (eight
valence electrons); this is especially true of the nonmetals of the second period of the periodic table (C, N, O, and F). For example,
each atom of a group 14 element has four electrons in its outermost shell and therefore requires four more electrons to reach an
octet. These four electrons can be gained by forming four covalent bonds, as illustrated here for carbon in CCl4 (carbon
tetrachloride) and silicon in SiH4 (silane). Because hydrogen only needs two electrons to fill its valence shell, it is an exception to
the octet rule and only needs to form one bond. The transition elements and inner transition elements also do not follow the octet
rule since they have d and f electrons involved in their valence shells.

Group 15 elements such as nitrogen have five valence electrons in the atomic Lewis symbol: one lone pair and three unpaired
electrons. To obtain an octet, these atoms form three covalent bonds, as in NH3 (ammonia). Oxygen and other atoms in group 16
obtain an octet by forming two covalent bonds:
Double and Triple Bonds

As previously mentioned, when a pair of atoms shares one pair of electrons, we call this a single bond. However, a pair of atoms
may need to share more than one pair of electrons in order to achieve the requisite octet. A double bond forms when two pairs of
electrons are shared between a pair of atoms, as between the carbon and oxygen atoms in CH2O (formaldehyde) and between the
two carbon atoms in C2H4 (ethylene):
A triple bond forms when three electron pairs are shared by a pair of atoms, as in carbon monoxide (CO) and the cyanide ion
(CN–):
Writing Lewis Structures with the Octet Rule

For very simple molecules and molecular ions, we can write the Lewis structures by merely pairing up the unpaired electrons on
the constituent atoms. See these examples:
For more complicated molecules and molecular ions, it is helpful to follow the step-by-step procedure outlined here:
1. Determine the total number of valence (outer shell) electrons among all the atoms. For cations, subtract one electron for each
positive charge. For anions, add one electron for each negative charge.
2. Draw a skeleton structure of the molecule or ion, arranging the atoms around a central atom. (Generally, the least
electronegative element should be placed in the center.) Connect each atom to the central atom with a single bond (one electron
pair).
3. Distribute the remaining electrons as lone pairs on the terminal atoms (except hydrogen), completing an octet around each
atom.

4. Place all remaining electrons on the central atom.
5. Rearrange the electrons of the outer atoms to make multiple bonds with the central atom in order to obtain octets wherever
possible.
Let us determine the Lewis structures of SiH4, CHO , NO+, and OF2 as examples in following this procedure:
−
2
1. Determine the total number of valence (outer shell) electrons in the molecule or ion.
For a molecule, we add the number of valence electrons on each atom in the molecule:
SiH (4.4.1)
4
Si: 4 valence electrons/atom × 1 atom = 4 (4.4.2)
+H: 1 valence electron/atom × 4 atoms = 4 (4.4.3)

––––––––––––––––––––––––––––––––––––––––––
= 8 valence electrons (4.4.4)
For a negative ion, such as CHO , we add the number of valence electrons on the atoms to the number of negative charges
−
on the ion (one electron is gained for each single negative charge):
−
CHO
2
C: 4 valence electrons/atom × 1 atom = 4
H: 1 valence electron/atom × 1 atom = 1
O: 6 valence electrons/atom × 2 atoms = 12
+ 1 additional electron = 1
––––––––––––––––––––––––––––––––––––––––
= 18 valence electrons
For a positive ion, such as NO+, we add the number of valence electrons on the atoms in the ion and then subtract the
number of positive charges on the ion (one electron is lost for each single positive charge) from the total number of valence
electrons:
+
NO
N: 5 valence electrons/atom × 1 atom = 5
O: 6 valence electron/atom × 1 atom = 6
+ −1 electron (positive charge) = −1

––––––––––––––––––––––––––––––––––––––––––
Since OF2 is a neutral molecule, we simply add the number of valence electrons:
OF
2
O: 6 valence electrons/atom × 1 atom =6
+ F: 7 valence electrons/atom × 2 atoms = 14

–––––––––––––––––––––––––––––––––––––––––––––
2. Draw a skeleton structure of the molecule or ion, arranging the atoms around a central atom and connecting each atom to the
central atom with a single (one electron pair) bond. (Note that we denote ions with brackets around the structure, indicating the
charge outside the brackets:)
3. When several arrangements of atoms are possible, as for CHO , we must use experimental evidence to choose the correct one.
−
In general, the less electronegative elements are more likely to be central atoms. In CHO , the less electronegative carbon
−
atom occupies the central position with the oxygen and hydrogen atoms surrounding it. Other examples include P in POCl3, S in
SO2, and Cl in ClO . An exception is that hydrogen is almost never a central atom. As the most electronegative element,
−
fluorine also cannot be a central atom.

4. Distribute the remaining electrons as lone pairs on the terminal atoms (except hydrogen) to complete their valence shells with
an octet of electrons.
There are no remaining electrons on SiH4, so it is unchanged:

5. Place all remaining electrons on the central atom.
For SiH4, CHO , and NO+, there are no remaining electrons; we already placed all of the electrons determined in Step 1.
−
For OF2, we had 16 electrons remaining in Step 3, and we placed 12, leaving 4 to be placed on the central atom:
6. Rearrange the electrons of the outer atoms to make multiple bonds with the central atom in order to obtain octets wherever
possible.
SiH4: Si already has an octet, so nothing needs to be done.
CHO : We have distributed the valence electrons as lone pairs on the oxygen atoms, but the carbon atom lacks an octet:
−
NO+: For this ion, we added eight outer electrons, but neither atom has an octet. We cannot add any more electrons since we
have already used the total that we found in Step 1, so we must move electrons to form a multiple bond:
This still does not produce an octet, so we must move another pair, forming a triple bond:
In OF2, each atom has an octet as drawn, so nothing changes.
 Example 4.4.1: Writing Lewis Structures
NASA’s Cassini-Huygens mission detected a large cloud of toxic hydrogen cyanide (HCN) on Titan, one of Saturn’s moons.
Titan also contains ethane (H3CCH3), acetylene (HCCH), and ammonia (NH3). What are the Lewis structures of these
molecules?
Solution
Calculate the number of valence electrons.
HCN: (1 × 1) + (4 × 1) + (5 × 1) = 10
H3CCH3: (1 × 3) + (2 × 4) + (1 × 3) = 14
HCCH: (1 × 1) + (2 × 4) + (1 × 1) = 10
NH3: (5 × 1) + (3 × 1) = 8
Draw a skeleton and connect the atoms with single bonds. Remember that H is never a central atom:
Where needed, distribute electrons to the terminal atoms:
HCN: six electrons placed on N

H3CCH3: no electrons remain

HCCH: no terminal atoms capable of accepting electrons
NH3: no terminal atoms capable of accepting electrons
Where needed, place remaining electrons on the central atom:
HCN: no electrons remain

H3CCH3: no electrons remain
HCCH: four electrons placed on carbon
NH3: two electrons placed on nitrogen
Where needed, rearrange electrons to form multiple bonds in order to obtain an octet on each atom:
HCN: form two more C–N bonds
H3CCH3: all atoms have the correct number of electrons
HCCH: form a triple bond between the two carbon atoms
NH3: all atoms have the correct number of electrons
 Exercise 4.4.1
Both carbon monoxide, CO, and carbon dioxide, CO2, are products of the combustion of fossil fuels. Both of these gases also
cause problems: CO is toxic and CO2 has been implicated in global climate change. What are the Lewis structures of these two
molecules?
Answer
 Fullerene Chemistry
Carbon soot has been known to man since prehistoric times, but it was not until fairly recently that the molecular structure of
the main component of soot was discovered. In 1996, the Nobel Prize in Chemistry was awarded to Richard Smalley, Robert
Curl, and Harold Kroto for their work in discovering a new form of carbon, the C60 buckminsterfullerene molecule. An entire
class of compounds, including spheres and tubes of various shapes, were discovered based on C60. This type of molecule,
called a fullerene, consists of a complex network of single- and double-bonded carbon atoms arranged in such a way that each
carbon atom obtains a full octet of electrons. Because of their size and shape, fullerenes can encapsulate other molecules, so
they have shown potential in various applications from hydrogen storage to targeted drug delivery systems. They also possess
unique electronic and optical properties that have been put to good use in solar powered devices and chemical sensors.
Exceptions to the Octet Rule

Many covalent molecules have central atoms that do not have eight electrons in their Lewis structures. These molecules fall into
three categories:
Odd-electron molecules have an odd number of valence electrons, and therefore have an unpaired electron.
Electron-deficient molecules have a central atom that has fewer electrons than needed for a noble gas configuration.
Hypervalent molecules have a central atom that has more electrons than needed for a noble gas configuration.

Odd-electron Molecules
We call molecules that contain an odd number of electrons free radicals. Nitric oxide, NO, is an example of an odd-electron
molecule; it is produced in internal combustion engines when oxygen and nitrogen react at high temperatures.
To draw the Lewis structure for an odd-electron molecule like NO, we follow the same five steps we would for other molecules,
but with a few minor changes:
1. Determine the total number of valence (outer shell) electrons. The sum of the valence electrons is 5 (from N) + 6 (from O) = 11.
The odd number immediately tells us that we have a free radical, so we know that not every atom can have eight electrons in its
valence shell.
2. Draw a skeleton structure of the molecule. We can easily draw a skeleton with an N–O single bond: N–O
3. Distribute the remaining electrons as lone pairs on the terminal atoms. In this case, there is no central atom, so we distribute the
electrons around both atoms. We give eight electrons to the more electronegative atom in these situations; thus oxygen has the
filled valence shell:
4. Place all remaining electrons on the central atom. Since there are no remaining electrons, this step does not apply.
5. Rearrange the electrons to make multiple bonds with the central atom in order to obtain octets wherever possible. We know that
an odd-electron molecule cannot have an octet for every atom, but we want to get each atom as close to an octet as possible. In
this case, nitrogen has only five electrons around it. To move closer to an octet for nitrogen, we take one of the lone pairs from
oxygen and use it to form a NO double bond. (We cannot take another lone pair of electrons on oxygen and form a triple bond
because nitrogen would then have nine electrons:)
Electron-deficient Molecules
We will also encounter a few molecules that contain central atoms that do not have a filled valence shell. Generally, these are
molecules with central atoms from groups 2 and 13 and outer atoms that are hydrogen or other atoms that do not form multiple
bonds. For example, in the Lewis structures of beryllium dihydride, BeH2, and boron trifluoride, BF3, the beryllium and boron
atoms each have only four and six electrons, respectively. It is possible to draw a structure with a double bond between a boron
atom and a fluorine atom in BF3, satisfying the octet rule, but experimental evidence indicates the bond lengths are closer to that
expected for B–F single bonds. This suggests the best Lewis structure has three B–F single bonds and an electron deficient boron.
The reactivity of the compound is also consistent with an electron deficient boron. However, the B–F bonds are slightly shorter
than what is actually expected for B–F single bonds, indicating that some double bond character is found in the actual molecule.
An atom like the boron atom in BF3, which does not have eight electrons, is very reactive. It readily combines with a molecule
containing an atom with a lone pair of electrons. For example, NH3 reacts with BF3 because the lone pair on nitrogen can be shared
with the boron atom:
Hypervalent Molecules
Elements in the second period of the periodic table (n = 2) can accommodate only eight electrons in their valence shell orbitals
because they have only four valence orbitals (one 2s and three 2p orbitals). Elements in the third and higher periods (n ≥ 3) have
more than four valence orbitals and can share more than four pairs of electrons with other atoms because they have empty d orbitals

in the same shell. Molecules formed from these elements are sometimes called hypervalent molecules.Table 4.4.5 shows the Lewis
structures for two hypervalent molecules, PCl5 and SF6.
Table 4.4.5: In PCl5, the central atom phosphorus shares five pairs of electrons. In SF6, sulfur shares six pairs of electrons.
In some hypervalent molecules, such as IF5 and XeF4, some of the electrons in the outer shell of the central atom are lone pairs:
When we write the Lewis structures for these molecules, we find that we have electrons left over after filling the valence shells of
the outer atoms with eight electrons. These additional electrons must be assigned to the central atom.
 Example 4.4.2: Octet Rule Violations
Xenon is a noble gas, but it forms a number of stable compounds. We examined XeF earlier. What are the Lewis structures of
4
XeF and XeF ?

2 6
Solution
We can draw the Lewis structure of any covalent molecule by following the six steps discussed earlier. In this case, we can
condense the last few steps, since not all of them apply.
Step 1: Calculate the number of valence electrons:
XeF
2
: 8 + (2 × 7) = 22
XeF
6
: 8 + (6 × 7) = 50
Step 2: Draw a skeleton joining the atoms by single bonds. Xenon will be the central atom because fluorine cannot be a
central atom:
Step 3: Distribute the remaining electrons.

XeF2: We place three lone pairs of electrons around each F atom, accounting for 12 electrons and giving each F atom 8 electrons.
Thus, six electrons (three lone pairs) remain. These lone pairs must be placed on the Xe atom. This is acceptable because Xe atoms
have empty valence shell d orbitals and can accommodate more than eight electrons. The Lewis structure of XeF2 shows two
bonding pairs and three lone pairs of electrons around the Xe atom:
XeF6: We place three lone pairs of electrons around each F atom, accounting for 36 electrons. Two electrons remain, and this lone
pair is placed on the Xe atom:

 Exercise 4.4.2: interhalogens
The halogens form a class of compounds called the interhalogens, in which halogen atoms covalently bond to each other. Write
the Lewis structures for the interhalogens BrCl and ICl .
3
−
4
Answer
Summary
Valence electronic structures can be visualized by drawing Lewis symbols (for atoms and monatomic ions) and Lewis structures
(for molecules and polyatomic ions). Lone pairs, unpaired electrons, and single, double, or triple bonds are used to indicate where
the valence electrons are located around each atom in a Lewis structure. Most structures—especially those containing second row
elements—obey the octet rule, in which every atom (except H) is surrounded by eight electrons. Exceptions to the octet rule occur
for odd-electron molecules (free radicals), electron-deficient molecules, and hypervalent molecules.
Glossary
double bond
covalent bond in which two pairs of electrons are shared between two atoms
free radical
molecule that contains an odd number of electrons
hypervalent molecule
molecule containing at least one main group element that has more than eight electrons in its valence shell
Lewis structure
diagram showing lone pairs and bonding pairs of electrons in a molecule or an ion
Lewis symbol
symbol for an element or monatomic ion that uses a dot to represent each valence electron in the element or ion
lone pair
two (a pair of) valence electrons that are not used to form a covalent bond
octet rule
guideline that states main group atoms will form structures in which eight valence electrons interact with each nucleus, counting
bonding electrons as interacting with both atoms connected by the bond
single bond
bond in which a single pair of electrons is shared between two atoms

triple bond
bond in which three pairs of electrons are shared between two atoms
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Compute formal charges for atoms in any Lewis structure
Use formal charges to identify the most reasonable Lewis structure for a given molecule
Explain the concept of resonance and draw Lewis structures representing resonance forms for a given molecule
Previously, we discussed how to write Lewis structures for molecules and polyatomic ions. In some cases, however, there is
seemingly more than one valid structure for a molecule. We can use the concept of formal charges to help us predict the most
appropriate Lewis structure when more than one is reasonable.
Calculating Formal Charge

The formal charge of an atom in a molecule is the hypothetical charge the atom would have if we could redistribute the electrons in
the bonds evenly between the atoms. Another way of saying this is that formal charge results when we take the number of valence
electrons of a neutral atom, subtract the nonbonding electrons, and then subtract the number of bonds connected to that atom in the
Lewis structure.
Thus, we calculate formal charge as follows:
1
formal charge = # valence shell electrons (free atom) − # lone pair electrons − # bonding electrons
2
We can double-check formal charge calculations by determining the sum of the formal charges for the whole structure. The sum of
the formal charges of all atoms in a molecule must be zero; the sum of the formal charges in an ion should equal the charge of the
ion.
We must remember that the formal charge calculated for an atom is not the actual charge of the atom in the molecule. Formal
charge is only a useful bookkeeping procedure; it does not indicate the presence of actual charges.
 Example 4.5.1: Calculating Formal Charge from Lewis Structures

Assign formal charges to each atom in the interhalogen ion ICl . −
Solution
We divide the bonding electron pairs equally for all I– Cl bonds:
We assign lone pairs of electrons to their atoms. Each Cl atom now has seven electrons assigned to it, and the I atom has eight.
Subtract this number from the number of valence electrons for the neutral atom:
I: 7 – 8 = –1
Cl: 7 – 7 = 0
The sum of the formal charges of all the atoms equals –1, which is identical to the charge of the ion (–1).

 Exercise 4.5.1
Calculate the formal charge for each atom in the carbon monoxide molecule:
Answer
C −1, O +1
 Example 4.5.2: Calculating Formal Charge from Lewis Structures
Assign formal charges to each atom in the interhalogen molecule BrCl . 3
Solution
Assign one of the electrons in each Br–Cl bond to the Br atom and one to the Cl atom in that bond:
Assign the lone pairs to their atom. Now each Cl atom has seven electrons and the Br atom has seven electrons.
Subtract this number from the number of valence electrons for the neutral atom. This gives the formal charge:
Br: 7 – 7 = 0
Cl: 7 – 7 = 0
All atoms in BrCl
3
have a formal charge of zero, and the sum of the formal charges totals zero, as it must in a neutral
molecule.
 Exercise 4.5.2
Determine the formal charge for each atom in NCl . 3
Answer
N: 0; all three Cl atoms: 0
Using Formal Charge to Predict Molecular Structure

The arrangement of atoms in a molecule or ion is called its molecular structure. In many cases, following the steps for writing
Lewis structures may lead to more than one possible molecular structure—different multiple bond and lone-pair electron
placements or different arrangements of atoms, for instance. A few guidelines involving formal charge can be helpful in deciding
which of the possible structures is most likely for a particular molecule or ion.

 Predicting Molecular Structure Guidelines
1. A molecular structure in which all formal charges are zero is preferable to one in which some formal charges are not zero.
2. If the Lewis structure must have nonzero formal charges, the arrangement with the smallest nonzero formal charges is
preferable.
3. Lewis structures are preferable when adjacent formal charges are zero or of the opposite sign.
4. When we must choose among several Lewis structures with similar distributions of formal charges, the structure with the
negative formal charges on the more electronegative atoms is preferable.
To see how these guidelines apply, let us consider some possible structures for carbon dioxide, CO . We know from our previous
2
discussion that the less electronegative atom typically occupies the central position, but formal charges allow us to understand why
this occurs. We can draw three possibilities for the structure: carbon in the center and double bonds, carbon in the center with a
single and triple bond, and oxygen in the center with double bonds:
Three Lewis structures are shown. The left and right structures show a carbon atom double bonded to two oxygen atoms, each of
which has two lone pairs of electrons. The center structure shows a carbon atom that is triple bonded to an oxygen atom with one
lone pair of electrons and single bonded to an oxygen atom with three lone pairs of electrons. The third structure shows an oxygen
atom double bonded to another oxygen atom with to lone pairs of electrons. The first oxygen atom is also double bonded to a
carbon atom with two lone pairs of electrons.
Comparing the three formal charges, we can definitively identify the structure on the left as preferable because it has only formal
charges of zero (Guideline 1).
As another example, the thiocyanate ion, an ion formed from a carbon atom, a nitrogen atom, and a sulfur atom, could have three
different molecular structures: CNS , NCS , or CSN . The formal charges present in each of these molecular structures can help
– – –
us pick the most likely arrangement of atoms. Possible Lewis structures and the formal charges for each of the three possible
structures for the thiocyanate ion are shown here:
Two rows of structures and numbers are shown. The top row is labeled, “Structure” and depicts three Lewis structures and the
bottom row is labeled, “Formal charge.” The left structure shows a carbon atom double bonded to a nitrogen atom with two lone
electron pairs on one side and double bonded to a sulfur atom with two lone electron pairs on the other. The structure is surrounded
by brackets and has a superscripted negative sign. Below this structure are the numbers negative one, zero, and zero. The middle
structure shows a carbon atom with two lone pairs of electrons double bonded to a nitrogen atom that is double bonded to a sulfur
atom with two lone electron pairs. The structure is surrounded by brackets and has a superscripted negative sign. Below this
structure are the numbers negative two, positive one, and zero. The right structure shows a carbon atom with two lone electron
pairs double bonded to a sulfur atom that is double bonded to a nitrogen atom with two lone electron pairs. The structure is
surrounded by brackets and has a superscripted negative sign. Below this structure are the numbers negative two, positive two, and
one.
Note that the sum of the formal charges in each case is equal to the charge of the ion (–1). However, the first arrangement of atoms
is preferred because it has the lowest number of atoms with nonzero formal charges (Guideline 2). Also, it places the least
electronegative atom in the center, and the negative charge on the more electronegative element (Guideline 4).
 Example 4.5.3: Using Formal Charge to Determine Molecular Structure
Nitrous oxide, N2O, commonly known as laughing gas, is used as an anesthetic in minor surgeries, such as the routine
extraction of wisdom teeth. Which is the likely structure for nitrous oxide?

Solution Determining formal charge yields the following:
The structure with a terminal oxygen atom best satisfies the criteria for the most stable distribution of formal charge:
The number of atoms with formal charges are minimized (Guideline 2), and there is no formal charge larger than one
(Guideline 2). This is again consistent with the preference for having the less electronegative atom in the central position.
 Exercise 4.5.3
Which is the most likely molecular structure for the nitrite (NO ) ion?
−
Answer
–
ONO
Resonance
You may have noticed that the nitrite anion in Example 4.5.3 can have two possible structures with the atoms in the same positions.
The electrons involved in the N–O double bond, however, are in different positions:
Two Lewis structures are shown. The left structure shows an oxygen atom with three lone pairs of electrons single bonded to a
nitrogen atom with one lone pair of electrons that is double bonded to an oxygen with two lone pairs of electrons. Brackets
surround this structure, and there is a superscripted negative sign. The right structure shows an oxygen atom with two lone pairs of
electrons double bonded to a nitrogen atom with one lone pair of electrons that is single bonded to an oxygen atom with three lone
pairs of electrons. Brackets surround this structure, and there is a superscripted negative sign.
If nitrite ions do indeed contain a single and a double bond, we would expect for the two bond lengths to be different. A double
bond between two atoms is shorter (and stronger) than a single bond between the same two atoms. Experiments show, however,
that both N–O bonds in NO have the same strength and length, and are identical in all other properties.
−
2
It is not possible to write a single Lewis structure for NO in which nitrogen has an octet and both bonds are equivalent. Instead,
−
we use the concept of resonance: if two or more Lewis structures with the same arrangement of atoms can be written for a molecule
or ion, the actual distribution of electrons is an average of that shown by the various Lewis structures. The actual distribution of
electrons in each of the nitrogen-oxygen bonds in NO is the average of a double bond and a single bond. We call the individual
−
Lewis structures resonance forms. The actual electronic structure of the molecule (the average of the resonance forms) is called a
resonance hybrid of the individual resonance forms. A double-headed arrow between Lewis structures indicates that they are
resonance forms. Thus, the electronic structure of the NO ion is shown as:
−

Two Lewis structures are shown with a double headed arrow drawn between them. The left structure shows an oxygen atom with
two lone pairs of electrons double bonded to a nitrogen atom with one lone pair of electrons that is single bonded to an oxygen
atom with three lone pairs of electrons. Brackets surround this structure, and there is a superscripted negative sign. The right
structure shows an oxygen atom with three lone pairs of electrons single bonded to a nitrogen atom with one lone pair of electrons
that is double bonded to an oxygen atom with two lone pairs of electrons. Brackets surround this structure, and there is a
superscripted negative sign.
We should remember that a molecule described as a resonance hybrid never possesses an electronic structure described by either
resonance form. It does not fluctuate between resonance forms; rather, the actual electronic structure is always the average of that
shown by all resonance forms. George Wheland, one of the pioneers of resonance theory, used a historical analogy to describe the
relationship between resonance forms and resonance hybrids. A medieval traveler, having never before seen a rhinoceros, described
it as a hybrid of a dragon and a unicorn because it had many properties in common with both. Just as a rhinoceros is neither a
dragon sometimes nor a unicorn at other times, a resonance hybrid is neither of its resonance forms at any given time. Like a
rhinoceros, it is a real entity that experimental evidence has shown to exist. It has some characteristics in common with its
resonance forms, but the resonance forms themselves are convenient, imaginary images (like the unicorn and the dragon).
The carbonate anion, CO , provides a second example of resonance:
2−
3
Three Lewis structures are shown with double headed arrows in between. Each structure is surrounded by brackets, and each has a
superscripted two negative sign. The left structure depicts a carbon atom bonded to three oxygen atoms. It is single bonded to two
of these oxygen atoms, each of which has three lone pairs of electrons, and double bonded to the third, which has two lone pairs of
electrons. The double bond is located between the lower left oxygen atom and the carbon atom. The central and right structures are
the same as the first, but the position of the double bonded oxygen has moved to the lower right oxygen in the central structure and
to the top oxygen in the right structure.
One oxygen atom must have a double bond to carbon to complete the octet on the central atom. All oxygen atoms, however, are
equivalent, and the double bond could form from any one of the three atoms. This gives rise to three resonance forms of the
carbonate ion. Because we can write three identical resonance structures, we know that the actual arrangement of electrons in the
carbonate ion is the average of the three structures. Again, experiments show that all three C–O bonds are exactly the same.
Summary
In a Lewis structure, formal charges can be assigned to each atom by treating each bond as if one-half of the electrons are assigned
to each atom. These hypothetical formal charges are a guide to determining the most appropriate Lewis structure. A structure in
which the formal charges are as close to zero as possible is preferred. Resonance occurs in cases where two or more Lewis
structures with identical arrangements of atoms but different distributions of electrons can be written. The actual distribution of
electrons (the resonance hybrid) is an average of the distribution indicated by the individual Lewis structures (the resonance forms).
Key Equations
1
formal charge = # valence shell electrons (free atom) − # one pair electrons − # bonding electrons
2
Glossary
formal charge
charge that would result on an atom by taking the number of valence electrons on the neutral atom and subtracting the
nonbonding electrons and the number of bonds (one-half of the bonding electrons)

molecular structure
arrangement of atoms in a molecule or ion
resonance
situation in which one Lewis structure is insufficient to describe the bonding in a molecule and the average of multiple
structures is observed
resonance forms
two or more Lewis structures that have the same arrangement of atoms but different arrangements of electrons
resonance hybrid
average of the resonance forms shown by the individual Lewis structures
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Describe the energetics of covalent and ionic bond formation and breakage
Use the Born-Haber cycle to compute lattice energies for ionic compounds
Use average covalent bond energies to estimate enthalpies of reaction
A bond’s strength describes how strongly each atom is joined to another atom, and therefore how much energy is required to break
the bond between the two atoms. In this section, you will learn about the bond strength of covalent bonds, and then compare that to
the strength of ionic bonds, which is related to the lattice energy of a compound.
Bond Strength: Covalent Bonds

Stable molecules exist because covalent bonds hold the atoms together. We measure the strength of a covalent bond by the energy
required to break it, that is, the energy necessary to separate the bonded atoms. Separating any pair of bonded atoms requires
energy; the stronger a bond, the greater the energy required to break it. The energy required to break a specific covalent bond in
one mole of gaseous molecules is called the bond energy or the bond dissociation energy. The bond energy for a diatomic molecule,
D X–Y , is defined as the standard enthalpy change for the endothermic reaction:
X Y(g) ⟶ X(g) + Y(g) DX−Y = ΔH ° (4.6.1)
For example, the bond energy of the pure covalent H–H bond, Δ H –H , is 436 kJ per mole of H–H bonds broken:
H2(g) ⟶ 2 H(g) DH −H = ΔH ° = 436kJ (4.6.2)
Breaking a bond always require energy to be added to the molecule. Correspondingly,

making a bond always releases energy.
Molecules with three or more atoms have two or more bonds. The sum of all bond energies in such a molecule is equal to the
standard enthalpy change for the endothermic reaction that breaks all the bonds in the molecule. For example, the sum of the four
C–H bond energies in CH4, 1660 kJ, is equal to the standard enthalpy change of the reaction:
A reaction is shown with Lewis structures. The first structure shows a carbon atom single bonded to four hydrogen atoms with the
symbol, “( g )” written next to it. A right-facing arrow points to the letter “C” and the symbol “( g ),” which is followed by a plus
sign. Next is the number 4, the letter “H” and the symbol, “( g ).” To the right of this equation is another equation: capital delta H
superscript degree symbol equals 1660 k J.
The average C–H bond energy, D , is 1660/4 = 415 kJ/mol because there are four moles of C–H bonds broken per mole of the
C –H
reaction. Although the four C–H bonds are equivalent in the original molecule, they do not each require the same energy to break;
once the first bond is broken (which requires 439 kJ/mol), the remaining bonds are easier to break. The 415 kJ/mol value is the
average, not the exact value required to break any one bond.
The strength of a bond between two atoms increases as the number of electron pairs in the bond increases. Generally, as the bond
strength increases, the bond length decreases. Thus, we find that triple bonds are stronger and shorter than double bonds between
the same two atoms; likewise, double bonds are stronger and shorter than single bonds between the same two atoms. Average bond
energies for some common bonds appear in Table 4.6.2, and a comparison of bond lengths and bond strengths for some common
bonds appears in Table 4.6.2. When one atom bonds to various atoms in a group, the bond strength typically decreases as we move
down the group. For example, C–F is 439 kJ/mol, C–Cl is 330 kJ/mol, and C–Br is 275 kJ/mol.
Table 4.6.1 : Bond Energies (kJ/mol)
Bond Bond Energy Bond Bond Energy Bond Bond Energy
H–H 436 C–S 260 F–Cl 255

Bond Bond Energy Bond Bond Energy Bond Bond Energy
H–C 415 C–Cl 330 F–Br 235
H–N 390 C–Br 275 Si–Si 230
H–O 464 C–I 240 Si–P 215
H–F 569 N–N 160 Si–S 225
H–Si 395 N = N 418 Si–Cl 359
H–P 320 N ≡ N 946 Si–Br 290
H–S 340 N–O 200 Si–I 215
H–Cl 432 N–F 270 P–P 215
H–Br 370 N–P 210 P–S 230
H–I 295 N–Cl 200 P–Cl 330
C–C 345 N–Br 245 P–Br 270
C = C 611 O–O 140 P–I 215
C ≡ C 837 O = O 498 S–S 215
C–N 290 O–F 160 S–Cl 250
C = N 615 O–Si 370 S–Br 215
C ≡ N 891 O–P 350 Cl–Cl 243
C–O 350 O–Cl 205 Cl–Br 220
C = O 741 O–I 200 Cl–I 210
C ≡ O 1080 F–F 160 Br–Br 190
C–F 439 F–Si 540 Br–I 180
C–Si 360 F–P 489 I–I 150
C–P 265 F–S 285
Table 4.6.2 : Average Bond Lengths and Bond Energies for Some Common Bonds
Bond Bond Length (Å) Bond Energy (kJ/mol)
C–C 1.54 345
C = C 1.34 611
C ≡ C 1.20 837
C–N 1.43 290
C = N 1.38 615
C ≡ N 1.16 891
C–O 1.43 350
C = O 1.23 741
C ≡ O 1.13 1080
We can use bond energies to calculate approximate enthalpy changes for reactions where enthalpies of formation are not available.
Calculations of this type will also tell us whether a reaction is exothermic or endothermic.

An exothermic reaction (ΔH negative, heat produced) results when the bonds in the products are stronger than the bonds
in the reactants.
An endothermic reaction (ΔH positive, heat absorbed) results when the bonds in the products are weaker than those in the
reactants.
The enthalpy change, ΔH, for a chemical reaction is approximately equal to the sum of the energy required to break all bonds in the
reactants (energy “in”, positive sign) plus the energy released when all bonds are formed in the products (energy “out,” negative
sign). This can be expressed mathematically in the following way:
ΔH = ∑ Dbonds broken − ∑ Dbonds formed (4.6.3)
In this expression, the symbol Σ means “the sum of” and D represents the bond energy in kilojoules per mole, which is always a
positive number. The bond energy is obtained from a table and will depend on whether the particular bond is a single, double, or
triple bond. Thus, in calculating enthalpies in this manner, it is important that we consider the bonding in all reactants and products.
Because D values are typically averages for one type of bond in many different molecules, this calculation provides a rough
estimate, not an exact value, for the enthalpy of reaction.
Consider the following reaction:
H + Cl ⟶ 2 HCl (4.6.4)
2 (g) 2 (g) (g)
or
H– H + Cl– Cl ⟶ 2 H– Cl (4.6.5)
(g) (g) (g)
To form two moles of HCl, one mole of H–H bonds and one mole of Cl–Cl bonds must be broken. The energy required to break
these bonds is the sum of the bond energy of the H–H bond (436 kJ/mol) and the Cl–Cl bond (243 kJ/mol). During the reaction,
two moles of H–Cl bonds are formed (bond energy = 432 kJ/mol), releasing 2 × 432 kJ; or 864 kJ. Because the bonds in the
products are stronger than those in the reactants, the reaction releases more energy than it consumes:
ΔH = ∑ Dbonds broken − ∑ Dbonds f ormed
= [ DH−H + DCl−Cl ] − 2 DH−Cl
= [436 + 243] − 2(432) = −185 kJ
This excess energy is released as heat, so the reaction is exothermic. Table T2 gives a value for the standard molar enthalpy of
formation of HCl(g), ΔH , of –92.307 kJ/mol. Twice that value is –184.6 kJ, which agrees well with the answer obtained earlier
∘
f
for the formation of two moles of HCl.
 Example 4.6.1: Using Bond Energies to Approximate Enthalpy Changes
Methanol, CH3OH, may be an excellent alternative fuel. The high-temperature reaction of steam and carbon produces a
mixture of the gases carbon monoxide, CO, and hydrogen, H2, from which methanol can be produced. Using the bond energies
in Table 4.6.2, calculate the approximate enthalpy change, ΔH, for the reaction here:
C O(g) + 2H 2(g) ⟶ C H3 OH(g)
Solution
First, we need to write the Lewis structures of the reactants and the products:

A set of Lewis diagrams show a chemical reaction. The first structure shows a carbon atom with a lone pair of electrons triple
bonded to an oxygen with a lone pair of electrons. To the right of this structure is a plus sign, then the number 2 followed by a
hydrogen atom single bonded to a hydrogen atom. To the right of this structure is a right-facing arrow followed by a hydrogen
atom single bonded to a carbon atom that is single bonded to two hydrogen atoms and an oxygen atom with two lone pairs of
electrons. The oxygen atom is also single bonded to a hydrogen atom.
From this, we see that ΔH for this reaction involves the energy required to break a C–O triple bond and two H–H single bonds,
as well as the energy produced by the formation of three C–H single bonds, a C–O single bond, and an O–H single bond. We
can express this as follows (via Equation 4.6.3):
ΔH = ∑ Dbonds broken − ∑ Dbonds f ormed
ΔH = [ DC≡O + 2(DH−H )] − [3(DC−H ) + DC−O + DO−H ]
Using the bond energy values in Table 4.6.2, we obtain:
ΔH = [1080 + 2(436)] − [3(415) + 350 + 464]
= −107 kJ
We can compare this value to the value calculated based on ΔH data from Appendix G:
∘
f
∘ ∘ ∘
ΔH = [ΔH CH OH(g)] − [ΔH CO(g) + 2 × ΔH H ]
f 3 f f 2
= [−201.0] − [−110.52 + 2 × 0]
= −90.5 kJ
Note that there is a fairly significant gap between the values calculated using the two different methods. This occurs because D
values are the average of different bond strengths; therefore, they often give only rough agreement with other data.
 Exercise 4.6.1
Ethyl alcohol, CH3CH2OH, was one of the first organic chemicals deliberately synthesized by humans. It has many uses in
industry, and it is the alcohol contained in alcoholic beverages. It can be obtained by the fermentation of sugar or synthesized
by the hydration of ethylene in the following reaction:
A set of Lewis structures show a chemical reaction. The first structure shows two carbon atoms that are double bonded
together and are each single bonded to two hydrogen atoms. This structure is followed by a plus sign, then an oxygen atom
with two lone pairs of electrons single bonded to two hydrogen atoms. A right-facing arrow leads to a carbon atom single
bonded to three hydrogen atoms and a second carbon atom. The second carbon atom is single bonded to two hydrogen atoms
and an oxygen atom with two lone pairs of electrons. The oxygen atom is single bonded to a hydrogen atom as well.
Using the bond energies in Table 4.6.2, calculate an approximate enthalpy change, ΔH, for this reaction.
Answer
–35 kJ
Ionic Bond Strength and Lattice Energy

An ionic compound is stable because of the electrostatic attraction between its positive and negative ions. The lattice energy of a
compound is a measure of the strength of this attraction. The lattice energy (ΔH ) of an ionic compound is defined as the
lattice
energy required to separate one mole of the solid into its component gaseous ions. For the ionic solid MX, the lattice energy is the
enthalpy change of the process:

+ n−
M X(s) ⟶ M n +X ΔHlattice (4.6.6)
(g) (g)
Note that we are using the convention where the ionic solid is separated into ions, so our lattice energies will be endothermic
(positive values). Some texts use the equivalent but opposite convention, defining lattice energy as the energy released when
separate ions combine to form a lattice and giving negative (exothermic) values. Thus, if you are looking up lattice energies in
another reference, be certain to check which definition is being used. In both cases, a larger magnitude for lattice energy indicates a
more stable ionic compound. For sodium chloride, ΔHlattice = 769 kJ. Thus, it requires 769 kJ to separate one mole of solid NaCl
into gaseous Na+ and Cl– ions. When one mole each of gaseous Na+ and Cl– ions form solid NaCl, 769 kJ of heat is released.
The lattice energy ΔH of an ionic crystal can be expressed by the following equation (derived from Coulomb’s law,
lattice
governing the forces between electric charges):

+ −
C (Z )(Z )
ΔHlattice = (4.6.7)
Ro
in which
C is a constant that depends on the type of crystal structure;
Z and Z are the charges on the ions; and
+ –
R is the interionic distance (the sum of the radii of the positive and negative ions).
o
Thus, the lattice energy of an ionic crystal increases rapidly as the charges of the ions increase and the sizes of the ions decrease.
When all other parameters are kept constant, doubling the charge of both the cation and anion quadruples the lattice energy. For
example, the lattice energy of LiF (Z+ and Z– = 1) is 1023 kJ/mol, whereas that of MgO (Z+ and Z– = 2) is 3900 kJ/mol (Ro is
nearly the same—about 200 pm for both compounds).
Different interatomic distances produce different lattice energies. For example, we can compare the lattice energy of MgF2 (2957
kJ/mol) to that of MgI2 (2327 kJ/mol) to observe the effect on lattice energy of the smaller ionic size of F– as compared to I–.
 Example 4.6.2: Lattice Energy Comparisons
The precious gem ruby is aluminum oxide, Al2O3, containing traces of Cr3+. The compound Al2Se3 is used in the fabrication of
some semiconductor devices. Which has the larger lattice energy, Al2O3 or Al2Se3?
Solution
In these two ionic compounds, the charges Z+ and Z– are the same, so the difference in lattice energy will mainly depend upon
Ro. The O2– ion is smaller than the Se2– ion. Thus, Al2O3 would have a shorter interionic distance than Al2Se3, and Al2O3
would have the larger lattice energy.
 Exercise 4.6.2
Zinc oxide, ZnO, is a very effective sunscreen. How would the lattice energy of ZnO compare to that of NaCl?
Answer
ZnO would have the larger lattice energy because the Z values of both the cation and the anion in ZnO are greater, and the
interionic distance of ZnO is smaller than that of NaCl.
The Born-Haber Cycle

It is not possible to measure lattice energies directly. However, the lattice energy can be calculated using the equation given in the
previous section or by using a thermochemical cycle. The Born-Haber cycle is an application of Hess’s law that breaks down the
formation of an ionic solid into a series of individual steps:
ΔH , the standard enthalpy of formation of the compound
∘
f
IE, the ionization energy of the metal

EA, the electron affinity of the nonmetal

ΔHs , the enthalpy of sublimation of the metal
∘
D, the bond dissociation energy of the nonmetal

ΔHlattice, the lattice energy of the compound
Figure 4.6.1 diagrams the Born-Haber cycle for the formation of solid cesium fluoride.
Figure 4.6.1 : The Born-Haber cycle shows the relative energies of each step involved in the formation of an ionic solid from the
necessary elements in their reference states.
A diagram is shown. An upward facing arrow is drawn to the far left of the chart and is labeled “H increasing.” A horizontal line is
drawn at the bottom of the chart. A downward-facing, vertical arrow to the left side of this line is labeled, “Overall change.” Beside
this arrow is another label, “capital delta H subscript f, equals negative 553.5 k J per mol, ( Enthalpy of formation ).” Three
horizontal lines, one above the other, and all above the bottom line, are labeled, from bottom to top, as: “C s ( s ), plus sign, one
half F subscript 2, ( g ),” “C s ( g ), plus sign, one half F subscript 2, ( g ),” and “C s, superscript positive sign, ( g ), plus sign, one
half F subscript 2, ( g ).” Each of these lines is connected by an upward-facing vertical arrow. Each arrow is labeled, “capital delta
H subscript 1, equals 76.5 k J per mol, ( Enthalpy of sublimation ),” “capital delta H subscript 2, equals 375.7 k J per mol, (
ionization energy ),” and “capital delta H subscript 3 equals 79.4 k J / mol ( one half dissociation energy ).” Another horizontal line
is drawn in the center top portion of the diagram and is labeled “C s, superscript positive sign, ( g ), plus sign, F, ( g ).” There is one
more horizontal line drawn to the right of the overall diagram and located halfway down the image. An arrow connects the top line
to this line and is labeled, “capital delta H equals negative 328.2 k J / mol ( electron affinity ).” The line is labeled, “C s superscript
positive sign ( g ) plus F superscript negative sign ( g ).” The arrow connecting this line to the bottom line is labeled, “negative
capital delta H subscript lattice equals negative 756.9 k J / mol.” The arrow points to a label on the bottom line which reads, “C s F
( s ).”
We begin with the elements in their most common states, Cs(s) and F2(g). The ΔH represents the conversion of solid cesium into
∘
s
a gas, and then the ionization energy converts the gaseous cesium atoms into cations. In the next step, we account for the energy
required to break the F–F bond to produce fluorine atoms. Converting one mole of fluorine atoms into fluoride ions is an
exothermic process, so this step gives off energy (the electron affinity) and is shown as decreasing along the y-axis. We now have
one mole of Cs cations and one mole of F anions. These ions combine to produce solid cesium fluoride. The enthalpy change in
this step is the negative of the lattice energy, so it is also an exothermic quantity. The total energy involved in this conversion is
equal to the experimentally determined enthalpy of formation, ΔH , of the compound from its elements. In this case, the overall
f
∘
change is exothermic.
Hess’s law can also be used to show the relationship between the enthalpies of the individual steps and the enthalpy of formation.
Table 4.6.3 shows this for cesium fluoride, CsF.
Table 4.6.3 : Enthalpies of Select Transitions
Enthalpy of sublimation of Cs(s) Cs(s) ⟶ Cs(g)
∘
ΔH = ΔHs = 77 kJ/mol
1 1
One-half of the bond energy of F2 F (g) ⟶ F(g)
2
ΔH = D = 79 kJ/mol
2 2
Ionization energy of Cs(g) Cs(g) ⟶ Cs

+
(g) + e
−
ΔH = I E = 376 kJ/mol
Negative of the electron affinity of F F(g) + e

−
⟶ F
−
(g) ΔH = −EA = −328 kJ/mol
Negative of the lattice energy of CsF(s) Cs

+
(g) + F
−
(g) ⟶ CsF(s) ΔH = −ΔHlattic e = ?

1
∘ ∘
ΔH = ΔH = ΔHs + D + I E + (−EA) + (−ΔHlattic e )
f
Enthalpy of formation of CsF(s), add steps 1–5 1
2
Cs(s) + F (g) ⟶ CsF(s) = −554 kJ/mol

2
2
Thus, the lattice energy can be calculated from other values. For cesium chloride, using this data, the lattice energy is:
ΔHlattice = (411 + 109 + 122 + 496 + 368) kJ = 770 kJ
The Born-Haber cycle may also be used to calculate any one of the other quantities in the equation for lattice energy, provided that
the remainder is known. For example, if the relevant enthalpy of sublimation ΔH , ionization energy (IE), bond dissociation
∘
s
enthalpy (D), lattice energy ΔHlattice, and standard enthalpy of formation ΔH are known, the Born-Haber cycle can be used to
∘
f
determine the electron affinity of an atom.

Lattice energies calculated for ionic compounds are typically much larger than bond dissociation energies measured for covalent
bonds. Whereas lattice energies typically fall in the range of 600–4000 kJ/mol (some even higher), covalent bond dissociation
energies are typically between 150–400 kJ/mol for single bonds. Keep in mind, however, that these are not directly comparable
values. For ionic compounds, lattice energies are associated with many interactions, as cations and anions pack together in an
extended lattice. For covalent bonds, the bond dissociation energy is associated with the interaction of just two atoms.
Summary
The strength of a covalent bond is measured by its bond dissociation energy, that is, the amount of energy required to break that
particular bond in a mole of molecules. Multiple bonds are stronger than single bonds between the same atoms. The enthalpy of a
reaction can be estimated based on the energy input required to break bonds and the energy released when new bonds are formed.
For ionic bonds, the lattice energy is the energy required to separate one mole of a compound into its gas phase ions. Lattice energy
increases for ions with higher charges and shorter distances between ions. Lattice energies are often calculated using the Born-
Haber cycle, a thermochemical cycle including all of the energetic steps involved in converting elements into an ionic compound.
Key Equations
Bond energy for a diatomic molecule: XY(g) ⟶ X(g) + Y(g) D
X–Y
= ΔH °
Enthalpy change: ΔH = ƩDbonds broken – ƩDbonds formed

Lattice energy for a solid MX: MX(s) ⟶ M (g) + X (g) n+ n−
ΔHlattice
+ −
C(Z )(Z )
Lattice energy for an ionic crystal: ΔH lattice =
Ro
Footnotes
1. This question is taken from the Chemistry Advanced Placement Examination and is used with the permission of the Educational
Testing Service.
Glossary
bond energy
(also, bond dissociation energy) energy required to break a covalent bond in a gaseous substance
Born-Haber cycle
thermochemical cycle relating the various energetic steps involved in the formation of an ionic solid from the relevant elements
lattice energy (ΔHlattice)
energy required to separate one mole of an ionic solid into its component gaseous ions
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7.5: Strengths of Ionic and Covalent Bonds is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

Predict the structures of small molecules using valence shell electron pair repulsion (VSEPR) theory
Explain the concepts of polar covalent bonds and molecular polarity
Assess the polarity of a molecule based on its bonding and structure
Thus far, we have used two-dimensional Lewis structures to represent molecules. However, molecular structure is actually three-
dimensional, and it is important to be able to describe molecular bonds in terms of their distances, angles, and relative
arrangements in space (Figure 4.7.1). A bond angle is the angle between any two bonds that include a common atom, usually
measured in degrees. A bond distance (or bond length) is the distance between the nuclei of two bonded atoms along the straight
line joining the nuclei. Bond distances are measured in Ångstroms (1 Å = 10–10 m) or picometers (1 pm = 10–12 m, 100 pm = 1 Å).
Figure 4.7.1 : Bond distances (lengths) and angles are shown for the formaldehyde molecule, H2CO.
A pair of images are shown. The left image shows a carbon atom with three atoms bonded in a triangular arrangement around it.
There are two hydrogen atoms bonded on the left side of the carbon and the angle between them is labeled, “118 degrees” and,
“Bond angle.” The carbon is also double bonded to an oxygen atom. The double bond is shaded and there is a bracket which labels
the bond, “Bond length ( angstrom ), ( center to center ),” and, “1.21 angstrom.” The right image shows a ball-and-stick model of
the same elements. The hydrogen atoms are white, the carbon atom is black, and the oxygen atom is red."
VSEPR Theory
Valence shell electron-pair repulsion theory (VSEPR theory) enables us to predict the molecular structure, including approximate
bond angles around a central atom, of a molecule from an examination of the number of bonds and lone electron pairs in its Lewis
structure. The VSEPR model assumes that electron pairs in the valence shell of a central atom will adopt an arrangement that
minimizes repulsions between these electron pairs by maximizing the distance between them. The electrons in the valence shell of
a central atom form either bonding pairs of electrons, located primarily between bonded atoms, or lone pairs. The electrostatic
repulsion of these electrons is reduced when the various regions of high electron density assume positions as far from each other as
possible.
VSEPR theory predicts the arrangement of electron pairs around each central atom and, usually, the correct arrangement of atoms
in a molecule. We should understand, however, that the theory only considers electron-pair repulsions. Other interactions, such as
nuclear-nuclear repulsions and nuclear-electron attractions, are also involved in the final arrangement that atoms adopt in a
particular molecular structure.
As a simple example of VSEPR theory, let us predict the structure of a gaseous BeF2 molecule. The Lewis structure of BeF2
(Figure 4.7.2) shows only two electron pairs around the central beryllium atom. With two bonds and no lone pairs of electrons on
the central atom, the bonds are as far apart as possible, and the electrostatic repulsion between these regions of high electron
density is reduced to a minimum when they are on opposite sides of the central atom. The bond angle is 180° (Figure 4.7.2).

Figure 4.7.2 : The BeF2 molecule adopts a linear structure in which the two bonds are as far apart as possible, on opposite sides of
the Be atom.
A Lewis structure is shown. A fluorine atom with three lone pairs of electrons is single bonded to a beryllium atom which is single
bonded to a fluorine atom with three lone pairs of electrons. The angle of the bonds between the two fluorine atoms and the
beryllium atom is labeled, “180 degrees.”
Figure 4.7.3 illustrates this and other electron-pair geometries that minimize the repulsions among regions of high electron density
(bonds and/or lone pairs). Two regions of electron density around a central atom in a molecule form a linear geometry; three
regions form a trigonal planar geometry; four regions form a tetrahedral geometry; five regions form a trigonal bipyramidal
geometry; and six regions form an octahedral geometry.

Figure 4.7.3 : The basic electron-pair geometries predicted by VSEPR theory maximize the space around any region of electron
density (bonds or lone pairs).
A table with four rows and six columns is shown. The header column contains the phrases, “Number of regions,” “Spatial
arrangement,” “Wedge/dash Notation,” and “Electron pair Geometry.” The first row reads: “Two regions of high electron density (
bonds and/or unshared pairs )”, “Three regions of high electron density ( bonds and/or unshared pairs ),” “Four regions of high
electron density ( bonds and/or unshared pairs ),” “Five regions of high electron density ( bonds and/or unshared pairs ),” and “Six
regions of high electron density ( bonds and/or unshared pairs ).” The second row shows diagrams of orbitals. The first image
shows two oval-shaped orbs with an arrow indicating an angle of 180 degrees. The second image shows three oval-shaped orbs
with an arrow indicating an angle of 120 degrees. The third image shows four oval-shaped orbs with an arrow indicating an angle
of 109.5 degrees. The fourth image shows five oval-shaped orbs with an arrow indicating an angle of 90 and 120 degrees. The fifth
image shows six oval-shaped orbs with an arrow indicating an angle of 90 degrees. The third row contains Lewis structures. The
first structure shows a beryllium atom single bonded to two hydrogen atoms. The second structure shows a boron atom single
bonded to three hydrogen atoms. The third structure shows a carbon atom single bonded to four hydrogen atoms. The fourth
structure shows a phosphorus atom single bonded to five fluorine atoms. The fifth structure shows a sulfur atom single bonded to
six fluorine atoms. The fourth row contains the phrases “Linear; 180 degree angle,” Trigonal Planar; all angles 120 degrees,”
“Tetrahedral; all angles 109.5 degrees,” “Trigonal bipyramidal; angles of 90 degrees and 120 degrees. An attached atom may be
equatorial, ( in the plane of the triangle ), or axial, ( above the plane of the triangle ),” and “Octahedral; 90 degrees or 180 degrees.”
Electron-pair Geometry versus Molecular Structure

It is important to note that electron-pair geometry around a central atom is not the same thing as its molecular structure. The
electron-pair geometries shown in Figure 4.7.3 describe all regions where electrons are located, bonds as well as lone pairs.
Molecular structure describes the location of the atoms, not the electrons.
We differentiate between these two situations by naming the geometry that includes all electron pairs the electron-pair geometry.
The structure that includes only the placement of the atoms in the molecule is called the molecular structure. The electron-pair
geometries will be the same as the molecular structures when there are no lone electron pairs around the central atom, but they will
be different when there are lone pairs present on the central atom.

Figure 4.7.4 : The molecular structure of the methane molecule, CH4, is shown with a tetrahedral arrangement of the hydrogen
atoms. VSEPR structures like this one are often drawn using the wedge and dash notation, in which solid lines represent bonds in
the plane of the page, solid wedges represent bonds coming up out of the plane, and dashed lines represent bonds going down into
the plane.
A Lewis structure shows a carbon atom single bonded to four hydrogen atoms. This structure uses wedges and dashes to give it a
three dimensional appearance.
For example, the methane molecule, CH4, which is the major component of natural gas, has four bonding pairs of electrons around
the central carbon atom; the electron-pair geometry is tetrahedral, as is the molecular structure (Figure 4.7.4). On the other hand,
the ammonia molecule, NH3, also has four electron pairs associated with the nitrogen atom, and thus has a tetrahedral electron-pair
geometry. One of these regions, however, is a lone pair, which is not included in the molecular structure, and this lone pair
influences the shape of the molecule (Figure 4.7.5).
Figure 4.7.5 : (a) The electron-pair geometry for the ammonia molecule is tetrahedral with one lone pair and three single bonds. (b)
The trigonal pyramidal molecular structure is determined from the electron-pair geometry. (c) The actual bond angles deviate
slightly from the idealized angles because the lone pair takes up a larger region of space than do the single bonds, causing the HNH
angle to be slightly smaller than 109.5°.
Three images are shown and labeled, “a,” “b,” and “c.” Image a shows a nitrogen atom single bonded to three hydrogen atoms.
There are four oval-shaped orbs that surround each hydrogen and one facing away from the rest of the molecule. These orbs are
located in a tetrahedral arrangement. Image b shows a ball-and-stick model of the nitrogen single bonded to the three hydrogen
atoms. Image c is the same as image a, but there are four curved, double headed arrows that circle the molecule and are labeled,
“106.8 degrees.”
Small distortions from the ideal angles in Figure 4.7.5 can result from differences in repulsion between various regions of electron
density. VSEPR theory predicts these distortions by establishing an order of repulsions and an order of the amount of space
occupied by different kinds of electron pairs. The order of electron-pair repulsions from greatest to least repulsion is:
lone pair-lone pair > lone pair-bonding pair > bonding pair-bonding pair
This order of repulsions determines the amount of space occupied by different regions of electrons. A lone pair of electrons
occupies a larger region of space than the electrons in a triple bond; in turn, electrons in a triple bond occupy more space than those
in a double bond, and so on. The order of sizes from largest to smallest is:
lone pair > triple bond > double bond > single bond
Consider formaldehyde, H2CO, which is used as a preservative for biological and anatomical specimens. This molecule has regions
of high electron density that consist of two single bonds and one double bond. The basic geometry is trigonal planar with 120°
bond angles, but we see that the double bond causes slightly larger angles (121°), and the angle between the single bonds is slightly
smaller (118°).
In the ammonia molecule, the three hydrogen atoms attached to the central nitrogen are not arranged in a flat, trigonal planar
molecular structure, but rather in a three-dimensional trigonal pyramid (Figure 4.7.6) with the nitrogen atom at the apex and the
three hydrogen atoms forming the base. The ideal bond angles in a trigonal pyramid are based on the tetrahedral electron pair
geometry. Again, there are slight deviations from the ideal because lone pairs occupy larger regions of space than do bonding
electrons. The H–N–H bond angles in NH3 are slightly smaller than the 109.5° angle in a regular tetrahedron (Figure 4.7.6)
because the lone pair-bonding pair repulsion is greater than the bonding pair-bonding pair repulsion. The ideal molecular structures
are predicted based on the electron-pair geometries for various combinations of lone pairs and bonding pairs.

Figure 4.7.6 : The molecular structures are identical to the electron-pair geometries when there are no lone pairs present (first
column). For a particular number of electron pairs (row), the molecular structures for one or more lone pairs are determined based
on modifications of the corresponding electron-pair geometry.
A table is shown that is comprised of six rows and six columns. The header row reads: “Number of Electron Pairs,” “Electron pair
geometries; 0 lone pair,” “1 lone pair,” “2 lone pairs,” “3 lone pairs,” and “4 lone pairs.” The first column contains the numbers 2,
3, 4, 5, and 6. The first space in the second column contains a structure in which the letter E is single bonded to the letter X on each
side. The angle of the bonds is labeled with a curved, double headed arrow and the value, “180 degrees.” The structure is labeled,
“Linear.” The second space in the second column contains a structure in which the letter E is single bonded to the letter X on three
sides. The angle between the bonds is labeled with a curved, double headed arrow and the value, “120 degrees.” The structure is
labeled, “Trigonal planar.” The third space in the second column contains a structure in which the letter E is single bonded to the
letter X four times. The angle between the bonds is labeled with a curved, double headed arrow and the value, “109 degrees.” The
structure is labeled, “Tetrahedral.” The fourth space in the second column contains a structure in which the letter E is single bonded
to the letter X on five sides. The angle between the bonds is labeled with a curved, double headed arrow and the values “90 and 120
degrees.” The structure is labeled, “Trigonal bipyramid.” The fifth space in the second column contains a structure in which the
letter E is single bonded to the letter X on six sides. The angle between the bonds is labeled with a curved, double headed arrow
and the value, “90 degrees.” The structure is labeled, “Octahedral.” The first space in the third column is empty while the second
contains a structure in which the letter E is single bonded to the letter X on each side and has a lone pair of electrons. The angle
between the bonds is labeled with a curved, double headed arrow and the value, “less than 120 degrees.” The structure is labeled,
“Bent or angular.” The third space in the third column contains a structure in which the letter E is single bonded to the letter X three
times and to a lone pair of electrons. It is labeled with a curved, double headed arrow and the value, “less than 109 degrees.” The
structure is labeled, “Trigonal pyramid.” The fourth space in the third column contains a structure in which the letter E is single
bonded to the letter X on four sides and has a lone pair of electrons. The bond angle is labeled with a curved, double headed arrow
and the values, “less than 90 and less than 120 degrees.” The structure is labeled, “Sawhorse or seesaw.” The fifth space in the third
column contains a structure in which the letter E is single bonded to the letter X on five sides and has a lone pair of electrons. The
bond angle is labeled with a curved, double headed arrow and the value, “less than 90 degrees.” The structure is labeled, “Square
pyramidal.” The first and second spaces in the fourth column are empty while the third contains a structure in which the letter E is
single bonded to the letter X on each side and has two lone pairs of electrons. The bond angle is labeled with a curved, double
headed arrow and the value, “less than less than 109 degrees.” The structure is labeled, “Bent or angular.” The fourth space in the
fourth column contains a structure in which the letter E is single bonded to the letter X three times and to two lone pairs of
electrons. The bond angle is labeled with a curved, double headed arrow and the value, “less than 90 degrees.” The structure is
labeled, “T - shape.” The fifth space in the fourth column contains a structure in which the letter E is single bonded to the letter X
on four sides and has two lone pairs of electrons. The bond angle is labeled with a curved, double headed arrow and the value “90
degrees.” The structure is labeled, “Square planar.” The first, second and third spaces in the fifth column are empty while the fourth
contains a structure in which the letter E is single bonded to the letter X on each side and has three lone pairs of electrons. The

bond angle is labeled with a curved, double headed arrow and the value, “180 degrees.” The structure is labeled, “Linear.” The fifth
space in the fifth column contains a structure in which the letter E is single bonded to the letter X three times and to three lone pairs
of electrons. The bond angle is labeled with a curved, double headed arrow and the value, “less than 90 degrees.” The structure is
labeled, “T - shape.” The first, second, third, and fourth spaces in the sixth column are empty while the fifth contains a structure in
which the letter E is single bonded to the letter X on each side and has four lone pairs of electrons. The bond angle is labeled with a
curved, double headed arrow and the value “180 degrees.” The structure is labeled, “Linear.” All the structures use wedges and
dashes to give them three dimensional appearances.
According to VSEPR theory, the terminal atom locations (Xs in Figure 4.7.7) are equivalent within the linear, trigonal planar, and
tetrahedral electron-pair geometries (the first three rows of the table). It does not matter which X is replaced with a lone pair
because the molecules can be rotated to convert positions. For trigonal bipyramidal electron-pair geometries, however, there are
two distinct X positions (Figure 4.7.7a): an axial position (if we hold a model of a trigonal bipyramid by the two axial positions,
we have an axis around which we can rotate the model) and an equatorial position (three positions form an equator around the
middle of the molecule). The axial position is surrounded by bond angles of 90°, whereas the equatorial position has more space
available because of the 120° bond angles. In a trigonal bipyramidal electron-pair geometry, lone pairs always occupy equatorial
positions because these more spacious positions can more easily accommodate the larger lone pairs.
Theoretically, we can come up with three possible arrangements for the three bonds and two lone pairs for the ClF3 molecule
(Figure 4.7.7). The stable structure is the one that puts the lone pairs in equatorial locations, giving a T-shaped molecular structure.
Figure 4.7.7 : (a) In a trigonal bipyramid, the two axial positions are located directly across from one another, whereas the three
equatorial positions are located in a triangular arrangement. (b–d) The two lone pairs (red lines) in ClF3 have several possible
arrangements, but the T-shaped molecular structure (b) is the one actually observed, consistent with the larger lone pairs both
occupying equatorial positions.
Four sets of images are shown and labeled, “a,” “b,” “c,” and “d.” Each image is separated by a dashed vertical line. Image a shows
a six-faced, bi-pyramidal structure where the central vertical axis is labeled, “Axial,” and the horizontal plane is labeled,
“Equatorial.” Image b shows a pair of diagrams in the same shape as image a, but in these diagrams, the left has a chlorine atom in
the center while the right has a chlorine atom in the center, two fluorine atoms on the upper and lower ends, and one fluorine in the
left horizontal position. Image c shows a pair of diagrams in the same shape as image a, but in these diagrams, the left has a
chlorine atom in the center while the right has a chlorine atom in the center and three fluorine atoms in each horizontal position.
Image d shows a pair of diagrams in the same shape as image a, but in these diagrams, the left has a chlorine atom in the center
while the right has a chlorine atom in the center, two fluorine atoms in the horizontal positions, and one in the axial bottom
position.
When a central atom has two lone electron pairs and four bonding regions, we have an octahedral electron-pair geometry. The two
lone pairs are on opposite sides of the octahedron (180° apart), giving a square planar molecular structure that minimizes lone pair-
lone pair repulsions.
 Predicting Electron Pair Geometry and Molecular Structure

The following procedure uses VSEPR theory to determine the electron pair geometries and the molecular structures:
1. Write the Lewis structure of the molecule or polyatomic ion.
2. Count the number of regions of electron density (lone pairs and bonds) around the central atom. A single, double, or triple
bond counts as one region of electron density.
3. Identify the electron-pair geometry based on the number of regions of electron density: linear, trigonal planar, tetrahedral,
trigonal bipyramidal, or octahedral (Figure 4.7.7, first column).
4. Use the number of lone pairs to determine the molecular structure (Figure 4.7.7 ). If more than one arrangement of lone
pairs and chemical bonds is possible, choose the one that will minimize repulsions, remembering that lone pairs occupy
more space than multiple bonds, which occupy more space than single bonds. In trigonal bipyramidal arrangements,
repulsion is minimized when every lone pair is in an equatorial position. In an octahedral arrangement with two lone pairs,
repulsion is minimized when the lone pairs are on opposite sides of the central atom.

The following examples illustrate the use of VSEPR theory to predict the molecular structure of molecules or ions that have no
lone pairs of electrons. In this case, the molecular structure is identical to the electron pair geometry.
 Example 4.7.1: Predicting Electron-pair Geometry and Molecular Structure
Predict the electron-pair geometry and molecular structure for each of the following:
a. carbon dioxide, CO2, a molecule produced by the combustion of fossil fuels
b. boron trichloride, BCl3, an important industrial chemical
Solution
(a) We write the Lewis structure of CO2 as:
This shows us two regions of high electron density around the carbon atom—each double bond counts as one region, and there
are no lone pairs on the carbon atom. Using VSEPR theory, we predict that the two regions of electron density arrange
themselves on opposite sides of the central atom with a bond angle of 180°. The electron-pair geometry and molecular
structure are identical, and CO2 molecules are linear.
(b) We write the Lewis structure of BCl3 as:
Thus we see that BCl3 contains three bonds, and there are no lone pairs of electrons on boron. The arrangement of three
regions of high electron density gives a trigonal planar electron-pair geometry. The B–Cl bonds lie in a plane with 120° angles
between them. BCl3 also has a trigonal planar molecular structure.
The electron-pair geometry and molecular structure of BCl3 are both trigonal planar. Note that the VSEPR geometry indicates
the correct bond angles (120°), unlike the Lewis structure shown above.
 Exercise 4.7.1
Carbonate, CO , is a common polyatomic ion found in various materials from eggshells to antacids. What are the electron-
2−
pair geometry and molecular structure of this polyatomic ion?
Answer
The electron-pair geometry is trigonal planar and the molecular structure is trigonal planar. Due to resonance, all three C–O
bonds are identical. Whether they are single, double, or an average of the two, each bond counts as one region of electron
density.
 Example 4.7.2: Predicting Electron-pair Geometry and Molecular Structure
Two of the top 50 chemicals produced in the United States, ammonium nitrate and ammonium sulfate, both used as fertilizers,
contain the ammonium ion. Predict the electron-pair geometry and molecular structure of the NH cation.
+

Solution
We write the Lewis structure of NH as: +
4
Figure 4.7.7 ).
Figure 4.7.8 : The ammonium ion displays a tetrahedral electron-pair geometry as well as a tetrahedral molecular structure.
 Exercise 4.7.2
Identify a molecule with trigonal bipyramidal molecular structure.
Answer
Any molecule with five electron pairs around the central atoms including no lone pairs will be trigonal bipyramidal. PF is 5
a common example
The next several examples illustrate the effect of lone pairs of electrons on molecular structure.
 Example 4.7.3: Lone Pairs on the Central Atom
Predict the electron-pair geometry and molecular structure of a water molecule.
Solution
The Lewis structure of H2O indicates that there are four regions of high electron density around the oxygen atom: two lone
pairs and two chemical bonds:
Figure 4.7.9 . Thus, the electron-pair geometry is tetrahedral and the molecular structure is bent with an angle slightly less than
109.5°. In fact, the bond angle is 104.5°.

Figure 4.7.9 : (a) H2O has four regions of electron density around the central atom, so it has a tetrahedral electron-pair
geometry. (b) Two of the electron regions are lone pairs, so the molecular structure is bent.
 Exercise 4.7.3
The hydronium ion, H3O+, forms when acids are dissolved in water. Predict the electron-pair geometry and molecular structure
of this cation.
Answer
electron pair geometry: tetrahedral; molecular structure: trigonal pyramidal
 Example 4.7.4: SF4 Sulfur tetrafluoride,
Predicting Electron-pair Geometry and Molecular Structure: SF4, is extremely valuable for the preparation of fluorine-
containing compounds used as herbicides (i.e., SF4 is used as a fluorinating agent). Predict the electron-pair geometry and
molecular structure of a SF4 molecule.
Solution
The Lewis structure of SF4 indicates five regions of electron density around the sulfur atom: one lone pair and four bonding
pairs:
Figure 4.7.10 ).
Figure 4.7.10 : (a) SF4 has a trigonal bipyramidal arrangement of the five regions of electron density. (b) One of the regions is a
lone pair, which results in a seesaw-shaped molecular structure.

 Exercise 4.7.4
Predict the electron pair geometry and molecular structure for molecules of XeF2.
Answer
The electron-pair geometry is trigonal bipyramidal. The molecular structure is linear.
 Example 4.7.4: XeF4
Of all the noble gases, xenon is the most reactive, frequently reacting with elements such as oxygen and fluorine. Predict the
electron-pair geometry and molecular structure of the XeF4 molecule.
Solution
The Lewis structure of XeF4 indicates six regions of high electron density around the xenon atom: two lone pairs and four
bonds:
Figure 4.7.11 : The five atoms are all in the same plane and have a square planar molecular structure.
Figure 4.7.11 : (a) XeF4 adopts an octahedral arrangement with two lone pairs (red lines) and four bonds in the electron-pair
geometry. (b) The molecular structure is square planar with the lone pairs directly across from one another.
 Exercise 4.7.4
In a certain molecule, the central atom has three lone pairs and two bonds. What will the electron pair geometry and molecular
structure be?
Answer
electron pair geometry: trigonal bipyramidal; molecular structure: linear
Molecular Structure for Multicenter Molecules

When a molecule or polyatomic ion has only one central atom, the molecular structure completely describes the shape of the
molecule. Larger molecules do not have a single central atom, but are connected by a chain of interior atoms that each possess a
“local” geometry. The way these local structures are oriented with respect to each other also influences the molecular shape, but
such considerations are largely beyond the scope of this introductory discussion. For our purposes, we will only focus on
determining the local structures.

 Example 4.7.5: Predicting Structure in Multicenter Molecules
The Lewis structure for the simplest amino acid, glycine, H2NCH2CO2H, is shown here. Predict the local geometry for the
nitrogen atom, the two carbon atoms, and the oxygen atom with a hydrogen atom attached:
Solution
Consider each central atom independently. The electron-pair geometries:

nitrogen––four regions of electron density; tetrahedral
carbon (CH2)––four regions of electron density; tetrahedral
carbon (CO2)—three regions of electron density; trigonal planar
oxygen (OH)—four regions of electron density; tetrahedral
The local structures:
nitrogen––three bonds, one lone pair; trigonal pyramidal
carbon (CH2)—four bonds, no lone pairs; tetrahedral
carbon (CO2)—three bonds (double bond counts as one bond), no lone pairs; trigonal planar
oxygen (OH)—two bonds, two lone pairs; bent (109°)
 Exercise 4.7.5
Another amino acid is alanine, which has the Lewis structure shown here. Predict the electron-pair geometry and local
structure of the nitrogen atom, the three carbon atoms, and the oxygen atom with hydrogen attached:
Answer
electron-pair geometries: nitrogen––tetrahedral; carbon (CH)—tetrahedral; carbon (CH3)—tetrahedral; carbon (CO2)—
trigonal planar; oxygen (OH)—tetrahedral; local structures: nitrogen—trigonal pyramidal; carbon (CH)—tetrahedral;
carbon (CH3)—tetrahedral; carbon (CO2)—trigonal planar; oxygen (OH)—bent (109°)
 Example 4.7.6: Molecular Simulation

Using this molecular shape simulator allows us to control whether bond angles and/or lone pairs are displayed by checking or
unchecking the boxes under “Options” on the right. We can also use the “Name” checkboxes at bottom-left to display or hide
the electron pair geometry (called “electron geometry” in the simulator) and/or molecular structure (called “molecular shape”
in the simulator).
Build the molecule HCN in the simulator based on the following Lewis structure:

H– C ≡ N
Click on each bond type or lone pair at right to add that group to the central atom. Once you have the complete molecule, rotate it
to examine the predicted molecular structure. What molecular structure is this?
Solution
The molecular structure is linear.
 Exercise 4.7.6
Build a more complex molecule in the simulator. Identify the electron-group geometry, molecular structure, and bond angles.
Then try to find a chemical formula that would match the structure you have drawn.
Answer
Answers will vary. For example, an atom with four single bonds, a double bond, and a lone pair has an octahedral electron-
group geometry and a square pyramidal molecular structure. XeOF4 is a molecule that adopts this structure.
Molecular Polarity and Dipole Moment

As discussed previously, polar covalent bonds connect two atoms with differing electronegativities, leaving one atom with a partial
positive charge (δ+) and the other atom with a partial negative charge (δ–), as the electrons are pulled toward the more
electronegative atom. This separation of charge gives rise to a bond dipole moment. The magnitude of a bond dipole moment is
represented by the Greek letter mu (µ) and is given by
μ = Qr (4.7.1)
where
Q is the magnitude of the partial charges (determined by the electronegativity difference) and
r is the distance between the charges:
This bond moment can be represented as a vector, a quantity having both direction and magnitude (Figure 4.7.12). Dipole vectors
are shown as arrows pointing along the bond from the less electronegative atom toward the more electronegative atom. A small
plus sign is drawn on the less electronegative end to indicate the partially positive end of the bond. The length of the arrow is
proportional to the magnitude of the electronegativity difference between the two atoms.
Figure 4.7.12 : (a) There is a small difference in electronegativity between C and H, represented as a short vector. (b) The
electronegativity difference between B and F is much larger, so the vector representing the bond moment is much longer.
A whole molecule may also have a separation of charge, depending on its molecular structure and the polarity of each of its bonds.
If such a charge separation exists, the molecule is said to be a polar molecule (or dipole); otherwise the molecule is said to be
nonpolar. The dipole moment measures the extent of net charge separation in the molecule as a whole. We determine the dipole
moment by adding the bond moments in three-dimensional space, taking into account the molecular structure.
For diatomic molecules, there is only one bond, so its bond dipole moment determines the molecular polarity. Homonuclear
diatomic molecules such as Br2 and N2 have no difference in electronegativity, so their dipole moment is zero. For heteronuclear
molecules such as CO, there is a small dipole moment. For HF, there is a larger dipole moment because there is a larger difference
in electronegativity.
When a molecule contains more than one bond, the geometry must be taken into account. If the bonds in a molecule are arranged
such that their bond moments cancel (vector sum equals zero), then the molecule is nonpolar. This is the situation in CO2 (Figure
4.7.13A). Each of the bonds is polar, but the molecule as a whole is nonpolar. From the Lewis structure, and using VSEPR theory,
we determine that the CO2 molecule is linear with polar C=O bonds on opposite sides of the carbon atom. The bond moments
cancel because they are pointed in opposite directions. In the case of the water molecule (Figure 4.7.13B), the Lewis structure

again shows that there are two bonds to a central atom, and the electronegativity difference again shows that each of these bonds
has a nonzero bond moment. In this case, however, the molecular structure is bent because of the lone pairs on O, and the two bond
moments do not cancel. Therefore, water does have a net dipole moment and is a polar molecule (dipole).
Figure 4.7.13 : The overall dipole moment of a molecule depends on the individual bond dipole moments and how they are
arranged. (a) Each CO bond has a bond dipole moment, but they point in opposite directions so that the net CO2 molecule is
nonpolar. (b) In contrast, water is polar because the OH bond moments do not cancel out.
The OCS molecule has a structure similar to CO2, but a sulfur atom has replaced one of the oxygen atoms. To determine if this
molecule is polar, we draw the molecular structure. VSEPR theory predicts a linear molecule:
The C–O bond is considerably polar. Although C and S have very similar electronegativity values, S is slightly more
electronegative than C, and so the C-S bond is just slightly polar. Because oxygen is more electronegative than sulfur, the oxygen
end of the molecule is the negative end.
Chloromethane, CH3Cl, is another example of a polar molecule. Although the polar C–Cl and C–H bonds are arranged in a
tetrahedral geometry, the C–Cl bonds have a larger bond moment than the C–H bond, and the bond moments do not completely
cancel each other. All of the dipoles have a upward component in the orientation shown, since carbon is more electronegative than
hydrogen and less electronegative than chlorine:
When we examine the highly symmetrical molecules BF3 (trigonal planar), CH4 (tetrahedral), PF5 (trigonal bipyramidal), and SF6
(octahedral), in which all the polar bonds are identical, the molecules are nonpolar. The bonds in these molecules are arranged such
that their dipoles cancel. However, just because a molecule contains identical bonds does not mean that the dipoles will always
cancel. Many molecules that have identical bonds and lone pairs on the central atoms have bond dipoles that do not cancel.
Examples include H2S and NH3. A hydrogen atom is at the positive end and a nitrogen or sulfur atom is at the negative end of the
polar bonds in these molecules:
To summarize, to be polar, a molecule must:

1. Contain at least one polar covalent bond.
2. Have a molecular structure such that the sum of the vectors of each bond dipole moment does not cancel.
Properties of Polar Molecules

Polar molecules tend to align when placed in an electric field with the positive end of the molecule oriented toward the negative
plate and the negative end toward the positive plate (Figure 4.7.14). We can use an electrically charged object to attract polar

molecules, but nonpolar molecules are not attracted. Also, polar solvents are better at dissolving polar substances, and nonpolar
solvents are better at dissolving nonpolar substances.
Figure 4.7.14 : (a) Molecules are always randomly distributed in the liquid state in the absence of an electric field. (b) When an
electric field is applied, polar molecules like HF will align to the dipoles with the field direction.
 Example 4.7.7: Polarity Simulations
Open the molecule polarity simulation and select the “Three Atoms” tab at the top. This should display a molecule ABC with
three electronegativity adjustors. You can display or hide the bond moments, molecular dipoles, and partial charges at the right.
Turning on the Electric Field will show whether the molecule moves when exposed to a field, similar to Figure 4.7.14.
Use the electronegativity controls to determine how the molecular dipole will look for the starting bent molecule if:
a. A and C are very electronegative and B is in the middle of the range.
b. A is very electronegative, and B and C are not.
Solution
a. Molecular dipole moment points immediately between A and C.
b. Molecular dipole moment points along the A–B bond, toward A.
 Exercise 4.7.7
Determine the partial charges that will give the largest possible bond dipoles.
Answer
The largest bond moments will occur with the largest partial charges. The two solutions above represent how unevenly the
electrons are shared in the bond. The bond moments will be maximized when the electronegativity difference is greatest.
The controls for A and C should be set to one extreme, and B should be set to the opposite extreme. Although the
magnitude of the bond moment will not change based on whether B is the most electronegative or the least, the direction of
the bond moment will.

Summary
VSEPR theory predicts the three-dimensional arrangement of atoms in a molecule. It states that valence electrons will assume an
electron-pair geometry that minimizes repulsions between areas of high electron density (bonds and/or lone pairs). Molecular
structure, which refers only to the placement of atoms in a molecule and not the electrons, is equivalent to electron-pair geometry
only when there are no lone electron pairs around the central atom. A dipole moment measures a separation of charge. For one
bond, the bond dipole moment is determined by the difference in electronegativity between the two atoms. For a molecule, the
overall dipole moment is determined by both the individual bond moments and how these dipoles are arranged in the molecular
structure. Polar molecules (those with an appreciable dipole moment) interact with electric fields, whereas nonpolar molecules do
not.
Glossary
axial position
location in a trigonal bipyramidal geometry in which there is another atom at a 180° angle and the equatorial positions are at a
90° angle
bond angle
angle between any two covalent bonds that share a common atom
bond distance
(also, bond length) distance between the nuclei of two bonded atoms
bond dipole moment

separation of charge in a bond that depends on the difference in electronegativity and the bond distance represented by partial
charges or a vector
dipole moment
property of a molecule that describes the separation of charge determined by the sum of the individual bond moments based on
the molecular structure
electron-pair geometry
arrangement around a central atom of all regions of electron density (bonds, lone pairs, or unpaired electrons)
equatorial position
one of the three positions in a trigonal bipyramidal geometry with 120° angles between them; the axial positions are located at a
90° angle
linear
shape in which two outside groups are placed on opposite sides of a central atom
molecular structure
structure that includes only the placement of the atoms in the molecule
octahedral
shape in which six outside groups are placed around a central atom such that a three-dimensional shape is generated with four
groups forming a square and the other two forming the apex of two pyramids, one above and one below the square plane
polar molecule
(also, dipole) molecule with an overall dipole moment
tetrahedral
shape in which four outside groups are placed around a central atom such that a three-dimensional shape is generated with four
corners and 109.5° angles between each pair and the central atom
trigonal bipyramidal

shape in which five outside groups are placed around a central atom such that three form a flat triangle with 120° angles
between each pair and the central atom, and the other two form the apex of two pyramids, one above and one below the
triangular plane
trigonal planar
shape in which three outside groups are placed in a flat triangle around a central atom with 120° angles between each pair and
the central atom
valence shell electron-pair repulsion theory (VSEPR)

theory used to predict the bond angles in a molecule based on positioning regions of high electron density as far apart as
possible to minimize electrostatic repulsion
vector
quantity having magnitude and direction
This page titled 4.7: Molecular Structure and Polarity is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
7.6: Molecular Structure and Polarity is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

7.1: Ionic Bonding
Q7.1.1
Does a cation gain protons to form a positive charge or does it lose electrons?
S7.1.1
The protons in the nucleus do not change during normal chemical reactions. Only the outer electrons move. Positive charges form
when electrons are lost.
Q7.1.2
Iron(III) sulfate [Fe2(SO4)3] is composed of Fe3+ and SO 2−
4
ions. Explain why a sample of iron(III) sulfate is uncharged.
Q7.1.3
Which of the following atoms would be expected to form negative ions in binary ionic compounds and which would be expected to
form positive ions: P, I, Mg, Cl, In, Cs, O, Pb, Co?
S7.1.3
P, I, Cl, and O would form anions because they are nonmetals. Mg, In, Cs, Pb, and Co would form cations because they are metals.
Q7.1.4
Which of the following atoms would be expected to form negative ions in binary ionic compounds and which would be expected to
form positive ions: Br, Ca, Na, N, F, Al, Sn, S, Cd?
Q7.1.5
Predict the charge on the monatomic ions formed from the following atoms in binary ionic compounds:
a. P
b. Mg
c. Al
d. O
e. Cl
f. Cs
S7.1.5
P3–; Mg2+; Al3+; O2–; Cl–; Cs+
Q7.1.6
Predict the charge on the monatomic ions formed from the following atoms in binary ionic compounds:
1. I
2. Sr
3. K
4. N
5. S
6. In
S7.1.6
1. I-
2. Sr2+
3. K+
4. N3-
5. S2-

6. In3+
Q7.1.7
Write the electron configuration for each of the following ions:
1. As3–
2. I–
3. Be2+
4. Cd2+
5. O2–
6. Ga3+
7. Li+
8. (h) N3–
9. (i) Sn2+
10. (j) Co2+
11. (k) Fe2+
12. (l) As3+
S7.1.7
[Ar]4s23d104p6; [Kr]4d105s25p6 1s2 [Kr]4d10; [He]2s22p6; [Ar]3d10; 1s2 (h) [He]2s22p6 (i) [Kr]4d105s2 (j) [Ar]3d7 (k) [Ar]3d6, (l)
[Ar]3d104s2
Q7.1.8
Write the electron configuration for the monatomic ions formed from the following elements (which form the greatest
concentration of monatomic ions in seawater):
1. Cl
2. Na
3. Mg
4. Ca
5. K
6. Br
7. Sr
8. (h) F
Q7.1.9
Write out the full electron configuration for each of the following atoms and for the monatomic ion found in binary ionic
compounds containing the element:
a. Al
b. Br
c. Sr
d. Li
e. As
f. S
S7.1.9
1s22s22p63s23p1; Al3+: 1s22s22p6; 1s22s22p63s23p63d104s24p5; 1s22s22p63s23p63d104s24p6; 1s22s22p63s23p63d104s24p65s2;
Sr2+: 1s22s22p63s23p63d104s24p6; 1s22s1;
Li+: 1s2; 1s22s22p63s23p63d104s24p3; 1s22s22p63s23p63d104s24p6; 1s22s22p63s23p4; 1s22s22p63s23p6
Q7.1.10
From the labels of several commercial products, prepare a list of six ionic compounds in the products. For each compound, write
the formula. (You may need to look up some formulas in a suitable reference.)

Why is it incorrect to speak of a molecule of solid NaCl?
NaCl consists of discrete ions arranged in a crystal lattice, not covalently bonded molecules.
What information can you use to predict whether a bond between two atoms is covalent or ionic?
Predict which of the following compounds are ionic and which are covalent, based on the location of their constituent atoms in the
periodic table:
1. Cl2CO
2. MnO
3. NCl3
4. CoBr2
5. K2S
6. CO
7. CaF2
8. (h) HI
9. (i) CaO
10. (j) IBr
11. (k) CO2
ionic: (b), (d), (e), (g), and (i); covalent: (a), (c), (f), (h), (j), and (k)
Explain the difference between a nonpolar covalent bond, a polar covalent bond, and an ionic bond.
From its position in the periodic table, determine which atom in each pair is more electronegative:
1. Br or Cl
2. N or O
3. S or O
4. P or S
5. Si or N
6. Ba or P
7. N or K
Cl; O; O; S; N; P; N
From its position in the periodic table, determine which atom in each pair is more electronegative:
1. N or P
2. N or Ge
3. S or F
4. Cl or S
5. H or C
6. Se or P
7. C or Si
From their positions in the periodic table, arrange the atoms in each of the following series in order of increasing electronegativity:
1. C, F, H, N, O
2. Br, Cl, F, H, I
3. F, H, O, P, S
4. Al, H, Na, O, P
5. Ba, H, N, O, As
H, C, N, O, F; H, I, Br, Cl, F; H, P, S, O, F; Na, Al, H, P, O; Ba, H, As, N, O
From their positions in the periodic table, arrange the atoms in each of the following series in order of increasing electronegativity:
1. As, H, N, P, Sb
2. Cl, H, P, S, Si

3. Br, Cl, Ge, H, Sr
4. Ca, H, K, N, Si
5. Cl, Cs, Ge, H, Sr
Which atoms can bond to sulfur so as to produce a positive partial charge on the sulfur atom?
N, O, F, and Cl
Which is the most polar bond?
1. C–C
2. C–H
3. N–H
4. O–H
5. Se–H
Identify the more polar bond in each of the following pairs of bonds:
1. HF or HCl
2. NO or CO
3. SH or OH
4. PCl or SCl
5. CH or NH
6. SO or PO
7. CN or NN
HF; CO; OH; PCl; NH; PO; CN
Which of the following molecules or ions contain polar bonds?
1. O3
2. S8
3. O2−
2
4. NO −
3
5. CO2
6. H2S
7. BH −
4

Q7.4.1
Write the Lewis symbols for each of the following ions:
a. As3–
b. I–
c. Be2+
d. O2–
e. Ga3+
f. Li+
g. N3–
S7.4.1
eight electrons:
eight electrons:

no electrons
Be2+;
eight electrons:
no electrons
Ga3+;
no electrons
Li+;
eight electrons:
Q7.4.2
Many monatomic ions are found in seawater, including the ions formed from the following list of elements. Write the Lewis
symbols for the monatomic ions formed from the following elements:
a. Cl
b. Na
c. Mg
d. Ca
e. K
f. Br
g. Sr
h. F
Q7.4.3
Write the Lewis symbols of the ions in each of the following ionic compounds and the Lewis symbols of the atom from which they
are formed:
1. MgS
2. Al2O3
3. GaCl3
4. K2O
5. Li3N
6. KF
(a)
Two Lewis structures are shown. The left shows the symbol M g with a superscripted two positive sign while the right shows the symbol S surrounded by eight dots and a superscripted two negative sign. ;
(b)
Two Lewis structures are shown. The left shows the symbol A l with a superscripted three positive sign while the right shows the symbol O surrounded by eight dots and a superscripted two negative sign. ;
(c)
Two Lewis structures are shown. The left shows the symbol G a with a superscripted three positive sign while the right shows the symbol C l surrounded by eight dots and a superscripted negative sign. ;
(d)
Two Lewis structures are shown. The left shows the symbol K with a superscripted positive sign while the right shows the symbol O surrounded by eight dots and a superscripted two negative sign. ;

(e)
Two Lewis structures are shown. The left shows the symbol L i with a superscripted positive sign while the right shows the symbol N surrounded by eight dots and a superscripted three negative sign. ;
(f)
Two Lewis structures are shown. The left shows the symbol K with a superscripted positive sign while the right shows the symbol F surrounded by eight dots and a superscripted negative sign.
In the Lewis structures listed here, M and X represent various elements in the third period of the periodic table. Write the formula
of each compound using the chemical symbols of each element:
(a)
Two Lewis structures are shown side-by-side, each surrounded by brackets. The left structure shows the symbol M with a superscripted two positive sign. The right shows the symbol X surrounded by four lone pairs
of electrons with a superscripted two negative sign outside of the brackets.
(b)
Two Lewis structures are shown side-by-side, each surrounded by brackets. The left structure shows the symbol M with a superscripted three positive sign. The right structure shows the symbol X surrounded by four
lone pairs of electrons with a superscripted negative sign and a subscripted three both outside of the brackets.
(c)
Two Lewis structures are shown side-by-side, each surrounded by brackets. The left structure shows the symbol M with a superscripted positive sign and a subscripted two outside of the brackets. The right structure
shows the symbol X surrounded by four lone pairs of electrons with a superscripted two negative sign outside of the brackets.
(d)
Two Lewis structures are shown side-by-side, each surrounded by brackets. The left structure shows the symbol M with a superscripted three positive sign and a subscripted two outside of the brackets. The right
structure shows the symbol X surrounded by four lone pairs of electrons with a superscripted two negative sign and subscripted three both outside of the brackets.
Write the Lewis structure for the diatomic molecule P2, an unstable form of phosphorus found in high-temperature phosphorus
vapor.
A Lewis diagram shows two phosphorus atoms triple bonded together each with one lone electron pair.
Write Lewis structures for the following:

a. H2
b. HBr
c. PCl3
d. SF2
e. H2CCH2
f. HNNH
g. H2CNH
h. (h) NO–
i. (i) N2
j. (j) CO
k. (k) CN–
a. O2
b. H2CO
c. AsF3
d. ClNO
e. SiCl4
f. H3O+
g. NH +
4
h. (h) BF −
4
i. (i) HCCH
j. (j) ClCN
k. (k) C 2+
2
(a)
A Lewis structure shows two oxygen atoms double bonded together, and each has two lone pairs of electrons.

In this case, the Lewis structure is inadequate to depict the fact that experimental studies have shown two unpaired electrons in
each oxygen molecule.
(b)
A Lewis structure shows a carbon atom that is single bonded to two hydrogen atoms and double bonded to an oxygen atom. The oxygen atom has two lone pairs of electrons. ;
(c)
A Lewis structure shows an arsenic atom single bonded to three fluorine atoms. Each fluorine atom has a lone pair of electrons. ;
(d)
A Lewis structure shows a nitrogen atom with a lone pair of electrons single bonded to a chlorine atom that has three lone pairs of electrons. The nitrogen is also double bonded to an oxygen which has two lone pairs
of electrons.
;
(e)
A Lewis structure shows a silicon atom that is single bonded to four chlorine atoms. Each chlorine atom has three lone pairs of electrons. ;
(f)
A Lewis structure shows an oxygen atom with a lone pair of electrons single bonded to three hydrogen atoms. The structure is surrounded by brackets with a superscripted positive sign. ;
(g)
A Lewis structure shows a nitrogen atom single bonded to four hydrogen atoms. The structure is surrounded by brackets with a superscripted positive sign. ;
(h)
A Lewis structure shows a boron atom single bonded to four fluorine atoms. Each fluorine atom has three lone pairs of electrons. The structure is surrounded by brackets with a superscripted negative sign. ;
(i)
A Lewis structure shows two carbon atoms that are triple bonded together. Each carbon is also single bonded to a hydrogen atom. ;
(j)
A Lewis structure shows a carbon atom that is triple bonded to a nitrogen atom that has one lone pair of electrons. The carbon is also single bonded to a chlorine atom that has three lone pairs of electrons. ;
(k)
A Lewis structure shows two carbon atoms joined with a triple bond. A superscripted 2 positive sign lies to the right of the second carbon.

1. ClF3
2. PCl5
3. BF3
4. PF −

1. SeF6
2. XeF4
3. SeCl +
3
4. Cl2BBCl2 (contains a B–B bond)

SeF6:
A Lewis structure shows a selenium atom single bonded to six fluorine atoms, each with three lone pairs of electrons. ;
XeF4:
A Lewis structure shows a xenon atom with two lone pairs of electrons. It is single bonded to four fluorine atoms each with three lone pairs of electrons. ;
SeCl
+
3
:
A Lewis structure shows a selenium atom with one lone pair of electrons single bonded to three chlorine atoms each with three lone pairs of electrons. The whole structure is surrounded by brackets. ;
Cl2BBCl2:

A Lewis structure shows two boron atoms that are single bonded together. Each is also single bonded to two chlorine atoms that both have three lone pairs of electrons.
Write Lewis structures for:

1. PO 3−
4
2. ICl −
4
3. SO 2−
3
4. HONO
Correct the following statement: “The bonds in solid PbCl2 are ionic; the bond in a HCl molecule is covalent. Thus, all of the
valence electrons in PbCl2 are located on the Cl– ions, and all of the valence electrons in a HCl molecule are shared between the H
and Cl atoms.”
Two valence electrons per Pb atom are transferred to Cl atoms; the resulting Pb2+ ion has a 6s2 valence shell configuration. Two of
the valence electrons in the HCl molecule are shared, and the other six are located on the Cl atom as lone pairs of electrons.
Write Lewis structures for the following molecules or ions:
1. SbH3
2. XeF2
3. Se8 (a cyclic molecule with a ring of eight Se atoms)
Methanol, H3COH, is used as the fuel in some race cars. Ethanol, C2H5OH, is used extensively as motor fuel in Brazil. Both
methanol and ethanol produce CO2 and H2O when they burn. Write the chemical equations for these combustion reactions using
Lewis structures instead of chemical formulas.
Two reactions are shown using Lewis structures. The top reaction shows a carbon atom, single bonded to three hydrogen atoms and single bonded to an oxygen atom with two lone pairs of electrons. The oxygen atom
is also bonded to a hydrogen atom. This is followed by a plus sign and the number one point five, followed by two oxygen atoms bonded together with a double bond and each with two lone pairs of electrons. A right-
facing arrow leads to a carbon atom that is double bonded to two oxygen atoms, each of which has two lone pairs of electrons. This structure is followed by a plus sign, a number two, and a structure made up of an
oxygen with two lone pairs of electrons single bonded to two hydrogen atoms. The bottom reaction shows a carbon atom, single bonded to three hydrogen atoms and single bonded to another carbon atom. The second
carbon atom is single bonded to two hydrogen atoms and one oxygen atom with two lone pairs of electrons. The oxygen atom is also bonded to a hydrogen atom. This is followed by a plus sign and the number three,
followed by two oxygen atoms bonded together with a double bond. Each oxygen atom has two lone pairs of electrons. A right-facing arrow leads to a number two and a carbon atom that is double bonded to two oxygen
atoms, each of which has two lone pairs of electrons. This structure is followed by a plus sign, a number three, and a structure made up of an oxygen with two lone pairs of electrons single bonded to two hydrogen atoms.
Many planets in our solar system contain organic chemicals including methane (CH4) and traces of ethylene (C2H4), ethane (C2H6),
propyne (H3CCCH), and diacetylene (HCCCCH). Write the Lewis structures for each of these molecules.
Carbon tetrachloride was formerly used in fire extinguishers for electrical fires. It is no longer used for this purpose because of the
formation of the toxic gas phosgene, Cl2CO. Write the Lewis structures for carbon tetrachloride and phosgene.
Two Lewis structures are shown. The left depicts a carbon atom single bonded to four chlorine atoms, each with three lone pairs of electrons. The right shows a carbon atom double bonded to an oxygen atom that has
two lone pairs of electrons. The carbon atom is also single bonded to two chlorine atoms, each of which has three lone pairs of electrons.
Identify the atoms that correspond to each of the following electron configurations. Then, write the Lewis symbol for the common
ion formed from each atom:
1. 1s22s22p5
2. 1s22s22p63s2
3. 1s22s22p63s23p64s23d10
4. 1s22s22p63s23p64s23d104p4
5. 1s22s22p63s23p64s23d104p1
The arrangement of atoms in several biologically important molecules is given here. Complete the Lewis structures of these
molecules by adding multiple bonds and lone pairs. Do not add any more atoms.
the amino acid serine:
A Lewis structure is shown. A nitrogen atom is single bonded to two hydrogen atoms and a carbon atom. The carbon atom is single bonded to a hydrogen atom and two other carbon atoms. One of these carbon atoms
is single bonded to two hydrogen atoms and an oxygen atom. The oxygen atom is bonded to a hydrogen atom. The other carbon atom is single bonded to two oxygen atoms, one of which is bonded to a hydrogen atom.
urea:
A Lewis structure is shown. A nitrogen atom is single bonded to two hydrogen atoms and a carbon atom. The carbon atom is single bonded to an oxygen atom and another nitrogen atom. That nitrogen atom is then
single bonded to two hydrogen atoms.
pyruvic acid:
A Lewis structure is shown. A carbon atom is single bonded to three hydrogen atoms and another carbon atom. The second carbon atom is single bonded to an oxygen atom and a third carbon atom. This carbon is
then single bonded to two oxygen atoms, one of which is single bonded to a hydrogen atom.
uracil:

A Lewis hexagonal ring structure is shown. From the top of the ring (moving clockwise), three carbon atoms, one nitrogen atom, a carbon atom, and a nitrogen atom are single bonded to each another. The top carbon
atom is single bonded to an oxygen atom. The second and third carbons and the nitrogen atom are each single bonded to a hydrogen atom. The next carbon atom is single bonded to an oxygen atom, and the last nitrogen
atom is single bonded to a hydrogen atom.
carbonic acid:
A Lewis structure is shown. A carbon atom is single bonded to three oxygen atoms. Two of those oxygen atoms are each single bonded to a hydrogen atom.
(a)
A Lewis structure is shown. A nitrogen atom is single bonded to two hydrogen atoms and a carbon atom. The carbon atom is single bonded to a hydrogen atom and two other carbon atoms. One of these carbon atoms
is single bonded to two hydrogen atoms and an oxygen atom. The oxygen atom is bonded to a hydrogen atom. The other carbon is single bonded to two oxygen atoms, one of which is bonded to a hydrogen atom. The
oxygen atoms have two lone pairs of electron dots, and the nitrogen atom has one lone pair of electron dots.
;
(b)
A Lewis structure is shown. A nitrogen atom is single bonded to two hydrogen atoms and a carbon atom. The carbon atom is single bonded to an oxygen atom and one nitrogen atom. That nitrogen atom is then single
bonded to two hydrogen atoms. The oxygen atom has two lone pairs of electron dots, and the nitrogen atoms have one lone pair of electron dots each.
;
(c)
A Lewis structure is shown. A carbon atom is single bonded to three hydrogen atoms and a carbon atom. The carbon atom is single bonded to an oxygen atom and a third carbon atom. This carbon is then single
bonded to two oxygen atoms, one of which is single bonded to a hydrogen atom. Each oxygen atom has two lone pairs of electron dots.
;
(d)
A Lewis hexagonal ring structure is shown. From the top of the ring, three carbon atoms, one nitrogen atom, a carbon atom and a nitrogen atom are single bonded to one another. The top carbon is single bonded to an
oxygen, the second and third carbons and the nitrogen atom are each single bonded to a hydrogen atom. The next carbon is single bonded to an oxygen atom and the last nitrogen is single bonded to a hydrogen atom. The
oxygen atoms have two lone pairs of electron dots, and the nitrogen atoms have one lone pair of electron dots.
;
(e)
A Lewis structure is shown. A carbon atom is single bonded to three oxygen atoms. Two of those oxygen atoms are each single bonded to a hydrogen atom. Each oxygen atom has two lone pairs of electron dots.
A compound with a molar mass of about 28 g/mol contains 85.7% carbon and 14.3% hydrogen by mass. Write the Lewis structure
for a molecule of the compound.
A compound with a molar mass of about 42 g/mol contains 85.7% carbon and 14.3% hydrogen by mass. Write the Lewis structure
for a molecule of the compound.
A Lewis structure is shown. A carbon atom is single bonded to three hydrogen atoms and another carbon atom. The second carbon atom is double bonded to another carbon atom and single bonded to a hydrogen
atom. The last carbon is single bonded to two hydrogen atoms.
Two arrangements of atoms are possible for a compound with a molar mass of about 45 g/mol that contains 52.2% C, 13.1% H, and
34.7% O by mass. Write the Lewis structures for the two molecules.
How are single, double, and triple bonds similar? How do they differ?
Each bond includes a sharing of electrons between atoms. Two electrons are shared in a single bond; four electrons are shared in a
double bond; and six electrons are shared in a triple bond.

Write resonance forms that describe the distribution of electrons in each of these molecules or ions.
1. selenium dioxide, OSeO
2. nitrate ion, NO −
3
3. nitric acid, HNO3 (N is bonded to an OH group and two O atoms)

4. benzene, C6H6:
A Lewis structure shows a hexagonal ring composed of six carbon atoms. They form single bonds to each another and single bonds to one hydrogen atom each.
the formate ion:

A Lewis structure shows a carbon atom single bonded to two oxygen atoms and a hydrogen atom. The structure is surrounded by brackets and there is a superscripted negative sign.
Write resonance forms that describe the distribution of electrons in each of these molecules or ions.
1. sulfur dioxide, SO2
2. carbonate ion, CO 2−
3

3. hydrogen carbonate ion, HCO (C is bonded to an OH group and two O atoms)
−
4. pyridine:
A Lewis structure depicts a hexagonal ring composed of five carbon atoms and one nitrogen atom. Each carbon atom is single bonded to a hydrogen atom.
the allyl ion:

A Lewis structure shows a carbon atom single bonded to two hydrogen atoms and a second carbon atom. The second carbon atom is single bonded to a hydrogen atom and a third carbon atom. The third carbon atom
is single bonded to two hydrogen atoms. The whole structure is surrounded by brackets, and there is a superscripted negative sign.
(a)
Two Lewis structures are shown with a double-headed arrow in between. The left structure shows a sulfur atom with a lone pair of electrons single bonded to the left to an oxygen atom with three lone pairs of
electrons. The sulfur atom is also double bonded on the right to an oxygen atom with two lone pairs of electrons. The right structure depicts the same atoms, but this time the double bond is between the left oxygen and
the sulfur atom. The lone pairs of electrons have also shifted to account for the change of bond types. The sulfur atom in the right structures, also has a third electron dot below it.
;
(b)
Three Lewis structures are shown, with double-headed arrows in between, each surrounded by brackets and a superscripted two negative sign. The left structure depicts a carbon atom bonded to three oxygen atoms. It
is single bonded to two of these oxygen atoms, each of which has three lone pairs of electrons, and double bonded to the third, which has two lone pairs of electrons. The double bond is located between the bottom
oxygen and the carbon. The central and right structures are the same as the first, but the position of the double bonded oxygen has moved to the left oxygen in the right structure while the central structure only has single
bonds. The lone pairs of electrons change to correspond with the bonds as well.
;
(c)
Two Lewis structures are shown, with a double-headed arrow in between, each surrounded by brackets and a superscripted negative sign. The left structure depicts a carbon atom bonded to three oxygen atoms. It is
single bonded to one of these oxygen atoms, which has three lone pairs of electrons, and double bonded to the other two, which have two lone pairs of electrons. One of the double bonded oxygen atoms also has a single
bond to a hydrogen atom. The right structure is the same as the first, but there is only one double bonded oxygen. The oxygen with the single bonded hydrogen now has a single bond to the carbon atom. The lone pairs of
electrons have also changed to correspond with the bonds.
;
(d)
Two Lewis structures are shown with a double-headed arrow in between. The left structure depicts a hexagonal ring composed of five carbon atoms, each single bonded to a hydrogen atom, and one nitrogen atom that
has a lone pair of electrons. The ring has alternating single and double bonds. The right structure is the same as the first, but each double bond has rotated to a new position.
;
(e)
Two Lewis structures are shown with a double-headed arrow in between. The left structure shows a carbon atom single bonded to two hydrogen atoms and a second carbon atom. The second carbon atom is single
bonded to a hydrogen atom and double bonded to a third carbon atom. The third carbon atom is single bonded to two hydrogen atoms. The whole structure is surrounded by brackets and a superscripted negative sign.
The right structure shows a carbon atom single bonded to two hydrogen atoms and double bonded to a second carbon atom. The second carbon atom is single bonded to a hydrogen atom and a third carbon atom. The
third carbon atom is single bonded to two hydrogen atoms. The whole structure is surrounded by brackets and a superscripted negative sign.
Write the resonance forms of ozone, O3, the component of the upper atmosphere that protects the Earth from ultraviolet radiation.
Sodium nitrite, which has been used to preserve bacon and other meats, is an ionic compound. Write the resonance forms of the
nitrite ion, NO . −
Two pairs of Lewis structures are shown with a double-headed arrow in between each pair. The left structure of the first pair shows a nitrogen atom with one lone pair of electrons single bonded to an oxygen atom
with three lone pairs of electrons. It is also double bonded to an oxygen with two lone pairs of electrons. The right image of this pair depicts the mirror image of the left. Both images are surrounded by brackets and a
superscripted negative sign. They are labeled, “For N O subscript two superscript negative sign.” The left structure of the second pair shows an oxygen atom with one lone pair of electrons single bonded to an oxygen
atom with three lone pairs of electrons. It is also double bonded to an oxygen atom with two lone pairs of electrons. The right structure appears as a mirror image of the left. These structures are labeled, “For O subscript
three.”
In terms of the bonds present, explain why acetic acid, CH3CO2H, contains two distinct types of carbon-oxygen bonds, whereas the
acetate ion, formed by loss of a hydrogen ion from acetic acid, only contains one type of carbon-oxygen bond. The skeleton
structures of these species are shown:
Two Lewis structures are shown with a double headed arrow in between. The left structure shows a carbon atom single bonded to three hydrogen atoms and a second carbon atom. The second carbon is single bonded
to two oxygen atoms. One of the oxygen atoms is single bonded to a hydrogen atom. The right structure, surrounded by brackets and with a superscripted negative sign, depicts a carbon atom single bonded to three
hydrogen atoms and a second carbon atom. The second carbon atom is single bonded to two oxygen atoms.
Write the Lewis structures for the following, and include resonance structures where appropriate. Indicate which has the strongest
carbon-oxygen bond.
1. CO2
2. CO
(a)
This structure shows a carbon atom double bonded to two oxygen atoms, each of which has two lone pairs of electrons.
(b)

The right structure of this pair shows a carbon atom with one lone pair of electrons triple bonded to an oxygen with one lone pair of electrons.
CO has the strongest carbon-oxygen bond because there is a triple bond joining C and O. CO2 has double bonds.
Toothpastes containing sodium hydrogen carbonate (sodium bicarbonate) and hydrogen peroxide are widely used. Write Lewis
structures for the hydrogen carbonate ion and hydrogen peroxide molecule, with resonance forms where appropriate.
Determine the formal charge of each element in the following:
1. HCl
2. CF4
3. PCl3
4. PF5
H: 0, Cl: 0; C: 0, F: 0; P: 0, Cl 0; P: 0, F: 0
Determine the formal charge of each element in the following:
1. H3O+
2. SO 2−
4
3. NH3
4. O 2−
5. H2O2
Calculate the formal charge of chlorine in the molecules Cl2, BeCl2, and ClF5.
Cl in Cl2: 0; Cl in BeCl2: 0; Cl in ClF5: 0
Calculate the formal charge of each element in the following compounds and ions:
1. F2CO
2. NO–
3. BF −
4. SnCl −
3
5. H2CCH2
6. ClF3
7. SeF6
8. (h) PO 3−
4
Draw all possible resonance structures for each of these compounds. Determine the formal charge on each atom in each of the
resonance structures:
1. O3
2. SO2
3. NO −
2
4. NO −
3
Two Lewis structures are shown with a double-headed arrow in between. The left structure shows an oxygen atom with one lone pair of electrons single bonded to an oxygen atom with three lone pairs of electrons. It
is also double bonded to an oxygen atom with two lone pairs of electrons. The symbols and numbers below this structure read, “( 0 ), ( positive 1 ), ( negative 1 ).” The phrase, “Formal charge,” and a right-facing arrow
lie to the left of this structure. The right structure appears as a mirror image of the left and the symbols and numbers below this structure read, “( negative 1 ), ( positive 1 ), ( 0 ).”
;
(b)
Two Lewis structures are shown, with a double-headed arrow in between. The left structure shows a sulfur atom with one lone pair of electrons single bonded to an oxygen atom with three lone pairs of electrons. The
sulfur atom also double bonded to an oxygen atom with two lone pairs of electrons. The symbols and numbers below this structure read, “( negative 1 ), ( positive 1 ), ( 0 ).” The right structure appears as a mirror image
of the left and the symbols and numbers below this structure read, “( 0 ), ( positive 1 ), ( negative 1 ).”
;
(c)
[Two Lewis structures are shown, with brackets surrounding each with a superscripted negative sign and a double ended arrow in between. The left structure shows a nitrogen atom with one lone pair of electrons
single bonded to an oxygen atom with three lone pairs of electrons and double bonded to an oxygen atom with two lone pairs of electrons. The symbols and numbers below this structure read “open parenthesis, 0, close
parenthesis, open parenthesis, 0, close parenthesis, open parenthesis, negative 1, close parenthesis. The right structure appears as a mirror image of the left and the symbols and numbers below this structure read “open
parenthesis, negative 1, close parenthesis, open parenthesis, 0, close parenthesis, open parenthesis, 0, close parenthesis.]
;
(d)

[Three Lewis structures are shown, with brackets surrounding each with a superscripted negative sign and a double ended arrow in between. The left structure shows a nitrogen atom single bonded to two oxygen
atoms, each with three lone pairs of electrons and double bonded to an oxygen atom with two lone pairs of electrons. The single bonded oxygen atoms are labeled, from the top of the structure and going clockwise, “open
parenthesis, negative 1, close parenthesis, open parenthesis, positive 1, close parenthesis”. The symbols and numbers below this structure read “open parenthesis, 0, close parenthesis, open parenthesis, negative 1, close
parenthesis. The middle structure shows a nitrogen atom single bonded to two oxygen atoms, each with three lone pairs of electrons, one of which is labeled “open parenthesis, positive 1, close parenthesis” and double
bonded to an oxygen atom with two lone pairs of electrons labeled “open parenthesis, 0, close parenthesis”. The symbols and numbers below this structure read “open parenthesis, negative 1, close parenthesis, open
parenthesis, negative 1, close parenthesis. The right structure shows a nitrogen atom single bonded to two oxygen atoms, each with three lone pairs of electrons and double bonded to an oxygen atom with two lone pairs
of electrons. One of the single bonded oxygen atoms is labeled, “open parenthesis, negative 1, close parenthesis while the double bonded oxygen is labeled, “open parenthesis, positive 1, close parenthesis”. The symbols
and numbers below this structure read “open parenthesis, negative 1, close parenthesis” and “open parenthesis, 0, close parenthesis”.]
Based on formal charge considerations, which of the following would likely be the correct arrangement of atoms in nitrosyl
chloride: ClNO or ClON?
Based on formal charge considerations, which of the following would likely be the correct arrangement of atoms in hypochlorous
acid: HOCl or OClH?
HOCl
Based on formal charge considerations, which of the following would likely be the correct arrangement of atoms in sulfur dioxide:
OSO or SOO?
Draw the structure of hydroxylamine, H3NO, and assign formal charges; look up the structure. Is the actual structure consistent
with the formal charges?
The structure that gives zero formal charges is consistent with the actual structure:
A Lewis structure shows a nitrogen atom with one lone pair of electrons single bonded to two hydrogen atoms and an oxygen atom which has two lone pairs of electrons. The oxygen atom is single bonded to a
hydrogen atom.
Iodine forms a series of fluorides (listed here). Write Lewis structures for each of the four compounds and determine the formal
charge of the iodine atom in each molecule:
1. IF
2. IF3
3. IF5
4. IF7
Write the Lewis structure and chemical formula of the compound with a molar mass of about 70 g/mol that contains 19.7%
nitrogen and 80.3% fluorine by mass, and determine the formal charge of the atoms in this compound.
NF3;
A Lewis structure shows a nitrogen atom with one lone pair of electrons single bonded to three fluorine atoms, each with three lone pairs of electrons.
Which of the following structures would we expect for nitrous acid? Determine the formal charges:
Two Lewis structures are shown, with the word “or” in between. The left structure shows a nitrogen atom single bonded to an oxygen atom with three lone pairs of electrons. It is also single bonded to a hydrogen
atom and double bonded to an oxygen atom with two lone pairs of electrons. The right structure shows a hydrogen atom single bonded to an oxygen atom with two lone pairs of electrons. The oxygen atom is single
bonded to a nitrogen atom which is double bonded to an oxygen atom with two lone pairs of electrons.
Sulfuric acid is the industrial chemical produced in greatest quantity worldwide. About 90 billion pounds are produced each year in
the United States alone. Write the Lewis structure for sulfuric acid, H2SO4, which has two oxygen atoms and two OH groups
bonded to the sulfur.
A Lewis structure shows a hydrogen atom single bonded to an oxygen atom with two lone pairs of electrons. The oxygen atom is single bonded to a sulfur atom. The sulfur atom is double bonded to two oxygen
atoms, each of which have three lone pairs of electrons, and single bonded to an oxygen atom with two lone pairs of electrons. This oxygen atom is single bonded to a hydrogen atom.

Which bond in each of the following pairs of bonds is the strongest?
1. C–C or C = C
2. C–N or C ≡ N
3. C ≡ O or C = O
4. H–F or H–Cl
5. C–H or O–H
6. C–N or C–O
Using the bond energies in Table, determine the approximate enthalpy change for each of the following reactions:
1. H (g) + Br
2 2
(g) ⟶ 2 HBr(g)
2. CH (g) + I
4 2
(g) ⟶ CH I(g) + HI(g)
3

3. (c) C 2
H (g) + 3 O (g) ⟶ 2 CO (g) + 2 H O(g)
4 2 2 2
1. −114 kJ;
2. 30 kJ;
3. (c) −1055 kJ
Using the bond energies in Table, determine the approximate enthalpy change for each of the following reactions:
1. Cl (g) + 3 F (g) ⟶ 2 ClF (g)
2 2 3
2. H C = C H (g) + H (g) ⟶ H CCH (g)

2 2 2 3 3
3. (c) 2 C H (g) + 7 O (g) ⟶ 4 CO (g) + 6 H

2 6 2 2 2
O(g)
When a molecule can form two different structures, the structure with the stronger bonds is usually the more stable form. Use bond
energies to predict the correct structure of the hydroxylamine molecule:
Two Lewis structures are shows with the word “or” written in between them. The left structure shows a nitrogen atom with one lone pair of electrons single bonded to two hydrogen atoms. It is also bonded to an
oxygen atom with two lone pairs of electrons. The oxygen atom is bonded to a hydrogen atom. The right structure shows a nitrogen atom single bonded to three hydrogen atoms and an oxygen atom with three lone pairs
of electrons.
The greater bond energy is in the figure on the left. It is the more stable form.
How does the bond energy of HCldiffer from the standard enthalpy of formation of HCl(g)?
Using the standard enthalpy of formation data in Appendix G, show how the standard enthalpy of formation of HCl(g) can be used
to determine the bond energy.
1 1
∘ ∘
HCl(g) ⟶ H (g) + Cl (g) ΔH = −ΔH
2 2 1 f[HCl(g)]
2 2
1
∘ ∘
H (g) ⟶ H(g) ΔH = ΔH
2 2 f[H(g)]
2
1
∘ ∘
Cl (g) ⟶ Cl(g) ΔH = ΔH
2 3 f[Cl(g)]
2
–––––––––––––––––––––––––––––––––––––––––––––––
∘ ∘ ∘ ∘
HCl(g) ⟶ H(g) + Cl(g) ΔH = ΔH + ΔH + ΔH
298 1 2 3
∘ ∘ ∘ ∘
DHCl = ΔH = ΔH + ΔH + ΔH (4.E.1)
298 f[HCl(g)] f[H(g)] f[Cl(g)]
= −(−92.307 kJ) + 217.97 kJ + 121.3 kJ (4.E.2)
= 431.6 kJ (4.E.3)
Using the standard enthalpy of formation data in Appendix G, calculate the bond energy of the carbon-sulfur double bond in CS2.
Using the standard enthalpy of formation data in Appendix G, determine which bond is stronger: the S–F bond in SF4(g) or in
SF6(g)?
The S–F bond in SF4 is stronger.
Using the standard enthalpy of formation data in Appendix G, determine which bond is stronger: the P–Cl bond in PCl3(g) or in
PCl5(g)?
Complete the following Lewis structure by adding bonds (not atoms), and then indicate the longest bond:
A Lewis structure is shown that is missing its bonds. It shows a horizontal row of six carbon atoms, equally spaced. Three hydrogen atoms are drawn around the first carbon, two around the second, one above the
fifth, and two by the sixth.
A Lewis structure is shown. A carbon atom that is single bonded to three hydrogen atoms is bonded to a second carbon atom. The second carbon atom is single bonded to two hydrogen atoms. The second carbon atom
is single bonded to a third carbon atom that is triple bonded to a fourth carbon atom and single bonded to a fifth carbon atom. The fifth carbon atom is single bonded to a hydrogen atom and double bonded to a sixth
carbon atom that is single bonded to two hydrogen atoms.
The C–C single bonds are longest.

Use the bond energy to calculate an approximate value of ΔH for the following reaction. Which is the more stable form of FNO2?
Two Lewis structures are shown with a right-facing arrow in between. The left structure shows a nitrogen atom double bonded to an oxygen atom with two lone pairs of electrons. It is also bonded to a fluorine atom
and another oxygen atom, each with three lone pairs of electrons. The right structure shows an oxygen atom with two lone pairs of electrons double bonded to a nitrogen atom with one lone pair of electrons. This
nitrogen atom is single bonded to an oxygen with two lone pairs of electrons. The oxygen atom is single bonded to a fluorine atom with three lone pairs of electrons.
Use principles of atomic structure to answer each of the following:1

1. The radius of the Ca atom is 197 pm; the radius of the Ca2+ ion is 99 pm. Account for the difference.
2. The lattice energy of CaO(s) is –3460 kJ/mol; the lattice energy of K2O is –2240 kJ/mol. Account for the difference.

3. (c) Given these ionization values, explain the difference between Ca and K with regard to their first and second ionization
energies.
Element First Ionization Energy (kJ/mol) Second Ionization Energy (kJ/mol)
K 419 3050
Ca 590 1140
The first ionization energy of Mg is 738 kJ/mol and that of Al is 578 kJ/mol. Account for this difference.
When two electrons are removed from the valence shell, the Ca radius loses the outermost energy level and reverts to the lower n =
3 level, which is much smaller in radius. The +2 charge on calcium pulls the oxygen much closer compared with K, thereby
increasing the lattice energy relative to a less charged ion. (c) Removal of the 4s electron in Ca requires more energy than removal
of the 4s electron in K because of the stronger attraction of the nucleus and the extra energy required to break the pairing of the
electrons. The second ionization energy for K requires that an electron be removed from a lower energy level, where the attraction
is much stronger from the nucleus for the electron. In addition, energy is required to unpair two electrons in a full orbital. For Ca,
the second ionization potential requires removing only a lone electron in the exposed outer energy level. In Al, the removed
electron is relatively unprotected and unpaired in a p orbital. The higher energy for Mg mainly reflects the unpairing of the 2s
electron.
The lattice energy of LiF is 1023 kJ/mol, and the Li–F distance is 200.8 pm. NaF crystallizes in the same structure as LiF but with a
Na–F distance of 231 pm. Which of the following values most closely approximates the lattice energy of NaF: 510, 890, 1023,
1175, or 4090 kJ/mol? Explain your choice.
For which of the following substances is the least energy required to convert one mole of the solid into separate ions?
1. MgO
2. SrO
3. (c) KF
4. CsF
5. MgF2
(d)
The reaction of a metal, M, with a halogen, X2, proceeds by an exothermic reaction as indicated by this equation:
M(s) + X (g) ⟶ MX (s) . For each of the following, indicate which option will make the reaction more exothermic. Explain
2 2
your answers.
1. a large radius vs. a small radius for M+2
2. a high ionization energy vs. a low ionization energy for M
3. (c) an increasing bond energy for the halogen
4. a decreasing electron affinity for the halogen
5. an increasing size of the anion formed by the halogen
The lattice energy of LiF is 1023 kJ/mol, and the Li–F distance is 201 pm. MgO crystallizes in the same structure as LiF but with a
Mg–O distance of 205 pm. Which of the following values most closely approximates the lattice energy of MgO: 256 kJ/mol, 512
kJ/mol, 1023 kJ/mol, 2046 kJ/mol, or 4008 kJ/mol? Explain your choice.
4008 kJ/mol; both ions in MgO have twice the charge of the ions in LiF; the bond length is very similar and both have the same
structure; a quadrupling of the energy is expected based on the equation for lattice energy
Which compound in each of the following pairs has the larger lattice energy? Note: Mg2+ and Li+ have similar radii; O2– and F–
have similar radii. Explain your choices.
1. MgO or MgSe
2. LiF or MgO
3. (c) Li2O or LiCl
4. Li2Se or MgO
Which compound in each of the following pairs has the larger lattice energy? Note: Ba2+ and

K+ have similar radii; S2– and Cl– have similar radii. Explain your choices.
1. K2O or Na2O
2. K2S or BaS
3. (c) KCl or BaS
4. BaS or BaCl2
Na2O; Na+ has a smaller radius than K+; BaS; Ba has a larger charge than K; (c) BaS; Ba and S have larger charges; BaS; S has a
larger charge
Which of the following compounds requires the most energy to convert one mole of the solid into separate ions?
1. MgO
2. SrO
3. (c) KF
4. CsF
5. MgF2
Which of the following compounds requires the most energy to convert one mole of the solid into separate ions?
1. K2S
2. K2O
3. (c) CaS
4. Cs2S
5. CaO
(e)
The lattice energy of KF is 794 kJ/mol, and the interionic distance is 269 pm. The Na–F
distance in NaF, which has the same structure as KF, is 231 pm. Which of the following values is the closest approximation of the
lattice energy of NaF: 682 kJ/mol, 794 kJ/mol, 924 kJ/mol, 1588 kJ/mol, or 3175 kJ/mol? Explain your answer.

Explain why the HOH molecule is bent, whereas the HBeH molecule is linear.
The placement of the two sets of unpaired electrons in water forces the bonds to assume a tetrahedral arrangement, and the
resulting HOH molecule is bent. The HBeH molecule (in which Be has only two electrons to bond with the two electrons from the
hydrogens) must have the electron pairs as far from one another as possible and is therefore linear.
What feature of a Lewis structure can be used to tell if a molecule’s (or ion’s) electron-pair geometry and molecular structure will
be identical?
Explain the difference between electron-pair geometry and molecular structure.
Space must be provided for each pair of electrons whether they are in a bond or are present as lone pairs. Electron-pair geometry
considers the placement of all electrons. Molecular structure considers only the bonding-pair geometry.
Why is the H–N–H angle in NH3 smaller than the H–C–H bond angle in CH4? Why is the H–N–H angle in NH
+
4
identical to the
H–C–H bond angle in CH4?
Explain how a molecule that contains polar bonds can be nonpolar.
As long as the polar bonds are compensated (for example. two identical atoms are found directly across the central atom from one
another), the molecule can be nonpolar.
As a general rule, MXn molecules (where M represents a central atom and X represents terminal atoms; n = 2 – 5) are polar if there
is one or more lone pairs of electrons on M. NH3 (M = N, X = H, n = 3) is an example. There are two molecular structures with
lone pairs that are exceptions to this rule. What are they?
Predict the electron pair geometry and the molecular structure of each of the following molecules or ions:
1. SF6
2. PCl5

3. (c) BeH2
4. CH +
1. Both the electron geometry and the molecular structure are octahedral.
2. Both the electron geometry and the molecular structure are trigonal bipyramid.
3. (c) Both the electron geometry and the molecular structure are linear.
4. Both the electron geometry and the molecular structure are trigonal planar.
Identify the electron pair geometry and the molecular structure of each of the following molecules or ions:
1. IF+
6
2. CF4
3. (c) BF3
4. SiF −
5. BeCl2
What are the electron-pair geometry and the molecular structure of each of the following molecules or ions?
1. ClF5
2. ClO −
3. (c) TeCl 2−
4. PCl3
5. SeF4
6. PH −
electron-pair geometry: octahedral, molecular structure: square pyramidal; electron-pair geometry: tetrahedral, molecular structure:
bent; (c) electron-pair geometry: octahedral, molecular structure: square planar; electron-pair geometry: tetrahedral, molecular
structure: trigonal pyramidal; electron-pair geometry: trigonal bypyramidal, molecular structure: seesaw; electron-pair geometry:
tetrahedral, molecular structure: bent (109°)
Predict the electron pair geometry and the molecular structure of each of the following ions:
1. H3O+
2. PCl −
3. (c) SnCl −
4. BrCl −
5. ICl3
6. XeF4
7. (g) SF2
Identify the electron pair geometry and the molecular structure of each of the following molecules:
1. ClNO (N is the central atom)
2. CS2
3. (c) Cl2CO (C is the central atom)
4. Cl2SO (S is the central atom)
5. SO2F2 (S is the central atom)
6. XeO2F2 (Xe is the central atom)
7. (g) ClOF (Cl is the central atom)
+
2
electron-pair geometry: trigonal planar, molecular structure: bent (120°); electron-pair geometry: linear, molecular structure: linear;
(c) electron-pair geometry: trigonal planar, molecular structure: trigonal planar; electron-pair geometry: tetrahedral, molecular
structure: trigonal pyramidal; electron-pair geometry: tetrahedral, molecular structure: tetrahedral; electron-pair geometry: trigonal
bipyramidal, molecular structure: seesaw; (g) electron-pair geometry: tetrahedral, molecular structure: trigonal pyramidal
Predict the electron pair geometry and the molecular structure of each of the following:
1. IOF5 (I is the central atom)
2. POCl3 (P is the central atom)
3. (c) Cl2SeO (Se is the central atom)

4. ClSO+ (S is the central atom)
5. F2SO (S is the central atom)
6. NO −
7. (g) SiO 4−
Which of the following molecules and ions contain polar bonds? Which of these molecules and ions have dipole moments?
1. ClF5
2. ClO −
2
3. (c) TeCl 2−
4
4. PCl3
5. SeF4
6. PH −
2
7. (g) XeF2
All of these molecules and ions contain polar bonds. Only ClF5, ClO , PCl3, SeF4, and PH have dipole moments.
−
2
−
Which of the molecules and ions in Exercise contain polar bonds? Which of these molecules and ions have dipole moments?
1. H3O+
2. PCl−
4
3. (c) SnCl −
3
4. BrCl −
4
5. ICl3
6. XeF4
7. (g) SF2
Which of the following molecules have dipole moments?
1. CS2
2. SeS2
3. (c) CCl2F2
4. PCl3 (P is the central atom)
5. ClNO (N is the central atom)
SeS2, CCl2F2, PCl3, and ClNO all have dipole moments.
Identify the molecules with a dipole moment:
1. SF4
2. CF4
3. (c) Cl2CCBr2
4. CH3Cl
5. H2CO
The molecule XF3 has a dipole moment. Is X boron or phosphorus?
P
The molecule XCl2 has a dipole moment. Is X beryllium or sulfur?
Is the Cl2BBCl2 molecule polar or nonpolar?
nonpolar
There are three possible structures for PCl2F3 with phosphorus as the central atom. Draw them and discuss how measurements of
dipole moments could help distinguish among them.
Describe the molecular structure around the indicated atom or atoms:
1. the sulfur atom in sulfuric acid, H2SO4 [(HO)2SO2]
2. the chlorine atom in chloric acid, HClO3 [HOClO2]
3. (c) the oxygen atom in hydrogen peroxide, HOOH

4. the nitrogen atom in nitric acid, HNO3 [HONO2]
5. the oxygen atom in the OH group in nitric acid, HNO3 [HONO2]
6. the central oxygen atom in the ozone molecule, O3
7. (g) each of the carbon atoms in propyne, CH3CCH
8. (h) the carbon atom in Freon, CCl2F2
9. (i) each of the carbon atoms in allene, H2CCCH2
tetrahedral; trigonal pyramidal; (c) bent (109°); trigonal planar; bent (109°); bent (109°); (g) CH3CCH tetrahedral, CH3CCH linear;
(h) tetrahedral; (i) H2CCCH2 linear; H2CCCH2 trigonal planar
Draw the Lewis structures and predict the shape of each compound or ion:
1. CO2
2. NO −
3. (c) SO3
4. SO 2−
A molecule with the formula AB2, in which A and B represent different atoms, could have one of three different shapes. Sketch and
name the three different shapes that this molecule might have. Give an example of a molecule or ion for each shape.
Three Lewis diagrams are shown. The first diagram shows the letter A single bonded to the left and right to the letter B. An example, “C O subscript 2,” and the term, “linear,” are written beside this diagram. The
second diagram shows the letter A with two lone pairs of electrons, single bonded to the left and lower right to the letter B. An example, “H subscript 2 O,” and the term, “bent with an approximately 109 degree angle,”
are written beside this diagram. The third diagram shows the letter A with one lone electron pair, single bonded to the left and lower right to the letter B. An example, “S O subscript 2,” and the term, “bent with an
approximately 120 degree angle,” are written beside this diagram.
A molecule with the formula AB3, in which A and B represent different atoms, could have one of three different shapes. Sketch and
name the three different shapes that this molecule might have. Give an example of a molecule or ion that has each shape.
Draw the Lewis electron dot structures for these molecules, including resonance structures where appropriate:
1. CS 2−
3
2. CS2
3. (c) CS
predict the molecular shapes for CS 2−
3
and CS2 and explain how you arrived at your predictions
(a)
The figure shows three Lewis structures that are each surrounded by brackets and have a superscripted 2 negative sign. They are written with a double-headed arrow in between each diagram. The first of this trio has a
carbon atom single bonded to two sulfur atoms, each of which has thee lone pairs of electrons, and double bonded to a third sulfur atom with two lone pairs of electrons. The second and third diagrams have the same
atoms present, but each time the double bond moves between a different carbon and sulfur pair. The lone electron pairs also shift to correspond with the bond changes.
;
(b)
The Lewis structure shows a carbon atom double bonded to two sulfur atoms, each of which has two lone pairs of electrons. ;
(c)
This diagram shows a carbon with one lone electron pair triple bonded to a sulfur with one lone electron pair. ;
CS includes three regions of electron density (all are bonds with no lone pairs); the shape is trigonal planar; CS2 has only two
2−
3
regions of electron density (all bonds with no lone pairs); the shape is linear
What is the molecular structure of the stable form of FNO2? (N is the central atom.)
A compound with a molar mass of about 42 g/mol contains 85.7% carbon and 14.3% hydrogen. What is its molecular structure?
The Lewis structure is made from three units, but the atoms must be rearranged:
A Lewis structure is shown in which a carbon atom is single bonded to three hydrogen atoms and a second carbon atom. The second carbon is single bonded to a hydrogen atom and double bonded to a third carbon
atom which is single bonded to two hydrogen atoms.
Use the simulation to perform the following exercises for a two-atom molecule:
1. Adjust the electronegativity value so the bond dipole is pointing toward B. Then determine what the electronegativity values
must be to switch the dipole so that it points toward A.
2. With a partial positive charge on A, turn on the electric field and describe what happens.
3. (c) With a small partial negative charge on A, turn on the electric field and describe what happens.

4. Reset all, and then with a large partial negative charge on A, turn on the electric field and describe what happens.
Use the simulation to perform the following exercises for a real molecule. You may need to rotate the molecules in three
dimensions to see certain dipoles.
1. Sketch the bond dipoles and molecular dipole (if any) for O3. Explain your observations.
2. Look at the bond dipoles for NH3. Use these dipoles to predict whether N or H is more electronegative.
3. (c) Predict whether there should be a molecular dipole for NH3 and, if so, in which direction it will point. Check the molecular
dipole box to test your hypothesis.
The molecular dipole points away from the hydrogen atoms.
Use the Molecule Shape simulator to build a molecule. Starting with the central atom, click on the double bond to add one double
bond. Then add one single bond and one lone pair. Rotate the molecule to observe the complete geometry. Name the electron group
geometry and molecular structure and predict the bond angle. Then click the check boxes at the bottom and right of the simulator to
check your answers.
Use the Molecule Shape simulator to explore real molecules. On the Real Molecules tab, select H2O. Switch between the “real”
and “model” modes. Explain the difference observed.
The structures are very similar. In the model mode, each electron group occupies the same amount of space, so the bond angle is
shown as 109.5°. In the “real” mode, the lone pairs are larger, causing the hydrogens to be compressed. This leads to the smaller
angle of 104.5°.
Use the Molecule Shape simulator to explore real molecules. On the Real Molecules tab, select “model” mode and S2O. What is
the model bond angle? Explain whether the “real” bond angle should be larger or smaller than the ideal model angle.
This page titled 4.E: Chemical Bonding and Molecular Geometry (Exercises) is shared under a CC BY license and was authored, remixed, and/or

CHAPTER OVERVIEW
5: Advanced Theories of Covalent Bonding

General Chemistry
We have examined the basic ideas of bonding, showing that atoms share electrons to form molecules with stable Lewis structures
and that we can predict the shapes of those molecules by valence shell electron pair repulsion (VSEPR) theory. These ideas provide
an important starting point for understanding chemical bonding. But these models sometimes fall short in their abilities to predict
the behavior of real substances. How can we reconcile the geometries of s, p, and d atomic orbitals with molecular shapes that
show angles like 120° and 109.5°? Furthermore, we know that electrons and magnetic behavior are related through electromagnetic
fields.
5.4: Multiple Bonds
Contributors
[email protected]).
This page titled 5: Advanced Theories of Covalent Bonding is shared under a CC BY license and was authored, remixed, and/or curated by
OpenStax.
1
We have examined the basic ideas of bonding, showing that atoms share electrons to form molecules with stable Lewis structures
and that we can predict the shapes of those molecules by valence shell electron pair repulsion (VSEPR) theory. These ideas provide
an important starting point for understanding chemical bonding. But these models sometimes fall short in their abilities to predict
the behavior of real substances. How can we reconcile the geometries of s, p, and d atomic orbitals with molecular shapes that
show angles like 120° and 109.5°? Furthermore, we know that electrons and magnetic behavior are related through electromagnetic
fields. Both N2 and O2 have fairly similar Lewis structures that contain lone pairs of electrons.
Two Lewis diagrams are shown. The diagram on the left shows two nitrogen atoms, represented by the letter N connected by three
lines and with a lone pair of electrons on each end of the structure. The diagram on the right shows two oxygen atoms, depicted by
the letter O, connected by two lines. Two pairs of electrons surround each oxygen to the top and ends of the structure.
Yet oxygen demonstrates very different magnetic behavior than nitrogen. We can pour liquid nitrogen through a magnetic field with
no visible interactions, while liquid oxygen is attracted to the magnet and floats in the magnetic field. We need to understand the
additional concepts of valence bond theory, orbital hybridization, and molecular orbital theory to understand these observations.
Figure 5.1.1 : Oxygen molecules orient randomly most of the time, as shown in the top magnified view. However, when we pour
liquid oxygen through a magnet, the molecules line up with the magnetic field, and the attraction allows them to stay suspended
between the poles of the magnet where the magnetic field is strongest. Other diatomic molecules (like N2) flow past the magnet.
The detailed explanation of bonding described in this chapter allows us to understand this phenomenon. (credit: modification of
work by Jefferson Lab)
A pitcher is shown pouring liquid oxygen through the gap between two magnets, where it has formed a solid disk. A call out box
near the stream of liquid oxygen shows an image of six pairs of spheres, spread apart from one another. Another call out box near
the solid disk shows ten pairs of spheres much closer together.
This page titled 5.1: Prelude to Covalent Bonding is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
8.0: Prelude to Covalent Bonding is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

Describe the formation of covalent bonds in terms of atomic orbital overlap
Define and give examples of σ and π bonds
As we know, a scientific theory is a strongly supported explanation for observed natural laws or large bodies of experimental data.
For a theory to be accepted, it must explain experimental data and be able to predict behavior. For example, VSEPR theory has
gained widespread acceptance because it predicts three-dimensional molecular shapes that are consistent with experimental data
collected for thousands of different molecules. However, VSEPR theory does not provide an explanation of chemical bonding.
There are successful theories that describe the electronic structure of atoms. We can use quantum mechanics to predict the specific
regions around an atom where electrons are likely to be located: A spherical shape for an s orbital, a dumbbell shape for a p orbital,
and so forth. However, these predictions only describe the orbitals around free atoms. When atoms bond to form molecules, atomic
orbitals are not sufficient to describe the regions where electrons will be located in the molecule. A more complete understanding
of electron distributions requires a model that can account for the electronic structure of molecules. One popular theory holds that a
covalent bond forms when a pair of electrons is shared by two atoms and is simultaneously attracted by the nuclei of both atoms. In
the following sections, we will discuss how such bonds are described by valence bond theory and hybridization.
Valence bond theory describes a covalent bond as the overlap of half-filled atomic orbitals (each containing a single electron) that
yield a pair of electrons shared between the two bonded atoms. We say that orbitals on two different atoms overlap when a portion
of one orbital and a portion of a second orbital occupy the same region of space. According to valence bond theory, a covalent bond
results when two conditions are met:
1. an orbital on one atom overlaps an orbital on a second atom and
2. the single electrons in each orbital combine to form an electron pair.
The mutual attraction between this negatively charged electron pair and the two atoms’ positively charged nuclei serves to
physically link the two atoms through a force we define as a covalent bond. The strength of a covalent bond depends on the extent
of overlap of the orbitals involved. Orbitals that overlap extensively form bonds that are stronger than those that have less overlap.
The energy of the system depends on how much the orbitals overlap. Figure 5.2.1 illustrates how the sum of the energies of two
hydrogen atoms (the colored curve) changes as they approach each other. When the atoms are far apart there is no overlap, and by
convention we set the sum of the energies at zero. As the atoms move together, their orbitals begin to overlap. Each electron begins
to feel the attraction of the nucleus in the other atom. In addition, the electrons begin to repel each other, as do the nuclei. While the
atoms are still widely separated, the attractions are slightly stronger than the repulsions, and the energy of the system decreases. (A
bond begins to form.) As the atoms move closer together, the overlap increases, so the attraction of the nuclei for the electrons
continues to increase (as do the repulsions among electrons and between the nuclei). At some specific distance between the atoms,
which varies depending on the atoms involved, the energy reaches its lowest (most stable) value. This optimum distance between
the two bonded nuclei is the bond distance between the two atoms. The bond is stable because at this point, the attractive and
repulsive forces combine to create the lowest possible energy configuration. If the distance between the nuclei were to decrease
further, the repulsions between nuclei and the repulsions as electrons are confined in closer proximity to each other would become
stronger than the attractive forces. The energy of the system would then rise (making the system destabilized), as shown at the far
left of Figure 5.2.1.

Figure 5.2.1 : The interaction of two hydrogen atoms changes as a function of distance. The energy of the system changes as the
atoms interact. The lowest (most stable) energy occurs at a distance of 74 pm, which is the bond length observed for the H2
molecule.
A pair of diagrams are shown and labeled “a” and “b”. Diagram a shows three consecutive images. The first image depicts two
separated blurry circles, each labeled with a positive sign and the term “H atom.” The phrase written under them reads,
“Sufficiently far apart to have no interaction.” The second image shows the same two circles, but this time they are much closer
together and are labeled, “Atoms begin to interact as they move closer together.” The third image shows the two circles
overlapping, labeled, “H subscript 2,” and, “Optimum distance to achieve lowest overall energy of system.” Diagram b shows a
graph on which the y-axis is labeled “Energy ( J ),” and the x-axis is labeled, “Internuclear distance ( p m ).” The midpoint of the y-
axis is labeled as zero. The curve on the graph begins at zero p m and high on the y-axis. The graph slopes downward steeply to a
point far below the zero joule line on the y-axis and the lowest point reads “0.74 p m” and “H bonded to H bond length.” It is also
labeled “ negative 7.24 times 10 superscript negative 19 J.” The graph then rises again to zero J. The graph is accompanied by the
same images from diagram a; the first image correlates to the point in the graph where it crosses the zero point on the y-axis, the
third image where the graph is lowest.
The bond energy is the difference between the energy minimum (which occurs at the bond distance) and the energy of the two
separated atoms. This is the quantity of energy released when the bond is formed. Conversely, the same amount of energy is
required to break the bond. For the H molecule shown in Figure 5.2.1, at the bond distance of 74 pm the system is
2
J lower in energy than the two separated hydrogen atoms. This may seem like a small number. However, we know
−19
7.24 × 10
from our earlier description of thermochemistry that bond energies are often discussed on a per-mole basis. For example, it requires
J to break one H–H bond, but it takes 4.36 × 10 J to break 1 mole of H–H bonds. A comparison of some bond
−19 5
7.24 × 10
lengths and energies is shown in Table 5.2.1. We can find many of these bonds in a variety of molecules, and this table provides
average values. For example, breaking the first C–H bond in CH4 requires 439.3 kJ/mol, while breaking the first C–H bond in
H– CH C H (a common paint thinner) requires 375.5 kJ/mol.
2 6 5
Table 5.2.1 : Representative Bond Energies and Lengths

Bond Length (pm) Energy (kJ/mol) Bond Length (pm) Energy (kJ/mol)
H–H 74 436 C–O 140.1 358
H–C 106.8 413 C = O 119.7 745
H–N 101.5 391 C ≡ O 113.7 1072
H–O 97.5 467 H–Cl 127.5 431
C–C 150.6 347 H–Br 141.4 366
C = C 133.5 614 H–I 160.9 298

Bond Length (pm) Energy (kJ/mol) Bond Length (pm) Energy (kJ/mol)
C ≡ C 120.8 839 O–O 148 146
C–N 142.1 305 O = O 120.8 498
C = N 130.0 615 F–F 141.2 159
C ≡ N 116.1 891 Cl–Cl 198.8 243
In addition to the distance between two orbitals, the orientation of orbitals also affects their overlap (other than for two s orbitals,
which are spherically symmetric). Greater overlap is possible when orbitals are oriented such that they overlap on a direct line
between the two nuclei. Figure 5.2.2 illustrates this for two p orbitals from different atoms; the overlap is greater when the orbitals
overlap end to end rather than at an angle.
Figure 5.2.2 : (a) The overlap of two p orbitals is greatest when the orbitals are directed end to end. (b) Any other arrangement
results in less overlap. The dots indicate the locations of the nuclei.
The overlap of two s orbitals (as in H2), the overlap of an s orbital and a p orbital (as in HCl), and the end-to-end overlap of two p
orbitals (as in Cl2) all produce sigma bonds (σ bonds), as illustrated in Figure 5.2.3. A σ bond is a covalent bond in which the
electron density is concentrated in the region along the internuclear axis; that is, a line between the nuclei would pass through the
center of the overlap region. Single bonds in Lewis structures are described as σ bonds in valence bond theory.
Figure 5.2.3 : Sigma (σ) bonds form from the overlap of the following: (a) two s orbitals, (b) an s orbital and a p orbital, and (c) two
p orbitals. The dots indicate the locations of the nuclei.
Three diagrams are shown and labeled “a,” “b,” and “c.” Diagram a shows two spherical orbitals lying side by side and
overlapping. Diagram b shows one spherical and one peanut-shaped orbital lying near one another so that the spherical orbital
overlaps with one end of the peanut-shaped orbital. Diagram c shows two peanut-shaped orbitals lying end to end so that one end
of each orbital overlaps the other.
A pi bond (π bond) is a type of covalent bond that results from the side-by-side overlap of two p orbitals, as illustrated in Figure
5.2.4. In a π bond, the regions of orbital overlap lie on opposite sides of the internuclear axis. Along the axis itself, there is a node,
that is, a plane with no probability of finding an electron.
Figure 5.2.4 : Pi (π) bonds form from the side-by-side overlap of two p orbitals. The dots indicate the location of the nuclei.
While all single bonds are σ bonds, multiple bonds consist of both σ and π bonds. As the Lewis structures suggest, O2 contains a
double bond, and N2 contains a triple bond. The double bond consists of one σ bond and one π bond, and the triple bond consists of
one σ bond and two π bonds. Between any two atoms, the first bond formed will always be a σ bond, but there can only be one σ
bond in any one location. In any multiple bond, there will be one σ bond, and the remaining one or two bonds will be π bonds.
These bonds are described in more detail later in this chapter.

A diagram contains three Lewis structures. The left most structure shows an H atom bonded to a C l atom by a single bond. The C l
atom has three lone pairs of electrons. The phrase “One sigma bond No pi bonds” is written below the drawing. The center
structure shows two O atoms bonded by a double bond. The O atoms each have two lone pairs of electrons. The phrase “One sigma
bond One pi bond” is written below the drawing. The right most structure shows two N atoms bonded by a triple bond. Each N
atom has a lone pairs of electrons. The phrase “One sigma bond Two pi bonds” is written below the drawing.
As seen in Table 5.2.1, an average carbon-carbon single bond is 347 kJ/mol, while in a carbon-carbon double bond, the π bond
increases the bond strength by 267 kJ/mol. Adding an additional π bond causes a further increase of 225 kJ/mol. We can see a
similar pattern when we compare other σ and π bonds. Thus, each individual π bond is generally weaker than a corresponding σ
bond between the same two atoms. In a σ bond, there is a greater degree of orbital overlap than in a π bond.
 Example 5.2.1: Counting σ and π Bonds
Butadiene, C4H6, is used to make synthetic rubber. Identify the number of σ and π bonds contained in this molecule.
Butadiene
Solution
There are six σ C–H bonds and one σ C–C bond, for a total of seven from the single bonds. There are two double bonds that
each have a π bond in addition to the σ bond. This gives a total nine σ and two π bonds overall.
 Exercise 5.2.1
Identify each illustration as depicting a σ or π bond:

a. side-by-side overlap of a 4p and a 2p orbital
b. end-to-end overlap of a 4p and 4p orbital
c. end-to-end overlap of a 4p and a 2p orbital
Answer
(a) is a π bond with a node along the axis connecting the nuclei while (b) and (c) are σ bonds that overlap along the axis.
Summary
Valence bond theory describes bonding as a consequence of the overlap of two separate atomic orbitals on different atoms that
creates a region with one pair of electrons shared between the two atoms. When the orbitals overlap along an axis containing the
nuclei, they form a σ bond. When they overlap in a fashion that creates a node along this axis, they form a π bond.

Glossary
overlap
coexistence of orbitals from two different atoms sharing the same region of space, leading to the formation of a covalent bond
node
plane separating different lobes of orbitals, where the probability of finding an electron is zero
pi bond (π bond)
covalent bond formed by side-by-side overlap of atomic orbitals; the electron density is found on opposite sides of the
internuclear axis
sigma bond (σ bond)

covalent bond formed by overlap of atomic orbitals along the internuclear axis
valence bond theory

description of bonding that involves atomic orbitals overlapping to form σ or π bonds, within which pairs of electrons are
shared
This page titled 5.2: Valence Bond Theory is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
8.1: Valence Bond Theory is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

Explain the concept of atomic orbital hybridization
Determine the hybrid orbitals associated with various molecular geometries
Thinking in terms of overlapping atomic orbitals is one way for us to explain how chemical bonds form in diatomic molecules.
However, to understand how molecules with more than two atoms form stable bonds, we require a more detailed model. As an
example, let us consider the water molecule, in which we have one oxygen atom bonding to two hydrogen atoms. Oxygen has the
electron configuration 1s22s22p4, with two unpaired electrons (one in each of the two 2p orbitals). Valence bond theory would
predict that the two O–H bonds form from the overlap of these two 2p orbitals with the 1s orbitals of the hydrogen atoms. If this
were the case, the bond angle would be 90°, as shown in Figure 5.3.1, because p orbitals are perpendicular to each other.
Experimental evidence shows that the bond angle is 104.5°, not 90°. The prediction of the valence bond theory model does not
match the real-world observations of a water molecule; a different model is needed.
Figure 5.3.1 : The hypothetical overlap of two of the 2p orbitals on an oxygen atom (red) with the 1s orbitals of two hydrogen
atoms (blue) would produce a bond angle of 90°. This is not consistent with experimental evidence.1
Two peanut-shaped orbitals lie perpendicular to one another. They overlap with spherical orbitals to the left and top of the diagram.
Quantum-mechanical calculations suggest why the observed bond angles in H2O differ from those predicted by the overlap of the
1s orbital of the hydrogen atoms with the 2p orbitals of the oxygen atom. The mathematical expression known as the wave
function, ψ, contains information about each orbital and the wavelike properties of electrons in an isolated atom. When atoms are
bound together in a molecule, the wave functions combine to produce new mathematical descriptions that have different shapes.
This process of combining the wave functions for atomic orbitals is called hybridization and is mathematically accomplished by the
linear combination of atomic orbitals, LCAO, (a technique that we will encounter again later). The new orbitals that result are
called hybrid orbitals. The valence orbitals in an isolated oxygen atom are a 2s orbital and three 2p orbitals. The valence orbitals in
an oxygen atom in a water molecule differ; they consist of four equivalent hybrid orbitals that point approximately toward the
corners of a tetrahedron (Figure 5.3.2). Consequently, the overlap of the O and H orbitals should result in a tetrahedral bond angle
(109.5°). The observed angle of 104.5° is experimental evidence for which quantum-mechanical calculations give a useful
explanation: Valence bond theory must include a hybridization component to give accurate predictions.
Figure 5.3.2 : (a) A water molecule has four regions of electron density, so VSEPR theory predicts a tetrahedral arrangement of
hybrid orbitals. (b) Two of the hybrid orbitals on oxygen contain lone pairs, and the other two overlap with the 1s orbitals of
hydrogen atoms to form the O–H bonds in H2O. This description is more consistent with the experimental structure.
Two diagrams are shown and labeled “a” and “b.” Diagram a shows two peanut-shaped orbitals lying in a tetrahedral arrangement
around the letter “O.” Diagram b shows the same two orbitals, but they now overlap to the top and to the left with two spherical
orbitals, each labeled “H.” A pair of electrons occupies each lobe of the peanut-shaped orbitals.

The following ideas are important in understanding hybridization:
1. Hybrid orbitals do not exist in isolated atoms. They are formed only in covalently bonded atoms.
2. Hybrid orbitals have shapes and orientations that are very different from those of the atomic orbitals in isolated atoms.
3. A set of hybrid orbitals is generated by combining atomic orbitals. The number of hybrid orbitals in a set is equal to the number
of atomic orbitals that were combined to produce the set.
4. All orbitals in a set of hybrid orbitals are equivalent in shape and energy.
5. The type of hybrid orbitals formed in a bonded atom depends on its electron-pair geometry as predicted by the VSEPR theory.
6. Hybrid orbitals overlap to form σ bonds. Unhybridized orbitals overlap to form π bonds.
In the following sections, we shall discuss the common types of hybrid orbitals.
sp Hybridization
The beryllium atom in a gaseous BeCl2 molecule is an example of a central atom with no lone pairs of electrons in a linear
arrangement of three atoms. There are two regions of valence electron density in the BeCl2 molecule that correspond to the two
covalent Be–Cl bonds. To accommodate these two electron domains, two of the Be atom’s four valence orbitals will mix to yield
two hybrid orbitals. This hybridization process involves mixing of the valence s orbital with one of the valence p orbitals to yield
two equivalent sp hybrid orbitals that are oriented in a linear geometry (Figure 5.3.3). In this figure, the set of sp orbitals appears
similar in shape to the original p orbital, but there is an important difference. The number of atomic orbitals combined always
equals the number of hybrid orbitals formed. The p orbital is one orbital that can hold up to two electrons. The sp set is two
equivalent orbitals that point 180° from each other. The two electrons that were originally in the s orbital are now distributed to the
two sp orbitals, which are half filled. In gaseous BeCl2, these half-filled hybrid orbitals will overlap with orbitals from the chlorine
atoms to form two identical σ bonds.
Figure 5.3.3 : Hybridization of an s orbital (blue) and a p orbital (red) of the same atom produces two sp hybrid orbitals (yellow).
Each hybrid orbital is oriented primarily in just one direction. Note that each sp orbital contains one lobe that is significantly larger
than the other. The set of two sp orbitals are oriented at 180°, which is consistent with the geometry for two domains.
A series of three diagrams connected by a right-facing arrow that is labeled, “Hybridization,” and a downward-facing arrow
labeled, “Gives a linear arrangement,” are shown. The first diagram shows a blue spherical orbital and a red, peanut-shaped orbital,
each placed on an X, Y, Z axis system. The second diagram shows the same two orbitals, but they are now purple and have one
enlarged lobe and one smaller lobe. Each lies along the x-axis in the drawing. The third diagram shows the same two orbitals, but
their smaller lobes now overlap along the x-axis while their larger lobes are located at and labeled as “180 degrees” from one
another.
We illustrate the electronic differences in an isolated Be atom and in the bonded Be atom in the orbital energy-level diagram in
Figure 5.3.4. These diagrams represent each orbital by a horizontal line (indicating its energy) and each electron by an arrow.
Energy increases toward the top of the diagram. We use one upward arrow to indicate one electron in an orbital and two arrows (up
and down) to indicate two electrons of opposite spin.

Figure 5.3.4 : This orbital energy-level diagram shows the sp hybridized orbitals on Be in the linear BeCl2 molecule. Each of the
two sp hybrid orbitals holds one electron and is thus half filled and available for bonding via overlap with a Cl 3p orbital.
A diagram is shown in two parts, connected by a right facing arrow labeled, “Hybridization.” The left diagram shows an up-facing
arrow labeled, “E.” To the lower right of the arrow is a short, horizontal line labeled, “2 s,” that has two vertical half-arrows facing
up and down on it. To the upper right of the arrow are a series of three short, horizontal lines labeled, “2 p.” Above these two sets
of lines is the phrase, “Orbitals in an isolated B e atom.” The right side of the diagram shows two short, horizontal lines placed
halfway up the space and each labeled, “s p.” An upward-facing half arrow is drawn vertically on each line. Above these lines are
two other short, horizontal lines, each labeled, “2 p.” Above these two sets of lines is the phrase, “Orbitals in the s p hybridized B e
in B e C l subscript 2.”
When atomic orbitals hybridize, the valence electrons occupy the newly created orbitals. The Be atom had two valence electrons,
so each of the sp orbitals gets one of these electrons. Each of these electrons pairs up with the unpaired electron on a chlorine atom
when a hybrid orbital and a chlorine orbital overlap during the formation of the Be–Cl bonds. Any central atom surrounded by just
two regions of valence electron density in a molecule will exhibit sp hybridization. Other examples include the mercury atom in the
linear HgCl2 molecule, the zinc atom in Zn(CH3)2, which contains a linear C–Zn–C arrangement, and the carbon atoms in HCCH
and CO2.
sp2 Hybridization
The valence orbitals of a central atom surrounded by three regions of electron density consist of a set of three sp2 hybrid orbitals
and one unhybridized p orbital. This arrangement results from sp2 hybridization, the mixing of one s orbital and two p orbitals to
produce three identical hybrid orbitals oriented in a trigonal planar geometry (Figure 5.3.5).

Figure 5.3.5 : The hybridization of an s orbital (blue) and two p orbitals (red) produces three equivalent sp2 hybridized orbitals
(yellow) oriented at 120° with respect to each other. The remaining unhybridized p orbital is not shown here, but is located along
the z axis.
labeled, “Gives a trigonal planar arrangement,” are shown. The first diagram shows a blue spherical orbital and two red, peanut-
shaped orbitals, each placed on an X, Y, Z axis system. The two red orbitals are located on the x and z axes, respectively. The
second diagram shows the same three orbitals, but they are now purple and have one enlarged lobe and one smaller lobe. Each lies
in a different axis in the drawing. The third diagram shows the same three orbitals, but their smaller lobes now overlap while their
larger lobes are located at and labeled as “120 degrees” from one another.
Although quantum mechanics yields the “plump” orbital lobes as depicted in Figure 5.3.5, sometimes for clarity these orbitals are
drawn thinner and without the minor lobes, as in Figure 5.3.6, to avoid obscuring other features of a given illustration. We will use
these “thinner” representations whenever the true view is too crowded to easily visualize.
Figure 5.3.6 : This alternate way of drawing the trigonal planar sp2 hybrid orbitals is sometimes used in more crowded figures.
Three balloon-like orbitals are shown, and connect together near their narrower ends in one plane. The angle between a pair of
lobes is labeled, “120 degrees.”
The observed structure of the borane molecule, BH3, suggests sp2 hybridization for boron in this compound. The molecule is
trigonal planar, and the boron atom is involved in three bonds to hydrogen atoms ( Figure 5.3.7).
Figure 5.3.7 : BH3 is an electron-deficient molecule with a trigonal planar structure.

A boron atom is shown connected to three hydrogen atoms, which are arranged around it like a pyramid. The angle from one line
connecting the boron atom to a hydrogen atom to another line connecting the boron atom to a hydrogen atom is labeled, “120
degrees.”
We can illustrate the comparison of orbitals and electron distribution in an isolated boron atom and in the bonded atom in BH3 as
shown in the orbital energy level diagram in Figure 5.3.8. We redistribute the three valence electrons of the boron atom in the three

sp2 hybrid orbitals, and each boron electron pairs with a hydrogen electron when B–H bonds form.
Figure 5.3.8 : In an isolated B atom, there are one 2s and three 2p valence orbitals. When boron is in a molecule with three regions
of electron density, three of the orbitals hybridize and create a set of three sp2 orbitals and one unhybridized 2p orbital. The three
half-filled hybrid orbitals each overlap with an orbital from a hydrogen atom to form three σ bonds in BH3.
arrow labeled “E.” To the lower right of the arrow is a short, horizontal line labeled, “2 s,” that has two vertical half-arrows facing
up and down on it. To the upper right of the arrow are a series of three short, horizontal lines labeled, “2 p.” Above both sets of
these lines is the phrase, “Orbitals in an isolated B atom.” One of the lines has a vertical, up-facing arrow drawn on it. The right
side of the diagram shows three short, horizontal lines placed halfway up the space and each labeled, “s p superscript 2.” An
upward-facing half arrow is drawn vertically on each line. Above these lines is one other short, horizontal line, labeled, “2 p.”
Above both sets of lines is the phrase, “Orbitals in the s p superscript 2 hybridized B atom in B H subscript 3.”
Any central atom surrounded by three regions of electron density will exhibit sp2 hybridization. This includes molecules with a
lone pair on the central atom, such as ClNO (Figure 5.3.9), or molecules with two single bonds and a double bond connected to the
central atom, as in formaldehyde, CH2O, and ethene, H2CCH2.
Figure 5.3.9 : The central atom(s) in each of the structures shown contain three regions of electron density and are sp2 hybridized.
As we know from the discussion of VSEPR theory, a region of electron density contains all of the electrons that point in one
direction. A lone pair, an unpaired electron, a single bond, or a multiple bond would each count as one region of electron density.
Three Lewis structures are shown. The left-hand structure shows a chlorine atom surrounded by three lone pairs of electrons single
bonded to a nitrogen atom with one lone pair of electrons and double bonded to an oxygen atom with two lone pairs of electrons.
The middle structure shows a carbon atom single bonded to two hydrogen atoms and double bonded to an oxygen atom that has
two lone pairs of electrons. The right-hand structure shows two carbon atoms, double bonded to one another and each single
bonded to two hydrogen atoms.
sp3 Hybridization
The valence orbitals of an atom surrounded by a tetrahedral arrangement of bonding pairs and lone pairs consist of a set of four sp3
hybrid orbitals. The hybrids result from the mixing of one s orbital and all three p orbitals that produces four identical sp3 hybrid
orbitals (Figure 5.3.10). Each of these hybrid orbitals points toward a different corner of a tetrahedron.

Figure 5.3.10 : The hybridization of an s orbital (blue) and three p orbitals (red) produces four equivalent sp3 hybridized orbitals
(yellow) oriented at 109.5° with respect to each other.
labeled, “Gives a tetrahedral arrangement,” are shown. The first diagram shows a blue spherical orbital and three red, peanut-
shaped orbitals, each placed on an x, y, z axis system. The three red orbitals are located on the x , y and z axes, respectively. The
second diagram shows the same four orbitals, but they are now purple and have one enlarged lobe and one smaller lobe. Each lies
in a different axis in the drawing. The third diagram shows the same four orbitals, but their smaller lobes now overlap to form a
tetrahedral structure.
A molecule of methane, CH4, consists of a carbon atom surrounded by four hydrogen atoms at the corners of a tetrahedron. The
carbon atom in methane exhibits sp3 hybridization. We illustrate the orbitals and electron distribution in an isolated carbon atom
and in the bonded atom in CH4 in Figure 5.3.11. The four valence electrons of the carbon atom are distributed equally in the hybrid
orbitals, and each carbon electron pairs with a hydrogen electron when the C–H bonds form.

Figure 5.3.11 : The four valence atomic orbitals from an isolated carbon atom all hybridize when the carbon bonds in a molecule
like CH4 with four regions of electron density. This creates four equivalent sp3 hybridized orbitals. Overlap of each of the hybrid
orbitals with a hydrogen orbital creates a C–H σ bond.
arrow labeled “E.” To the lower right of the arrow is a short, horizontal line labeled, “2 s,” that has two vertical half-arrows facing
up and down on it. To the upper right of the arrow are a series of three short, horizontal lines labeled, “2 p.” Two of the lines have a
vertical, up-facing arrow drawn on them. Above both sets of lines is the phrase, “Orbitals in an isolated C atom.” The right side of
the diagram shows four short, horizontal lines placed halfway up the space and each labeled, “s p superscript 3.” An upward-facing
half arrow is drawn vertically on each line. Above these lines is the phrase, “Orbitals in the s p superscript 3 hybridized C atom in
C H subscript 4.”
In a methane molecule, the 1s orbital of each of the four hydrogen atoms overlaps with one of the four sp3 orbitals of the carbon
atom to form a sigma (σ) bond. This results in the formation of four strong, equivalent covalent bonds between the carbon atom and
each of the hydrogen atoms to produce the methane molecule, CH4.
The structure of ethane, C2H6, is similar to that of methane in that each carbon in ethane has four neighboring atoms arranged at the
corners of a tetrahedron—three hydrogen atoms and one carbon atom (Figure 5.3.10). However, in ethane an sp3 orbital of one
carbon atom overlaps end to end with an sp3 orbital of a second carbon atom to form a σ bond between the two carbon atoms. Each
of the remaining sp3 hybrid orbitals overlaps with an s orbital of a hydrogen atom to form carbon–hydrogen σ bonds. The structure
and overall outline of the bonding orbitals of ethane are shown in Figure 5.3.12. The orientation of the two CH3 groups is not fixed
relative to each other. Experimental evidence shows that rotation around σ bonds occurs easily.
Figure 5.3.12 : (a) In the ethane molecule, C2H6, each carbon has four sp3 orbitals. (b) These four orbitals overlap to form seven σ
bonds.
Two diagrams are shown and labeled “a” and “b.” Diagram a shows two carbon atoms, each surrounded by their four s p subscript
three hybridized orbitals in a three dimensional arrangement. Each of the orbitals is shown overlapping with a spherical hydrogen
atom. Diagram b shows the same general arrangement, but the hydrogen atoms are just represented by an, “H” and their spherical
orbitals are not shown.
An sp3 hybrid orbital can also hold a lone pair of electrons. For example, the nitrogen atom in ammonia is surrounded by three
bonding pairs and a lone pair of electrons directed to the four corners of a tetrahedron. The nitrogen atom is sp3 hybridized with
one hybrid orbital occupied by the lone pair.
The molecular structure of water is consistent with a tetrahedral arrangement of two lone pairs and two bonding pairs of electrons.
Thus we say that the oxygen atom is sp3 hybridized, with two of the hybrid orbitals occupied by lone pairs and two by bonding
pairs. Since lone pairs occupy more space than bonding pairs, structures that contain lone pairs have bond angles slightly distorted
from the ideal. Perfect tetrahedra have angles of 109.5°, but the observed angles in ammonia (107.3°) and water (104.5°) are
slightly smaller. Other examples of sp3 hybridization include CCl4, PCl3, and NCl3.

sp3d and sp3d2 Hybridization
To describe the five bonding orbitals in a trigonal bipyramidal arrangement, we must use five of the valence shell atomic orbitals
(the s orbital, the three p orbitals, and one of the d orbitals), which gives five sp3d hybrid orbitals. With an octahedral arrangement
of six hybrid orbitals, we must use six valence shell atomic orbitals (the s orbital, the three p orbitals, and two of the d orbitals in its
valence shell), which gives six sp3d2 hybrid orbitals. These hybridizations are only possible for atoms that have d orbitals in their
valence subshells (that is, not those in the first or second period).
Figure 5.3.13 : The three compounds pictured exhibit sp3d hybridization in the central atom and a trigonal bipyramid form. SF4 and
C lF
4
+
have one lone pair of electrons on the central atom, and ClF3 has two lone pairs giving it the T-shape shown.
Three Lewis structures are shown along with designations of molecular shape. The left image shows a sulfur atom singly bonded to
four fluorine atoms. The sulfur atom has one lone pair of electrons while each fluorine has three. Two fluorine atoms are drawn
vertically up and down from the sulfur while the other two are shown going into and out of the page. The second structure shows
one chlorine atom singly bonded to three fluorine atoms. The chlorine has two lone pairs of electrons while each fluorine has three.
Two fluorine atoms are drawn vertically up and down from the sulfur while the other is shown horizontally. The right structure
shows a chlorine atom singly bonded to four fluorine atoms. The chlorine atom has one lone pair of electrons and a superscript plus
sign, while each fluorine has three lone pairs of electrons. Two fluorine atoms are drawn vertically up and down from the sulfur
while the other two are shown going into and out of the page.
In a molecule of phosphorus pentachloride, PCl5, there are five P–Cl bonds (thus five pairs of valence electrons around the
phosphorus atom) directed toward the corners of a trigonal bipyramid. We use the 3s orbital, the three 3p orbitals, and one of the 3d
orbitals to form the set of five sp3d hybrid orbitals (Figure 5.3.13) that are involved in the P–Cl bonds. Other atoms that exhibit
sp3d hybridization include the sulfur atom in SF4 and the chlorine atoms in ClF3 and in ClF . (The electrons on fluorine atoms are
+
4
omitted for clarity.)
Figure 5.3.14 : (a) The five regions of electron density around phosphorus in PCl5 require five hybrid sp3d orbitals. (b) These
orbitals combine to form a trigonal bipyramidal structure with each large lobe of the hybrid orbital pointing at a vertex. As before,
there are also small lobes pointing in the opposite direction for each orbital (not shown for clarity).
Two images are shown and labeled “a” and “b.” Image a depicts a ball-and-stick model in a trigonal bipyramidal arrangement.
Image b depicts the hybrid orbitals in the same arrangement and each is labeled, “s p superscript three d.”
The sulfur atom in sulfur hexafluoride, SF6, exhibits sp3d2 hybridization. A molecule of sulfur hexafluoride has six bonding pairs
of electrons connecting six fluorine atoms to a single sulfur atom. There are no lone pairs of electrons on the central atom. To bond
six fluorine atoms, the 3s orbital, the three 3p orbitals, and two of the 3d orbitals form six equivalent sp3d2 hybrid orbitals, each
directed toward a different corner of an octahedron. Other atoms that exhibit sp3d2 hybridization include the phosphorus atom in
PCl , the iodine atom in the interhalogens IF , IF5, ICl , IF and the xenon atom in XeF4.
− + − −
6 6 4 4

Figure 5.3.15 : (a) Sulfur hexafluoride, SF6, has an octahedral structure that requires sp3d2 hybridization. (b) The six sp3d2 orbitals
form an octahedral structure around sulfur. Again, the minor lobe of each orbital is not shown for clarity.
Two images are shown and labeled “a” and “b.” Image a depicts a ball-and-stick model in an octahedral arrangement. Image b
depicts the hybrid orbitals in the same arrangement and each is labeled, “s p superscript three d superscript two.”
Assignment of Hybrid Orbitals to Central Atoms

The hybridization of an atom is determined based on the number of regions of electron density that surround it. The geometrical
arrangements characteristic of the various sets of hybrid orbitals are shown in Figure 5.3.16. These arrangements are identical to
those of the electron-pair geometries predicted by VSEPR theory. VSEPR theory predicts the shapes of molecules, and hybrid
orbital theory provides an explanation for how those shapes are formed. To find the hybridization of a central atom, we can use the
following guidelines:
1. Determine the Lewis structure of the molecule.
2. Determine the number of regions of electron density around an atom using VSEPR theory, in which single bonds, multiple
bonds, radicals, and lone pairs each count as one region.
3. Assign the set of hybridized orbitals from Figure 5.3.16 that corresponds to this geometry.

Figure 5.3.16 : The shapes of hybridized orbital sets are consistent with the electron-pair geometries. For example, an atom
surrounded by three regions of electron density is sp2 hybridized, and the three sp2 orbitals are arranged in a trigonal planar fashion.
A table is shown that is composed of five columns and six rows. The header row contains the phrases, “Regions of electron
density,” “Arrangement,” (which has two columns below it), and “Hybridization,” (which has two columns below it). The first
column contains the numbers “2,” “3,” “4,” “5,” and “6.” The second column contains images of a line, a triangle, a three sided
pyramid, a trigonal bipyramid, and an eight-faced ocatahedron. The third column contains the terms, “Linear,” “Trigonal planar,”
“Tetrahedral,” “Trigonal bipyramidal,” and “Octahedral.” The fourth column contains the terms “s p,” “s p superscript 2,” “s p
superscript 3,” “s p superscript 3 d,” and “s p superscript 3 d superscript 2.” The last column contains drawings of the molecules
beginning with a peanut-shaped structure marked with an angle of “180 degrees.” The second structure is made up of three equal-
sized, rounded structures connected at one point with an angle of “120 degrees,” while the third structure is a three-dimensional
arrangement of four equal-sized, rounded structures labeled as “109.5 degrees.” The fourth structure is made up of five equal-sized,
rounded structures connected at “120 and 90 degrees,” while the fifth structure has six equal-sized, rounded structures connected at
“90 degrees.”
It is important to remember that hybridization was devised to rationalize experimentally

observed molecular geometries, not the other way around.
The model works well for molecules containing small central atoms, in which the valence electron pairs are close together in space.
However, for larger central atoms, the valence-shell electron pairs are farther from the nucleus, and there are fewer repulsions.
Their compounds exhibit structures that are often not consistent with VSEPR theory, and hybridized orbitals are not necessary to
explain the observed data.

Three Lewis structures are shown. The left structure shows an oxygen atom with two lone pairs of electrons single bonded to two
hydrogen atoms. The middle structure is made up of a sulfur atom with two lone pairs of electrons single bonded to two hydrogen
atoms. The right structure is made up of a tellurium atom with two lone pairs of electrons single bonded to two hydrogen atoms.
From left to right, the bond angles of each molecule decrease.
For example, we have discussed the H–O–H bond angle in H2O, 104.5°, which is more consistent with sp3 hybrid orbitals (109.5°)
on the central atom than with 2p orbitals (90°). Sulfur is in the same group as oxygen, and H2S has a similar Lewis structure.
However, it has a much smaller bond angle (92.1°), which indicates much less hybridization on sulfur than oxygen. Continuing
down the group, tellurium is even larger than sulfur, and for H2Te, the observed bond angle (90°) is consistent with overlap of the
5p orbitals, without invoking hybridization. We invoke hybridization where it is necessary to explain the observed structures.
 Example 5.3.1: Assigning Hybridization
Ammonium sulfate is important as a fertilizer. What is the hybridization of the sulfur atom in the sulfate ion, SO 2−
4
?
Solution
The Lewis structure of sulfate shows there are four regions of electron density.
Figure 5.3.16 ).
A structure is shown in which a sulfur atom is bonded to four oxygen atoms in a tetrahedral arrangement. Two of the oxygen
atoms have a negative charge.
 Exercise 5.3.1
What is the hybridization of the selenium atom in SeF4?
A Lewis structure is shown in which four fluorine atoms are each attached to one sulfur atom. Two of the attached fluorine
atoms are vertically attached up and down, while two are attached into and out of the page to the right. The sulfur also has one
lone pair of electrons attached to the left of the structure.
Answer
The selenium atom is sp3d hybridized.

 Example 5.3.2: Assigning Hybridization
Urea, NH2C(O)NH2, is sometimes used as a source of nitrogen in fertilizers. What is the hybridization of each nitrogen and
carbon atom in urea?
Solution
The Lewis structure of urea is
Figure 5.3.16 ). This is the hybridization of the nitrogen atoms in urea.

A Lewis structure is shown in which a carbon atom is double bonded to an oxygen atom that has two lone pairs of electrons.
The carbon atom forms single bonds to two nitrogen atoms. Each nitrogen is single bonded to two hydrogen atoms, and each
nitrogen atoms has one lone pair of electrons.
The carbon atom is surrounded by three regions of electron density, positioned in a trigonal planar arrangement. The
hybridization in a trigonal planar electron pair geometry is sp2 (Figure 5.3.16), which is the hybridization of the carbon atom in
urea.
 Exercise 5.3.1
Acetic acid, H3CC(O)OH, is the molecule that gives vinegar its odor and sour taste. What is the hybridization of the two
carbon atoms in acetic acid?
A Lewis structure is shown in which a carbon atom is double bonded to an oxygen atom that has two lone pairs of electrons
and single bonded to another oxygen atom that is single boned to a hydrogen atom. This second oxygen atom has two lone
pairs of electrons. The carbon is also single bonded to a carbon atom that is single bonded to three hydrogen atoms.
Answer
H3C, sp3; C(O)OH, sp2
Summary
We can use hybrid orbitals, which are mathematical combinations of some or all of the valence atomic orbitals, to describe the
electron density around covalently bonded atoms. These hybrid orbitals either form sigma (σ) bonds directed toward other atoms of
the molecule or contain lone pairs of electrons. We can determine the type of hybridization around a central atom from the
geometry of the regions of electron density about it. Two such regions imply sp hybridization; three, sp2 hybridization; four, sp3
hybridization; five, sp3d hybridization; and six, sp3d2 hybridization. Pi (π) bonds are formed from unhybridized atomic orbitals (p
or d orbitals).

Footnotes
1. Note that orbitals may sometimes be drawn in an elongated “balloon” shape rather than in a more realistic “plump” shape in
order to make the geometry easier to visualize.
Glossary
hybrid orbital
orbital created by combining atomic orbitals on a central atom
hybridization
model that describes the changes in the atomic orbitals of an atom when it forms a covalent compound
sp hybrid orbital
one of a set of two orbitals with a linear arrangement that results from combining one s and one p orbital
sp2 hybrid orbital

one of a set of three orbitals with a trigonal planar arrangement that results from combining one s and two p orbitals
sp3 hybrid orbital

one of a set of four orbitals with a tetrahedral arrangement that results from combining one s and three p orbitals
sp3d hybrid orbital

one of a set of five orbitals with a trigonal bipyramidal arrangement that results from combining one s, three p, and one d orbital
sp3d2 hybrid orbital

one of a set of six orbitals with an octahedral arrangement that results from combining one s, three p, and two d orbitals
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5.4: Multiple Bonds
Describe multiple covalent bonding in terms of atomic orbital overlap
Relate the concept of resonance to π-bonding and electron delocalization
The hybrid orbital model appears to account well for the geometry of molecules involving single covalent bonds. Is it also capable
of describing molecules containing double and triple bonds? We have already discussed that multiple bonds consist of σ and π
bonds. Next we can consider how we visualize these components and how they relate to hybrid orbitals. The Lewis structure of
ethene, C2H4, shows us that each carbon atom is surrounded by one other carbon atom and two hydrogen atoms.
Figure 5.4.2 ).
A Lewis structure is shown in which two carbon atoms are bonded together by a double bond. Each carbon atom is bonded to two
hydrogen atoms by a single bond.
Figure 5.4.1 : In ethene, each carbon atom is sp2 hybridized, and the sp2 orbitals and the p orbital are singly occupied. The hybrid
orbitals overlap to form σ bonds, while the p orbitals on each carbon atom overlap to form a π bond.
arrow labeled, “E.” To the lower right of the arrow is a short, horizontal line labeled, “2 s,” that has two vertical half-arrows facing
up and down on it. To the upper right of the arrow are a series of three short, horizontal lines labeled, “2 p.” Above both sets of
lines is the phrase, “Orbitals in an isolated C atom.” Two of the lines have vertical, up-facing arrows drawn on them. The right side
of the diagram shows three short, horizontal lines placed halfway up the space and each labeled, “s p superscript 2.” An upward-
facing half arrow is drawn vertically on each line. Above these lines is one other short, horizontal line, labeled, “p.” Above both
sets of lines is the phrase, “Orbitals in the s p superscript 2 hybridized C atom in C subscript 2 H subscript 4.”
The π bond in the C=C double bond results from the overlap of the third (remaining) 2p orbital on each carbon atom that is not
involved in hybridization. This unhybridized p orbital (lobes shown in red and blue in Figure 5.4.2) is perpendicular to the plane of
the sp2 hybrid orbitals. Thus the unhybridized 2p orbitals overlap in a side-by-side fashion, above and below the internuclear axis
and form a π bond.

Figure 5.4.2 : In the ethene molecule, C2H4, there are (a) five σ bonds. One C–C σ bond results from overlap of sp2 hybrid orbitals
on the carbon atom with one sp2 hybrid orbital on the other carbon atom. Four C–H bonds result from the overlap between the C
atoms' sp2 orbitals with s orbitals on the hydrogen atoms. (b) The π bond is formed by the side-by-side overlap of the two
unhybridized p orbitals in the two carbon atoms. The two lobes of the π bond are above and below the plane of the σ system.
Two diagrams are shown labeled, “a” and “b.” Diagram a shows two carbon atoms with three purple balloon-like orbitals arranged
in a plane around them and two red balloon-like orbitals arranged vertically and perpendicularly to the plane. There is an overlap of
two of the purple orbitals in between the two carbon atoms, and the other four purple orbitals that face the outside of the molecule
are shown interacting with spherical blue orbitals from four hydrogen atoms. Diagram b depicts a similar image to diagram a, but
the red, vertical orbitals are interacting above and below the plane of the molecule to form two areas labeled, “One pi bond.”
In an ethene molecule, the four hydrogen atoms and the two carbon atoms are all in the same plane. If the two planes of sp2 hybrid
orbitals tilted relative to each other, the p orbitals would not be oriented to overlap efficiently to create the π bond. The planar
configuration for the ethene molecule occurs because it is the most stable bonding arrangement. This is a significant difference
between σ and π bonds; rotation around single (σ) bonds occurs easily because the end-to-end orbital overlap does not depend on
the relative orientation of the orbitals on each atom in the bond. In other words, rotation around the internuclear axis does not
change the extent to which the σ bonding orbitals overlap because the bonding electron density is symmetric about the axis.
Rotation about the internuclear axis is much more difficult for multiple bonds; however, this would drastically alter the off-axis
overlap of the π bonding orbitals, essentially breaking the π bond.
A diagram of a carbon atom with two balloon-like purple orbitals labeled, “sp” arranged in a linear fashion around it is shown. Four
red balloon-like orbitals are aligned in pairs in the y and z axes around the carbon and are labeled, “unhybridized p orbital,” and,
“Second unhybridized p orbital.”
Figure 5.4.3 : Diagram of the two linear sp hybrid orbitals of a carbon atom, which lie in a straight line, and the two unhybridized p
orbitals at perpendicular angles.
In molecules with sp hybrid orbitals, two unhybridized p orbitals remain on the atom (Figure 5.4.3). We find this situation in
acetylene, H−C≡C−H, which is a linear molecule. The sp hybrid orbitals of the two carbon atoms overlap end to end to form a σ
bond between the carbon atoms (Figure 5.4.4). The remaining sp orbitals form σ bonds with hydrogen atoms. The two
unhybridized p orbitals per carbon are positioned such that they overlap side by side and, hence, form two π bonds. The two carbon
atoms of acetylene are thus bound together by one σ bond and two π bonds, giving a triple bond.

Figure 5.4.4 : (a) In the acetylene molecule, C2H2, there are two C–H σ bonds and a C≡C triple bond involving one C–C σ bond and
two C–C π bonds. The dashed lines, each connecting two lobes, indicate the side-by-side overlap of the four unhybridized p
orbitals. (b) This shows the overall outline of the bonds in C2H2. The two lobes of each of the π bonds are positioned across from
each other around the line of the C–C σ bond.
Two diagrams are shown and labeled, “a” and “b.” Diagram a shows two carbon atoms with two purple balloon-like orbitals
arranged in a plane around each of them, and four red balloon-like orbitals arranged along the y and z axes perpendicular to the
plane of the molecule. There is an overlap of two of the purple orbitals in between the two carbon atoms. The other two purple
orbitals that face the outside of the molecule are shown interacting with spherical blue orbitals from two hydrogen atoms. Diagram
b depicts a similar image to diagram a, but the red, vertical orbitals are interacting above and below and to the front and back of the
plane of the molecule to form two areas labeled, “One pi bond,” and, “Second pi bond,” each respectively.
Hybridization involves only σ bonds, lone pairs of electrons, and single unpaired electrons (radicals). Structures that account for
these features describe the correct hybridization of the atoms. However, many structures also include resonance forms. Remember
that resonance forms occur when various arrangements of π bonds are possible. Since the arrangement of π bonds involves only the
unhybridized orbitals, resonance does not influence the assignment of hybridization.
For example, molecule benzene has two resonance forms (Figure 5.4.5). We can use either of these forms to determine that each of
the carbon atoms is bonded to three other atoms with no lone pairs, so the correct hybridization is sp2. The electrons in the
unhybridized p orbitals form π bonds. Neither resonance structure completely describes the electrons in the π bonds. They are not
located in one position or the other, but in reality are delocalized throughout the ring. Valence bond theory does not easily address
delocalization. Bonding in molecules with resonance forms is better described by molecular orbital theory.
A diagram is shown that is made up of two Lewis structures connected by a double ended arrow. The left image shows six carbon
atoms bonded together with alternating double and single bonds to form a six-sided ring. Each carbon is also bonded to a hydrogen
atom by a single bond. The right image shows the same structure, but the double and single bonds in between the carbon atoms
have changed positions.
Figure 5.4.5 : Each carbon atom in benzene, C6H6, is sp2 hybridized, independently of which resonance form is considered. The
electrons in the π bonds are not located in one set of p orbitals or the other, but rather delocalized throughout the molecule.
 Example 5.4.1: Assignment of Hybridization Involving Resonance
Some acid rain results from the reaction of sulfur dioxide with atmospheric water vapor, followed by the formation of sulfuric
acid. Sulfur dioxide, SO , is a major component of volcanic gases as well as a product of the combustion of sulfur-containing
2
coal. What is the hybridization of the S atom in SO ? 2
Solution
The resonance structures of SO are 2

Two Lewis structures connected by a double-ended arrow are shown. The left structure shows a sulfur atom with one lone pair
of electrons and a positive sign which is single bonded on one side to an oxygen atom with three lone pairs of electrons and a
negative sign. The sulfur atom is double bonded on the other side to another oxygen atom with two lone pairs of electrons. The
right-hand structure is the same as the left except that the position of the double bonded oxygen atom is switched. In both
structures the attached oxygen atoms form an acute angle in terms of the sulfur atom.
The sulfur atom is surrounded by two bonds and one lone pair of electrons in either resonance structure. Therefore, the
electron-pair geometry is trigonal planar, and the hybridization of the sulfur atom is sp2.
 Exercise 5.4.1
Another acid in acid rain is nitric acid, HNO3, which is produced by the reaction of nitrogen dioxide, NO2, with atmospheric
water vapor. What is the hybridization of the nitrogen atom in NO2? (Note: the lone electron on nitrogen occupies a hybridized
orbital just as a lone pair would.)
Answer
sp2
Summary
Multiple bonds consist of a σ bond located along the axis between two atoms and one or two π bonds. The σ bonds are usually
formed by the overlap of hybridized atomic orbitals, while the π bonds are formed by the side-by-side overlap of unhybridized
orbitals. Resonance occurs when there are multiple unhybridized orbitals with the appropriate alignment to overlap, so the
placement of π bonds can vary.
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Outline the basic quantum-mechanical approach to deriving molecular orbitals from atomic orbitals
Describe traits of bonding and antibonding molecular orbitals
Calculate bond orders based on molecular electron configurations
Write molecular electron configurations for first- and second-row diatomic molecules
Relate these electron configurations to the molecules’ stabilities and magnetic properties
For almost every covalent molecule that exists, we can now draw the Lewis structure, predict the electron-pair geometry, predict
the molecular geometry, and come close to predicting bond angles. However, one of the most important molecules we know, the
oxygen molecule O2, presents a problem with respect to its Lewis structure. We would write the following Lewis structure for O2:
A Lewis structure is shown. It is made up of two oxygen atoms, each with two lone pairs of electrons, bonded together with a
double bond.
This electronic structure adheres to all the rules governing Lewis theory. There is an O=O double bond, and each oxygen atom has
eight electrons around it. However, this picture is at odds with the magnetic behavior of oxygen. By itself, O2 is not magnetic, but it
is attracted to magnetic fields. Thus, when we pour liquid oxygen past a strong magnet, it collects between the poles of the magnet
and defies gravity. Such attraction to a magnetic field is called paramagnetism, and it arises in molecules that have unpaired
electrons. And yet, the Lewis structure of O2 indicates that all electrons are paired. How do we account for this discrepancy?
Magnetic susceptibility measures the force experienced by a substance in a magnetic field. When we compare the weight of a
sample to the weight measured in a magnetic field (Figure 5.5.1), paramagnetic samples that are attracted to the magnet will appear
heavier because of the force exerted by the magnetic field. We can calculate the number of unpaired electrons based on the increase
in weight.
Figure 5.5.1 : A Gouy balance compares the mass of a sample in the presence of a magnetic field with the mass with the
electromagnet turned off to determine the number of unpaired electrons in a sample.
Experiments show that each O2 molecule has two unpaired electrons. The Lewis-structure model does not predict the presence of
these two unpaired electrons. Unlike oxygen, the apparent weight of most molecules decreases slightly in the presence of an
inhomogeneous magnetic field. Materials in which all of the electrons are paired are diamagnetic and weakly repel a magnetic
field. Paramagnetic and diamagnetic materials do not act as permanent magnets. Only in the presence of an applied magnetic field
do they demonstrate attraction or repulsion.

levitating frog
Video 5.5.1 : Water, like most molecules, contains all paired electrons. Living things contain a large percentage of water, so they
demonstrate diamagnetic behavior. If you place a frog near a sufficiently large magnet, it will levitate. You can see videos of
diamagnetic floating frogs, strawberries, and more (levitating frog [www.youtube.com])
Molecular orbital theory (MO theory) provides an explanation of chemical bonding that accounts for the paramagnetism of the
oxygen molecule. It also explains the bonding in a number of other molecules, such as violations of the octet rule and more
molecules with more complicated bonding (beyond the scope of this text) that are difficult to describe with Lewis structures.
Additionally, it provides a model for describing the energies of electrons in a molecule and the probable location of these electrons.
Unlike valence bond theory, which uses hybrid orbitals that are assigned to one specific atom, MO theory uses the combination of
atomic orbitals to yield molecular orbitals that are delocalized over the entire molecule rather than being localized on its constituent
atoms. MO theory also helps us understand why some substances are electrical conductors, others are semiconductors, and still
others are insulators. Table 5.5.1 summarizes the main points of the two complementary bonding theories. Both theories provide
different, useful ways of describing molecular structure.
Table $\PageIndex{1}$: Comparison of Bonding Theories
Valence Bond Theory Molecular Orbital Theory
considers bonds as localized between one pair of atoms considers electrons delocalized throughout the entire molecule
creates bonds from overlap of atomic orbitals (s, p, d…) and hybrid
combines atomic orbitals to form molecular orbitals (σ, σ*, π, π*)
orbitals (sp, sp2, sp3…)
creates bonding and antibonding interactions based on which orbitals

forms σ or π bonds
are filled
predicts molecular shape based on the number of regions of electron

predicts the arrangement of electrons in molecules
density
needs multiple structures to describe resonance
Molecular orbital theory describes the distribution of electrons in molecules in much the same way that the distribution of electrons
in atoms is described using atomic orbitals. Using quantum mechanics, the behavior of an electron in a molecule is still described
by a wave function, Ψ, analogous to the behavior in an atom. Just like electrons around isolated atoms, electrons around atoms in
molecules are limited to discrete (quantized) energies. The region of space in which a valence electron in a molecule is likely to be
found is called a molecular orbital (Ψ2). Like an atomic orbital, a molecular orbital is full when it contains two electrons with
opposite spin.
We will consider the molecular orbitals in molecules composed of two identical atoms (H2 or Cl2, for example). Such molecules
are called homonuclear diatomic molecules. In these diatomic molecules, several types of molecular orbitals occur.
The mathematical process of combining atomic orbitals to generate molecular orbitals is called the linear combination of atomic
orbitals (LCAO). The wave function describes the wavelike properties of an electron. Molecular orbitals are combinations of
atomic orbital wave functions. Combining waves can lead to constructive interference, in which peaks line up with peaks, or
destructive interference, in which peaks line up with troughs (Figure 5.5.2). In orbitals, the waves are three dimensional, and they
combine with in-phase waves producing regions with a higher probability of electron density and out-of-phase waves producing
nodes, or regions of no electron density.

Figure 5.5.2 : (a) When in-phase waves combine, constructive interference produces a wave with greater amplitude. (b) When out-
of-phase waves combine, destructive interference produces a wave with less (or no) amplitude.
A pair of diagrams are shown and labeled, “a” and “b.” Diagram a shows two identical waves with two crests and two troughs.
They are drawn one above the other with a plus sign in between and an equal sign to the right. To the right of the equal sign is a
much taller wave with a same number of troughs and crests. Diagram b shows two waves with two crests and two troughs, but they
are mirror images of one another rotated over a horizontal axis. They are drawn one above the other with a plus sign in between
and an equal sign to the right. To the right of the equal sign is a flat line.
There are two types of molecular orbitals that can form from the overlap of two atomic s orbitals on adjacent atoms. The two types
are illustrated in Figure 5.5.3. The in-phase combination produces a lower energy σs molecular orbital (read as "sigma-s") in which
most of the electron density is directly between the nuclei. The out-of-phase addition (which can also be thought of as subtracting
the wave functions) produces a higher energy σ molecular orbital (read as "sigma-s-star") molecular orbital in which there is a
∗
s
node between the nuclei. The asterisk signifies that the orbital is an antibonding orbital. Electrons in a σs orbital are attracted by
both nuclei at the same time and are more stable (of lower energy) than they would be in the isolated atoms. Adding electrons to
these orbitals creates a force that holds the two nuclei together, so we call these orbitals bonding orbitals. Electrons in the σ ∗
s
orbitals are located well away from the region between the two nuclei. The attractive force between the nuclei and these electrons
pulls the two nuclei apart. Hence, these orbitals are called antibonding orbitals. Electrons fill the lower-energy bonding orbital
before the higher-energy antibonding orbital, just as they fill lower-energy atomic orbitals before they fill higher-energy atomic
orbitals.
Figure 5.5.3 : Sigma (σ) and sigma-star (σ*) molecular orbitals are formed by the combination of two s atomic orbitals. The plus
(+) signs indicate the locations of nuclei.
A diagram is shown that depicts a vertical upward-facing arrow that lies to the left of all the other portions of the diagram and is
labeled, “E.” To the immediate right of the midpoint of the arrow are two circles each labeled with a positive sign, the letter S, and
the phrase, “Atomic orbitals.” These are followed by a right-facing horizontal arrow that points to the same two circles labeled with
plus signs, but they are now touching and are labeled, “Combine atomic orbitals.” Two right-facing arrows lead to the last portion
of the diagram, one facing upward and one facing downward. The upper arrow is labeled, “Subtract,” and points to two oblong
ovals labeled with plus signs, and the phrase, “Antibonding orbitals sigma subscript s superscript asterisk.” The lower arrow is
labeled, “Add,” and points to an elongated oval with two plus signs that is labeled, “Bonding orbital sigma subscript s.” The
heading over the last section of the diagram are the words, “Molecular orbitals.”
In p orbitals, the wave function gives rise to two lobes with opposite phases, analogous to how a two-dimensional wave has both
parts above and below the average. We indicate the phases by shading the orbital lobes different colors. When orbital lobes of the
same phase overlap, constructive wave interference increases the electron density. When regions of opposite phase overlap, the
destructive wave interference decreases electron density and creates nodes. When p orbitals overlap end to end, they create σ and
σ* orbitals (Figure 5.5.4). If two atoms are located along the x-axis in a Cartesian coordinate system, the two px orbitals overlap
end to end and form σpx (bonding) and σ (antibonding) (read as "sigma-p-x" and "sigma-p-x star," respectively). Just as with s-
∗
px
orbital overlap, the asterisk indicates the orbital with a node between the nuclei, which is a higher-energy, antibonding orbital.

Two horizontal rows of diagrams are shown. The upper diagram shows two equally-sized peanut-shaped orbitals with a plus sign in
between them connected to a merged orbital diagram by a right facing arrow. The merged diagram has a much larger oval at the
center and much smaller ovular orbitals on the edge. It is labeled, “sigma subscript p x.” The lower diagram shows two equally-
sized peanut-shaped orbitals with a plus sign in between them connected to a split orbital diagram by a right facing arrow. The split
diagram has a much larger oval at the outer ends and much smaller ovular orbitals on the inner edges. It is labeled, “sigma subscript
p x superscript asterisk”.
Figure 5.5.4 : Combining wave functions of two p atomic orbitals along the internuclear axis creates two molecular orbitals, σp and
σ .
∗
p
The side-by-side overlap of two p orbitals gives rise to a pi (π) bonding molecular orbital and a $π^*$ antibonding molecular
orbital, as shown in Figure 5.5.5. In valence bond theory, we describe π bonds as containing a nodal plane containing the
internuclear axis and perpendicular to the lobes of the p orbitals, with electron density on either side of the node. In molecular
orbital theory, we describe the π orbital by this same shape, and a π bond exists when this orbital contains electrons. Electrons in
this orbital interact with both nuclei and help hold the two atoms together, making it a bonding orbital. For the out-of-phase
combination, there are two nodal planes created, one along the internuclear axis and a perpendicular one between the nuclei.
Figure 5.5.5 : Side-by-side overlap of each two p orbitals results in the formation of two π molecular orbitals. Combining the out-
of-phase orbitals results in an antibonding molecular orbital with two nodes. One contains the internuclear axis, and one is
perpendicular to the axis. Combining the in-phase orbitals results in a bonding orbital. There is a node (blue plane) containing the
internuclear axis with the two lobes of the orbital located above and below this node.
Two horizontal rows of diagrams are shown. The upper and lower diagrams both begin with two vertical peanut-shaped orbitals
with a plus sign in between followed by a right-facing arrow. The upper diagram shows the same vertical peanut orbitals bending
slightly away from one another and separated by a dotted line. It is labeled, “pi subscript p superscript asterisk.” The lower diagram
shows the horizontal overlap of the two orbitals and is labeled, “pi subscript p.”
In the molecular orbitals of diatomic molecules, each atom also has two sets of p orbitals oriented side by side (py and pz), so these
four atomic orbitals combine pairwise to create two π orbitals and two π orbitals. The π and π orbitals are oriented at right
∗
py
∗
py
angles to the π and π orbitals. Except for their orientation, the πpy and πpz orbitals are identical and have the same energy; they
pz
∗
pz
are degenerate orbitals. The π and π antibonding orbitals are also degenerate and identical except for their orientation. A total
∗
py
∗
pz
of six molecular orbitals results from the combination of the six atomic p orbitals in two atoms: σ and σ , π and π , π and
px
∗
px py
∗
py pz
π .
∗
pz

 Example 5.5.1: Molecular Orbitals
Predict what type (if any) of molecular orbital would result from adding the wave functions so each pair of orbitals shown
overlap. The orbitals are all similar in energy.
Three diagrams are shown and labeled “a,” “b,” and “c.” Diagram a shows two horizontal peanut-shaped orbitals laying side-
by-side. They are labeled, “3 p subscript x and 3 p subscript x.” Diagram b shows one vertical and one horizontal peanut-
shaped orbital which are at right angles to one another. They are labeled, “3 p subscript x and 3 p subscript y.” Diagram c
shows two vertical peanut-shaped orbitals laying side-by-side and labeled, “3 p subscript y and 3 p subscript y.”
Solution
a. This is an in-phase combination, resulting in a σ3p orbital
b. This will not result in a new orbital because the in-phase component (bottom) and out-of-phase component (top) cancel out.
Only orbitals with the correct alignment can combine.
c. This is an out-of-phase combination, resulting in a π orbital.
∗
3p
 Exercise 5.5.1
Label the molecular orbital shown as σ or π, bonding or antibonding and indicate where the node occurs.
Two orbitals are shown lying end-to-end. Each has one enlarged and one small side. The small sides are facing one another
Answer
The orbital is located along the internuclear axis, so it is a σ orbital. There is a node bisecting the internuclear axis, so it is
an antibonding orbital.
Two orbitals are shown lying end-to-end. Each has one enlarged and one small side. The small sides are facing one another and are
separated by a vertical dotted line.
 Application: Computational Chemistry in Drug Design
While the descriptions of bonding described in this chapter involve many theoretical concepts, they also have many practical,
real-world applications. For example, drug design is an important field that uses our understanding of chemical bonding to
develop pharmaceuticals. This interdisciplinary area of study uses biology (understanding diseases and how they operate) to
identify specific targets, such as a binding site that is involved in a disease pathway. By modeling the structures of the binding
site and potential drugs, computational chemists can predict which structures can fit together and how effectively they will
bind (Figure 5.5.6). Thousands of potential candidates can be narrowed down to a few of the most promising candidates. These

candidate molecules are then carefully tested to determine side effects, how effectively they can be transported through the
body, and other factors. Dozens of important new pharmaceuticals have been discovered with the aid of computational
chemistry, and new research projects are underway.
Figure 5.5.6 : The molecule shown, HIV-1 protease, is an important target for pharmaceutical research. By designing molecules
that bind to this protein, scientists are able to drastically inhibit the progress of the disease.
A diagram of a molecule is shown. The image shows a tangle of ribbon-like, intertwined, pink and green curling lines with a
complex ball and stick model in the center.
Molecular Orbital Energy Diagrams

The relative energy levels of atomic and molecular orbitals are typically shown in a molecular orbital diagram (Figure 5.5.7). For a
diatomic molecule, the atomic orbitals of one atom are shown on the left, and those of the other atom are shown on the right. Each
horizontal line represents one orbital that can hold two electrons. The molecular orbitals formed by the combination of the atomic
orbitals are shown in the center. Dashed lines show which of the atomic orbitals combine to form the molecular orbitals. For each
pair of atomic orbitals that combine, one lower-energy (bonding) molecular orbital and one higher-energy (antibonding) orbital
result. Thus we can see that combining the six 2p atomic orbitals results in three bonding orbitals (one σ and two π) and three
antibonding orbitals (one σ* and two π*).

Figure 5.5.7 : This is the molecular orbital diagram for the homonuclear diatomic Be , showing the molecular orbitals of the
+
valence shell only. The molecular orbitals are filled in the same manner as atomic orbitals, using the Aufbau principle and Hund’s
rule.
A diagram is shown that has an upward-facing vertical arrow running along the left side labeled, “E.” At the bottom center of the
diagram is a horizontal line labeled, “sigma subscript 2 s,” that has two vertical half arrows drawn on it, one facing up and one
facing down. This line is connected to the right and left by upward-facing, dotted lines to two more horizontal lines, each labeled,
“2 s.” The line on the left has two vertical half arrows drawn on it, one facing up and one facing down while the line of the right
has one half arrow facing up drawn on it. These two lines are connected by upward-facing dotted lines to another line in the center
of the diagram, but further up from the first. It is labeled, “sigma subscript 2 s superscript asterisk.” This horizontal line has one
upward-facing vertical half-arrow drawn on it. Moving farther up the center of the diagram is a long horizontal line labeled, “sigma
subscript 2 p subscript x,” which lies below two horizontal lines. These two horizontal lines lie side-by-side, and labeled, “pi
subscript 2 p subscript y,” and, “pi subscript 2 p subscript z.” Both the bottom and top lines are connected to the right and left by
upward-facing, dotted lines to three more horizontal lines, each labeled, “2 p.” These sets of lines are connected by upward-facing
dotted lines to another single line and then pair of double lines in the center of the diagram, but farther up from the lower lines.
They are labeled, “sigma subscript 2 p subscript x superscript asterisk,” and, ““pi subscript 2 p subscript y superscript asterisk,”
and, “pi subscript 2 p subscript z superscript asterisk,” respectively. The left and right sides of the diagram have headers that read,
”Atomic orbitals,” while the center is header reads “Molecular orbitals”.
We predict the distribution of electrons in these molecular orbitals by filling the orbitals in the same way that we fill atomic
orbitals, by the Aufbau principle. Lower-energy orbitals fill first, electrons spread out among degenerate orbitals before pairing,
and each orbital can hold a maximum of two electrons with opposite spins (Figure 5.5.7). Just as we write electron configurations
for atoms, we can write the molecular electronic configuration by listing the orbitals with superscripts indicating the number of
electrons present. For clarity, we place parentheses around molecular orbitals with the same energy. In this case, each orbital is at a
different energy, so parentheses separate each orbital. Thus we would expect a diatomic molecule or ion containing seven electrons
(such as Be ) would have the molecular electron configuration (σ ) (σ ) (σ ) (σ ) . It is common to omit the core electrons
+
2 1s
2 ∗
1s
2
2s
2 ∗
2s
1
from molecular orbital diagrams and configurations and include only the valence electrons.
Bond Order
The filled molecular orbital diagram shows the number of electrons in both bonding and antibonding molecular orbitals. The net
contribution of the electrons to the bond strength of a molecule is identified by determining the bond order that results from the
filling of the molecular orbitals by electrons.
When using Lewis structures to describe the distribution of electrons in molecules, we define bond order as the number of bonding
pairs of electrons between two atoms. Thus a single bond has a bond order of 1, a double bond has a bond order of 2, and a triple
bond has a bond order of 3. We define bond order differently when we use the molecular orbital description of the distribution of
electrons, but the resulting bond order is usually the same. The MO technique is more accurate and can handle cases when the
Lewis structure method fails, but both methods describe the same phenomenon.
In the molecular orbital model, an electron contributes to a bonding interaction if it occupies a bonding orbital and it contributes to
an antibonding interaction if it occupies an antibonding orbital. The bond order is calculated by subtracting the destabilizing

(antibonding) electrons from the stabilizing (bonding) electrons. Since a bond consists of two electrons, we divide by two to get the
bond order. We can determine bond order with the following equation:
(number of bonding electrons) − (number of antibonding electrons)
bond order =
2
The order of a covalent bond is a guide to its strength; a bond between two given atoms becomes stronger as the bond order
increases. If the distribution of electrons in the molecular orbitals between two atoms is such that the resulting bond would have a
bond order of zero, a stable bond does not form. We next look at some specific examples of MO diagrams and bond orders.
Bonding in Diatomic Molecules

A dihydrogen molecule (H2) forms from two hydrogen atoms. When the atomic orbitals of the two atoms combine, the electrons
occupy the molecular orbital of lowest energy, the σ1s bonding orbital. A dihydrogen molecule, H2, readily forms because the
energy of a H2 molecule is lower than that of two H atoms. The σ1s orbital that contains both electrons is lower in energy than
either of the two 1s atomic orbitals.
A molecular orbital can hold two electrons, so both electrons in the H2 molecule are in the σ1s bonding orbital; the electron
configuration is (σ ) . We represent this configuration by a molecular orbital energy diagram (Figure 5.5.8) in which a single
1s
2
upward arrow indicates one electron in an orbital, and two (upward and downward) arrows indicate two electrons of opposite spin.
Figure 5.5.8 : The molecular orbital energy diagram predicts that H2 will be a stable molecule with lower energy than the separated
atoms.
A diagram is shown that has an upward-facing vertical arrow running along the left side labeled “E.” At the bottom center of the
“1 s,” and each with one vertical half-arrow facing up drawn on it. These two lines are connected by upward-facing dotted lines to
another line in the center of the diagram, but farther up from the first, and labeled, “sigma subscript 1 s superscript asterisk.” The
left and right sides of the diagram have headers that read, ”Atomic orbitals,” while the center header reads, “Molecular orbitals.”
The bottom left and right are labeled “H” while the center is labeled “H subscript 2.”
A dihydrogen molecule contains two bonding electrons and no antibonding electrons so we have
(2 − 0)
bond order in H = =1
2
2
Because the bond order for the H–H bond is equal to 1, the bond is a single bond.
A helium atom has two electrons, both of which are in its 1s orbital. Two helium atoms do not combine to form a dihelium
molecule, He2, with four electrons, because the stabilizing effect of the two electrons in the lower-energy bonding orbital would be
offset by the destabilizing effect of the two electrons in the higher-energy antibonding molecular orbital. We would write the
hypothetical electron configuration of He2 as (σ ) (σ ) as in Figure 5.5.9. The net energy change would be zero, so there is no
1s
2 ∗
1s
2
driving force for helium atoms to form the diatomic molecule. In fact, helium exists as discrete atoms rather than as diatomic
molecules. The bond order in a hypothetical dihelium molecule would be zero.
(2 − 2)
bond order in He = =0
2
2
A bond order of zero indicates that no bond is formed between two atoms.

Figure 5.5.9 : The molecular orbital energy diagram predicts that He2 will not be a stable molecule, since it has equal numbers of
bonding and antibonding electrons.
A diagram is shown that has an upward-facing vertical arrow running along the left side labeled, “E.” At the bottom center of the
“1 s,” and each with one vertical half-arrow facing up and one facing down drawn on it. These two lines are connected by upward-
facing dotted lines to another line in the center of the diagram, but farther up from the first, and labeled, “sigma subscript 1 s
superscript asterisk.” This line has one upward-facing and one downward-facing vertical arrow drawn on it. The left and right sides
of the diagram have headers that read, “Atomic orbitals,” while the center header reads, “Molecular orbitals.” The bottom left and
right are labeled, “H e,” while the center is labeled, “H e subscript 2.”
The Diatomic Molecules of the Second Period

Eight possible homonuclear diatomic molecules might be formed by the atoms of the second period of the periodic table: Li2, Be2,
B2, C2, N2, O2, F2, and Ne2. However, we can predict that the Be2 molecule and the Ne2 molecule would not be stable. We can see
this by a consideration of the molecular electron configurations (Table 5.5.1).
Table 5.5.1 : Electron Configuration and Bond Order for Molecular Orbitals in Homonuclear Diatomic Molecules of Period Two Elements
Molecule Electron Configuration Bond Order
Li2 2
(σ2s ) 1
Be2 (unstable) 2
(σ2s ) (σ
∗
2s
)
2
0
B2 2
(σ2s ) (σ
∗
2s
2
) (π2py , π2pz )
2
1
C2 2
(σ2s ) (σ
∗
2s
2
) (π2py , π2pz )
4
2
N2 2
(σ2s ) (σ
∗
2s
2 4 2
) (π2py , π2pz ) (σ2px ) 3
O2 2
(σ2s ) (σ
∗
2s
2 2 4
) (σ2px ) (π2py , π2pz ) (π
∗
2py
,π
∗
2pz
)
2
2
F2 2
(σ2s ) (σ
∗
2s
2 2 4
) (σ2px ) (π2py , π2pz ) (π
∗
2py
, π
∗
2pz
)
4
1
Ne2 (unstable) 2
(σ2s ) (σ
∗
2s
2 2 4
) (σ2px ) (π2py , π2pz ) (π
∗
2py
,π
∗
2pz
4
) (σ
∗
2px
2
) 0
We predict valence molecular orbital electron configurations just as we predict electron configurations of atoms. Valence electrons
are assigned to valence molecular orbitals with the lowest possible energies. Consistent with Hund’s rule, whenever there are two
or more degenerate molecular orbitals, electrons fill each orbital of that type singly before any pairing of electrons takes place.

Figure 5.5.10 : This shows the MO diagrams for each homonuclear diatomic molecule in the second period. The orbital energies
decrease across the period as the effective nuclear charge increases and atomic radius decreases. Between N2 and O2, the order of
the orbitals changes.
A graph is shown in which the y-axis is labeled, “E,” and appears as a vertical, upward-facing arrow. Across the top, the graph
reads, “L i subscript 2,” “B e subscript 2,” “B subscript 2,” “C subscript 2,” “N subscript 2,” “O subscript 2,” “F subscript 2,” and
“Ne subscript 2.” Directly below each of these element terms is a single pink line, and all lines are connected to one another by a
dashed line, to create an overall line that decreases in height as it moves from left to right across the graph. This line is labeled,
“sigma subscript 2 p x superscript asterisk”. Directly below each of these lines is a set of two pink lines, and all lines are connected
to one another by a dashed line, to create an overall line that decreases in height as it moves from left to right across the graph. It is
consistently lower than the first line. This line is labeled, “pi subscript 2 p y superscript asterisk,” and, “pi subscript 2 p z
superscript asterisk.” Directly below each of these double lines is a single pink line, and all lines are connected to one another by a
dashed line, to create an overall line that decreases in height as it moves from left to right across the graph. It has a distinctive drop
at the label, “O subscript 2.” This line is labeled, “sigma subscript 2 p x.” Directly below each of these lines is a set of two pink
lines, and all lines are connected to one another by a dashed line to create an overall line that decreases very slightly in height as it
moves from left to right across the graph. It is consistently lower than the third line until it reaches the point labeled, “O subscript
2.” This line is labeled, “pi subscript 2 p y,” and, “pi subscript 2 p z.” Directly below each of these lines is a single blue line, and all
lines are connected to one another by a dashed line to create an overall line that decreases in height as it moves from left to right
across the graph. This line is labeled, “sigma subscript 2 s superscript asterisk.” Finally, directly below each of these lines is a
single blue line, and all lines are connected to one another by a dashed line to create an overall line that decreases in height as it
moves from left to right across the graph. This line is labeled. “sigma subscript 2 s.”
As we saw in valence bond theory, σ bonds are generally more stable than π bonds formed from degenerate atomic orbitals.
Similarly, in molecular orbital theory, σ orbitals are usually more stable than π orbitals. However, this is not always the case. The
MOs for the valence orbitals of the second period are shown in Figure 5.5.10. Looking at Ne2 molecular orbitals, we see that the
order is consistent with the generic diagram shown in the previous section. However, for atoms with three or fewer electrons in the
p orbitals (Li through N) we observe a different pattern, in which the σp orbital is higher in energy than the πp set. Obtain the
molecular orbital diagram for a homonuclear diatomic ion by adding or subtracting electrons from the diagram for the neutral
molecule.
This switch in orbital ordering occurs because of a phenomenon called s-p mixing. s-p mixing does not create new orbitals; it
merely influences the energies of the existing molecular orbitals. The σs wavefunction mathematically combines with the σp
wavefunction, with the result that the σs orbital becomes more stable, and the σp orbital becomes less stable (Figure 5.5.11).
Similarly, the antibonding orbitals also undergo s-p mixing, with the σs* becoming more stable and the σp* becoming less stable.

Figure 5.5.11 : Without mixing, the MO pattern occurs as expected, with the σp orbital lower in energy than the σp orbitals. When s-
p mixing occurs, the orbitals shift as shown, with the σp orbital higher in energy than the πp orbitals.
A diagram is shown. At the bottom left of the diagram is a horizontal line that is connected to the right and left by upward-facing,
dotted lines to two more horizontal lines. Those two lines are connected by upward-facing dotted lines to another line in the center
of the diagram but farther up from the first. Each of the bottom two central lines has a vertical downward-facing arrow. Above this
structure is a horizontal line that is connected to the right and left by upward-facing, dotted lines to two sets of three horizontal
lines and those two lines are connected by upward-facing dotted lines to another line in the center of the diagram, but further up
from the first. In between the horizontal lines of this structure are two pairs of horizontal lines that are above the first line but below
the second and connected by dotted lines to the side horizontal lines. The bottom and top central lines each have an upward-facing
vertical arrow. These two structures are redrawn on the right side of the diagram, but this time, the central lines of the bottom
structure are moved downward in relation to the side lines. The upper portion of the structure has its central lines shifted upward in
relation to the side lines. This structure also shows the bottom line appearing above the set of two lines.
s-p mixing occurs when the s and p orbitals have similar energies. The energy difference between 2s and 2p orbitals in O, F, and Ne
is greater than that in Li, Be, B, C, and N. Because of this, O2, F2, and Ne exhibit negligible s-p mixing (not sufficient to change the
energy ordering), and their MO diagrams follow the normal pattern, as shown in Figure 5.5.7. All of the other period 2 diatomic
molecules do have s-p mixing, which leads to the pattern where the σp orbital is raised above the πp set.
Using the MO diagrams shown in Figure 5.5.11, we can add in the electrons and determine the molecular electron configuration
and bond order for each of the diatomic molecules. As shown in Table 5.5.1, Be2 and Ne2 molecules would have a bond order of 0,
and these molecules do not exist.
The combination of two lithium atoms to form a lithium molecule, Li2, is analogous to the formation of H2, but the atomic orbitals
involved are the valence 2s orbitals. Each of the two lithium atoms has one valence electron. Hence, we have two valence electrons
available for the σ2s bonding molecular orbital. Because both valence electrons would be in a bonding orbital, we would predict the
Li2 molecule to be stable. The molecule is, in fact, present in an appreciable concentration in lithium vapor at temperatures near the
boiling point of the element. All of the other molecules in Table 5.5.1 with a bond order greater than zero are also known.
The O2 molecule has enough electrons to half fill the (π , π ) level. We expect the two electrons that occupy these two
∗
2py
∗
2pz
degenerate orbitals to be unpaired, and this molecular electronic configuration for O2 is in accord with the fact that the oxygen
molecule has two unpaired electrons ( Figure 5.5.10). The presence of two unpaired electrons has proved to be difficult to explain
using Lewis structures, but the molecular orbital theory explains it quite well. In fact, the unpaired electrons of the oxygen
molecule provide a strong piece of support for the molecular orbital theory.
 Application: Band Theory in Extended Systems
When two identical atomic orbitals on different atoms combine, two molecular orbitals result (e.g., H in Figure 5.5.8). The
2
bonding orbital is lower in energy than the original atomic orbitals because the atomic orbitals are in-phase in the molecular
orbital. The antibonding orbital is higher in energy than the original atomic orbitals because the atomic orbitals are out-of-
phase.

In a solid, similar things happen, but on a much larger scale. Remember that even in a small sample there are a huge number of
atoms (typically > 1023 atoms), and therefore a huge number of atomic orbitals that may be combined into molecular orbitals.
When N valence atomic orbitals, all of the same energy and each containing one (1) electron, are combined, N/2 (filled)
bonding orbitals and N/2 (empty) antibonding orbitals will result. Each bonding orbital will show an energy lowering as the
atomic orbitals are mostly in-phase, but each of the bonding orbitals will be a little different and have slightly different
energies. The antibonding orbitals will show an increase in energy as the atomic orbitals are mostly out-of-phase, but each of
the antibonding orbitals will also be a little different and have slightly different energies. The allowed energy levels for all the
bonding orbitals are so close together that they form a band, called the valence band. Likewise, all the antibonding orbitals are
very close together and form a band, called the conduction band. Figure 5.5.12) shows the bands for three important classes of
materials: insulators, semiconductors, and conductors.
Figure 5.5.12 : Molecular orbitals in solids are so closely spaced that they are described as bands. The valence band is lower in
energy and the conduction band is higher in energy. The type of solid is determined by the size of the “band gap” between the
valence and conduction bands. Only a very small amount of energy is required to move electrons from the valence band to the
conduction band in a conductor, and so they conduct electricity well. In an insulator, the band gap is large, so that very few
electrons move, and they are poor conductors of electricity. Semiconductors are in between: they conduct electricity better than
insulators, but not as well as conductors.
This figure shows three diagrams. The first is labeled, “Insulator,” and it consists of two boxes. The “conduction” box is above
and the “valence” box is below. A large gap marked by 4 dashed lines contains a double-headed arrow. One head pointing
towards the “conduction box” and the other towards the “valence” box. The arrow is labeled, “Band gap.” The second diagram
is similar to the first, but the band gap is about half as large. This diagram is labeled, “Semiconductor.” The third diagram is
similar to the other two, but the band gap is about a fifth that of the “Semiconductor” diagram. This diagram is labeled,
“Conductor.”
In order to conduct electricity, electrons must move from the filled valence band to the empty conduction band where they can
move throughout the solid. The size of the band gap, or the energy difference between the top of the valence band and the
bottom of the conduction band, determines how easy it is to move electrons between the bands. Only a small amount of energy
is required in a conductor because the band gap is very small. This small energy difference is “easy” to overcome, so they are
good conductors of electricity. In an insulator, the band gap is so “large” that very few electrons move into the conduction
band; as a result, insulators are poor conductors of electricity. Semiconductors conduct electricity when “moderate” amounts of
energy are provided to move electrons out of the valence band and into the conduction band. Semiconductors, such as silicon,
are found in many electronics.
Semiconductors are used in devices such as computers, smartphones, and solar cells. Solar cells produce electricity when light
provides the energy to move electrons out of the valence band. The electricity that is generated may then be used to power a
light or tool, or it can be stored for later use by charging a battery. As of December 2014, up to 46% of the energy in sunlight
could be converted into electricity using solar cells.
 Example 5.5.2: Molecular Orbital Diagrams, Bond Order, and Number of Unpaired Electrons
Draw the molecular orbital diagram for the oxygen molecule, O2. From this diagram, calculate the bond order for O2. How
does this diagram account for the paramagnetism of O2?
Solution

We draw a molecular orbital energy diagram similar to that shown in Figure 5.5.7. Each oxygen atom contributes six electrons,
so the diagram appears as shown in Figure 5.5.7.
Figure 5.5.13 : The molecular orbital energy diagram for O2 predicts two unpaired electrons.
We calculate the bond order as
(8 − 4)
O = =2
2
2
Oxygen's paramagnetism is explained by the presence of two unpaired electrons in the (π2py, π2pz)* molecular orbitals.
 Exercise 5.5.2
The main component of air is N2. From the molecular orbital diagram of N2, predict its bond order and whether it is
diamagnetic or paramagnetic.
Answer
N2 has a bond order of 3 and is diamagnetic.
 Example 5.5.3: Ion Predictions with MO Diagrams
Give the molecular orbital configuration for the valence electrons in C 2−
2
. Will this ion be stable?
Solution
Looking at the appropriate MO diagram, we see that the π orbitals are lower in energy than the σp orbital. The valence electron
configuration for C2 is
2
(σ2s ) (σ
∗
2s
2
) (π2py , π2pz )
4
.
Adding two more electrons to generate the C 2−
2
anion will give a valence electron configuration of
2 ∗ 2 4 2
(σ2s ) (σ ) (π2py , π2pz ) (σ2px )
2s
Since this has six more bonding electrons than antibonding, the bond order will be 3, and the ion should be stable.

 Exercise 5.5.3
How many unpaired electrons would be present on a Be 2−
2
ion? Would it be paramagnetic or diamagnetic?
Answer
two, paramagnetic

Molecular orbital (MO) theory describes the behavior of electrons in a molecule in terms of combinations of the atomic wave
functions. The resulting molecular orbitals may extend over all the atoms in the molecule. Bonding molecular orbitals are formed
by in-phase combinations of atomic wave functions, and electrons in these orbitals stabilize a molecule. Antibonding molecular
orbitals result from out-of-phase combinations of atomic wave functions and electrons in these orbitals make a molecule less stable.
Molecular orbitals located along an internuclear axis are called σ MOs. They can be formed from s orbitals or from p orbitals
oriented in an end-to-end fashion. Molecular orbitals formed from p orbitals oriented in a side-by-side fashion have electron
density on opposite sides of the internuclear axis and are called π orbitals.
We can describe the electronic structure of diatomic molecules by applying molecular orbital theory to the valence electrons of the
atoms. Electrons fill molecular orbitals following the same rules that apply to filling atomic orbitals; Hund’s rule and the Aufbau
principle tell us that lower-energy orbitals will fill first, electrons will spread out before they pair up, and each orbital can hold a
maximum of two electrons with opposite spins. Materials with unpaired electrons are paramagnetic and attracted to a magnetic
field, while those with all-paired electrons are diamagnetic and repelled by a magnetic field. Correctly predicting the magnetic
properties of molecules is in advantage of molecular orbital theory over Lewis structures and valence bond theory.
This page titled 5.5: Molecular Orbital Theory is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
8.4: Molecular Orbital Theory is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

Chapter Exercises
1. Explain how σ and π bonds are similar and how they are different.
2. Draw a curve that describes the energy of a system with H and Cl atoms at varying distances. Then, find the minimum energy of
this curve two ways.
a. Use the bond energy found in Table 8.2.1 to calculate the energy for one single HCl bond (Hint: How many bonds are in a
mole?)
b. Use the enthalpy of reaction and the bond energies for H and C l to solve for the energy of one mole of HCl bonds.
2 2
∘
H2(g) + C l2(g) ⇌ 2H C l(g) ΔHrxn = −184.7 kJ/mol (5.E.1)
3. Explain why bonds occur at specific average bond distances instead of the atoms approaching each other infinitely close.
4. Use valence bond theory to explain the bonding in F2, HF, and ClBr. Sketch the overlap of the atomic orbitals involved in the
bonds.
5. Use valence bond theory to explain the bonding in O2. Sketch the overlap of the atomic orbitals involved in the bonds in O2.
6. How many σ and π bonds are present in the molecule HCN?
7. A friend tells you N2 has three π bonds due to overlap of the three p-orbitals on each N atom. Do you agree?
8. Draw the Lewis structures for CO2 and CO, and predict the number of σ and π bonds for each molecule.
a. CO2
b. CO
Solutions
1. Similarities: Both types of bonds result from overlap of atomic orbitals on adjacent atoms and contain a maximum of two
electrons. Differences: σ bonds are stronger and result from end-to-end overlap and all single bonds are σ bonds; π bonds between
the same two atoms are weaker because they result from side-by-side overlap, and multiple bonds contain one or more π bonds (in
addition to a σ bond).
2
When H and Cl are separate (the x axis) the energy is at a particular value. As they approach, it decreases to a minimum at 127 pm
(the bond distance), and then it increases sharply as you get closer.
a. (a) H–Cl431 kJ/mol 427kJmol×mol6.022×1023bonds×1000 JkJ=7.09×10−19
b. (b) We know Hess’s law related to bond energies: ΔH°=ƩΔH∘BDE(broken)−ƩΔH∘BDE(formed) We are given the enthalpy of
reaction
−184.7kJ/mol = (ΔH ∘ BDE(H – H ) + ΔH ∘ BDE(C l– C l)) − (2ΔH ∘ BDE(H – C l)) (5.E.2)
H – H is436kJ/molandC l– C lis243 (5.E.3)
– 184.7kJ/mol = (436 + 243)– 2x = 679– 2x (5.E.4)
2x = 863.7kJ/mol (5.E.5)

x = 432 kJ/mol (5.E.6)
This is very close to the value from part (a).

3. The specific average bond distance is the distance with the lowest energy. At distances less than the bond distance, the positive
charges on the two nuclei repel each other, and the overall energy increases.
4. The single bond present in each molecule results from overlap of the relevant orbitals: F 2p orbitals in F2, the H 1s and F 2p
orbitals in HF, and the Cl 3p orbital and Br 4p orbital in ClBr.
5. Bonding: One σ bond and one π bond. The s orbitals are filled and do not overlap. The p orbitals overlap along the axis to form a
σ bond and side by side to form the π bond.
6. H– C ≡ N has two σ (H–C and C–N) and two π (making the CN triple bond).
7. No, two of the p orbitals (one on each N) will be oriented end-to-end and will form a σ bond.
8. (a) 2 σ 2 π;
(b) 1 σ 2 π;
Chemistry End of Chapter Exercises

Why is the concept of hybridization required in valence bond theory?
Hybridization is introduced to explain the geometry of bonding orbitals in valance bond theory.
Give the shape that describes each hybrid orbital set:
(a) sp2
(b) sp3d
(c) sp
(d) sp3d2
Explain why a carbon atom cannot form five bonds using sp3d hybrid orbitals.
There are no d orbitals in the valence shell of carbon.
What is the hybridization of the central atom in each of the following?
(a) BeH2

(b) SF6
(c) PO 3−
(d) PCl5
A molecule with the formula AB3 could have one of four different shapes. Give the shape and the hybridization of the central A
atom for each.
trigonal planar, sp2; trigonal pyramidal (one lone pair on A) sp3; T-shaped (two lone pairs on A sp3d, or (three lone pairs on A)
sp3d2
Methionine, CH3SCH2CH2CH(NH2)CO2H, is an amino acid found in proteins. Draw a Lewis structure of this compound. What is
the hybridization type of each carbon, oxygen, the nitrogen, and the sulfur?
A Lewis structure is shown in which a carbon atom is single bonded to three hydrogen atoms and single bonded to a sulfur atom with two lone pairs of electrons. The sulfur atom is attached to a chain of four singly
bonded carbon atoms, the first two of which are single bonded to two hydrogen atoms each, and the third of which is single bonded to a hydrogen atom and single bonded to a nitrogen atom which has one lone electron
pair. The nitrogen atom is also single bonded to two hydrogen atoms. The fourth andfinal carbon in the chain is double bonded to an oxygen with two lone pairs of electrons and single bonded to an oxygen atom with two
lone pairs of electrons. The second oxygen atom is single bonded to a hydrogen atom.
Sulfuric acid is manufactured by a series of reactions represented by the following equations:

S (s) + 8 O (g) ⟶ 8 SO (g)
8 2 2
2 SO (g) + O (g) ⟶ 2 SO (g)

2 2 3
SO (g) + H O(l) ⟶ H SO (l)

3 2 2 4
Draw a Lewis structure, predict the molecular geometry by VSEPR, and determine the hybridization of sulfur for the following:
(a) circular S8 molecule
(b) SO2 molecule
(c) SO3 molecule
(d) H2SO4 molecule (the hydrogen atoms are bonded to oxygen atoms)
(a) Each S has a bent (109°) geometry, sp3
A Lewis structure is shown in which eight sulfur atoms, each with two lone pairs of eletrons, are single bonded together into an eight-sided ring.
(b) Bent (120°), sp2

Two Lewis structure are shown, connected by a double-ended arrow. The left structure shows a sulfur atom with one lone pair of electrons double bonded to an oxygen atom with two lone pairs of electrons on the left
and single bonded to an oxygen atom with three lone pairs of electrons on the right. The right structure shows the same molecule, except that the double bonded oxygen is on the right side of the sulfur and the single
bonded oxygen is to the left of the sulfur.
(c) Trigonal planar, sp2

A Lewis structure of a sulfur atom singly bonded to two oxygen atoms, each with three lone pairs of electrons, and double bonded to a third oxygen atom with two lone pairs of electrons is shown.
(d) Tetrahedral, sp3

A Lewis structure is shown in which a sulfur atom is single bonded to four oxygen atoms. Two of the oxygen atoms have three lone pairs of electrons while the other two each have two lone pairs of electrons and are
each singly bonded to a hydrogen atom.
Two important industrial chemicals, ethene, C2H4, and propene, C3H6, are produced by the steam (or thermal) cracking process:
2 C H (g) ⟶ C H (g) + C H (g) + CH (g) + H (g)
3 8 2 4 3 6 4 2
For each of the four carbon compounds, do the following:

(a) Draw a Lewis structure.
(b) Predict the geometry about the carbon atom.
(c) Determine the hybridization of each type of carbon atom.
For many years after they were discovered, it was believed that the noble gases could not form compounds. Now we know that
belief to be incorrect. A mixture of xenon and fluorine gases, confined in a quartz bulb and placed on a windowsill, is found to
slowly produce a white solid. Analysis of the compound indicates that it contains 77.55% Xe and 22.45% F by mass.
(a) What is the formula of the compound?
(b) Write a Lewis structure for the compound.

(c) Predict the shape of the molecules of the compound.
(d) What hybridization is consistent with the shape you predicted?
(a) XeF2
(b)
A Lewis structure is shown in which a xenon atom that has three lone pairs of electrons is single bonded to two fluorine atoms, each of which has three lone pairs of electrons.
(c) linear (d) sp3d

Consider nitrous acid, HNO2 (HONO).
(a) Write a Lewis structure.
(b) What are the electron pair and molecular geometries of the internal oxygen and nitrogen atoms in the HNO2 molecule?
(c) What is the hybridization on the internal oxygen and nitrogen atoms in HNO2?
Strike-anywhere matches contain a layer of KClO3 and a layer of P4S3. The heat produced by the friction of striking the match
causes these two compounds to react vigorously, which sets fire to the wooden stem of the match. KClO3 contains the ClO ion. −
P4S3 is an unusual molecule with the skeletal structure.

A Lewis structure is shown in which three phosphorus atoms are single bonded together to form a triangle. Each phosphorus is bonded to a sulfur atom by a vertical single bond and each of those sulfur atoms is then
bonded to a single phosphorus atom so that a six-sided ring is created with a sulfur in the middle.
(a) Write Lewis structures for P4S3 and the ClO ion. −
3
(b) Describe the geometry about the P atoms, the S atom, and the Cl atom in these species.
(c) Assign a hybridization to the P atoms, the S atom, and the Cl atom in these species.
(d) Determine the oxidation states and formal charge of the atoms in P4S3 and the ClO ion. −
(a)
Two Lewis structure are shown, the left of which depicts three phosphorus atoms single bonded together to form a triangle. Each phosphorus is bonded to a sulfur atom by a vertical single bond and each of those
sulfur atoms is then bonded to a single phosphorus atom so that a six-sided ring is created with a sulfur in the middle. Each sulfur atom in this structure has two lone pairs of electrons while each phosphorus has one lone
pair. The second Lewis structure shows a chlorine atom with one lone pair of electrons single bonded to three oxygen atoms, each of which has three lone pairs of electrons.
(b) P atoms, trigonal pyramidal; S atoms, bent, with two lone pairs; Cl atoms, trigonal pyramidal; (c) Hybridization about P, S, and
1
Cl is, in all cases, sp3; (d) Oxidation states P +1, S −1 , Cl +5, O –2. Formal charges: P 0; S 0; Cl +2: O –1
3
Identify the hybridization of each carbon atom in the following molecule. (The arrangement of atoms is given; you need to
determine how many bonds connect each pair of atoms.)
A Lewis structure is shown that is missing all of its bonds. Six carbon atoms form a chain. There are three hydrogen atoms located around the first carbon, two located around the second, one located near the fifth, and
two located around the sixth carbon.
Write Lewis structures for NF3 and PF5. On the basis of hybrid orbitals, explain the fact that NF3, PF3, and PF5 are stable
molecules, but NF5 does not exist.
Two Lewis structures are shown. The left structure shows a nitrogen atom with one lone pair of electrons single bonded to three fluorine atoms, each of which has three lone pairs of electrons. The right structure
shows a phosphorus atoms single bonded to five fluorine atoms, each of which has three lone pairs of electrons.
Phosphorus and nitrogen can form sp3 hybrids to form three bonds and hold one lone pair in PF3 and NF3, respectively. However,
nitrogen has no valence d orbitals, so it cannot form a set of sp3d hybrid orbitals to bind five fluorine atoms in NF5. Phosphorus has
d orbitals and can bind five fluorine atoms with sp3d hybrid orbitals in PF5.
In addition to NF3, two other fluoro derivatives of nitrogen are known: N2F4 and N2F2. What shapes do you predict for these two
molecules? What is the hybridization for the nitrogen in each molecule?
8.3: Multiple Bonds

The bond energy of a C–C single bond averages 347 kJ mol−1; that of a C≡C triple bond averages 839 kJ mol−1. Explain why the
triple bond is not three times as strong as a single bond.
A triple bond consists of one σ bond and two π bonds. A σ bond is stronger than a π bond due to greater overlap.
For the carbonate ion, CO , draw all of the resonance structures. Identify which orbitals overlap to create each bond.
2−
3

A useful solvent that will dissolve salts as well as organic compounds is the compound acetonitrile, H3CCN. It is present in paint
strippers.
(a) Write the Lewis structure for acetonitrile, and indicate the direction of the dipole moment in the molecule.
(b) Identify the hybrid orbitals used by the carbon atoms in the molecule to form σ bonds.
(c) Describe the atomic orbitals that form the π bonds in the molecule. Note that it is not necessary to hybridize the nitrogen atom.
(a)
A Lewis structure is shown in which a carbon atom is attached by single bonds to three hydrogen atoms. It is also attached by a single bond to a carbon atom that is triple bonded to a nitrogen atom with one lone
electron pair. Below the structure is a right facing arrow with its head near the nitrogen and its tail, which looks like a plus sign, located near the carbon atoms. The arrow is labeled, “dipole moment.”
(b) The terminal carbon atom uses sp3 hybrid orbitals, while the central carbon atom is sp hybridized. (c) Each of the two π bonds
is formed by overlap of a 2p orbital on carbon and a nitrogen 2p orbital.
For the molecule allene, H C = C = C H , give the hybridization of each carbon atom. Will the hydrogen atoms be in the same
2 2
plane or perpendicular planes?

Identify the hybridization of the central atom in each of the following molecules and ions that contain multiple bonds:
(a) ClNO (N is the central atom)
(b) CS2
(c) Cl2CO (C is the central atom)
(d) Cl2SO (S is the central atom)
(e) SO2F2 (S is the central atom)
(f) XeO2F2 (Xe is the central atom)
(g) ClOF (Cl is the central atom)
+
(a) sp ; (b) sp; (c) sp2; (d) sp3; (e) sp3; (f) sp3d; (g) sp3
2
Describe the molecular geometry and hybridization of the N, P, or S atoms in each of the following compounds.
(a) H3PO4, phosphoric acid, used in cola soft drinks
(b) NH4NO3, ammonium nitrate, a fertilizer and explosive
(c) S2Cl2, disulfur dichloride, used in vulcanizing rubber
(d) K4[O3POPO3], potassium pyrophosphate, an ingredient in some toothpastes
For each of the following molecules, indicate the hybridization requested and whether or not the electrons will be delocalized:
(a) ozone (O3) central O hybridization
(b) carbon dioxide (CO2) central C hybridization
(c) nitrogen dioxide (NO2) central N hybridization
(d) phosphate ion (PO 3−
4
) central P hybridization
(a) sp , delocalized; (b) sp, localized; (c) sp2, delocalized; (d) sp3, delocalized
2
For each of the following structures, determine the hybridization requested and whether the electrons will be delocalized:
(a) Hybridization of each carbon
A Lewis structure is shown in which a carbon atom is single bonded to three hydrogen atoms and a second carbon atom. This second carbon atom is, in turn, double bonded to an oxygen atom with two lone pairs of
electrons. The second carbon atom is also single bonded to another carbon atom that is single bonded to three hydrogen atoms.
(b) Hybridization of sulfur

A Lewis structure is shown in which a sulfur atom with two lone pairs of electrons and a positive sign is double bonded to an oxygen with two lone pairs of electrons. The sulfur atom is also single bonded to an
oxygen with three lone pairs of electrons with a negative sign. It is drawn in an angular shape.
(c) All atoms

A Lewis structure is shown in which a hexagonal ring structure is made up of five carbon atoms and one nitrogen atom with a lone pair of electrons. There are alternating double and single bonds in between each
carbon atom. Each carbon atom is also single bonded to one hydrogen atom.

Draw the orbital diagram for carbon in CO2 showing how many carbon atom electrons are in each orbital.
A diagram is shown in two parts, connected by a right facing arrow labeled, “Hybridization.” The left diagram shows an up-facing arrow labeled, “E.” To the lower right of the arrow is a short, horizontal line labeled,
“2 s,” that has two vertical half-arrows facing up and down on it. To the upper right of the arrow are a series of three short, horizontal lines labeled, “2 p.” Above both sets of lines is the phrase, “Orbitals in an isolated C
atom.” There are two upward facing arrows on two of these lines. The right side of the diagram shows two short, horizontal lines placed halfway up the space and each labeled, “s p.” An upward-facing half arrow is
drawn vertically on each line. Above these lines are two other short, horizontal lines, each labeled, “2 p,” and which have two upward facing arrows on them. Above both sets of lines is the phrase, “Orbitals in the s p
hybridized C in C O subscript 2.”
Each of the four electrons is in a separate orbital and overlaps with an electron on an oxygen atom.

Sketch the distribution of electron density in the bonding and antibonding molecular orbitals formed from two s orbitals and from
two p orbitals.
How are the following similar, and how do they differ?
(a) σ molecular orbitals and π molecular orbitals
(b) ψ for an atomic orbital and ψ for a molecular orbital
(c) bonding orbitals and antibonding orbitals
(a) Similarities: Both are bonding orbitals that can contain a maximum of two electrons. Differences: σ orbitals are end-to-end
combinations of atomic orbitals, whereas π orbitals are formed by side-by-side overlap of orbitals. (b) Similarities: Both are
quantum-mechanical constructs that represent the probability of finding the electron about the atom or the molecule. Differences: ψ
for an atomic orbital describes the behavior of only one electron at a time based on the atom. For a molecule, ψ represents a
mathematical combination of atomic orbitals. (c) Similarities: Both are orbitals that can contain two electrons. Differences:
Bonding orbitals result in holding two or more atoms together. Antibonding orbitals have the effect of destabilizing any bonding
that has occurred.
If molecular orbitals are created by combining five atomic orbitals from atom A and five atomic orbitals from atom B combine,
how many molecular orbitals will result?
Can a molecule with an odd number of electrons ever be diamagnetic? Explain why or why not.
An odd number of electrons can never be paired, regardless of the arrangement of the molecular orbitals. It will always be
paramagnetic.
Can a molecule with an even number of electrons ever be paramagnetic? Explain why or why not.
Why are bonding molecular orbitals lower in energy than the parent atomic orbitals?
Bonding orbitals have electron density in close proximity to more than one nucleus. The interaction between the bonding positively
charged nuclei and negatively charged electrons stabilizes the system.
Calculate the bond order for an ion with this configuration:
2 ∗ 2 2 4 ∗ ∗ 3
(σ2s ) (σ ) (σ2px ) (π2py , π2pz ) (π , π )
2s 2py 2pz
Explain why an electron in the bonding molecular orbital in the H2 molecule has a lower energy than an electron in the 1s atomic
orbital of either of the separated hydrogen atoms.
The pairing of the two bonding electrons lowers the energy of the system relative to the energy of the nonbonded electrons.
Predict the valence electron molecular orbital configurations for the following, and state whether they will be stable or unstable
ions.
(a) Na 2+
(b) Mg 2+
2
(c) Al 2+
2
(d) Si 2+
(e) P 2+

(f) S 2+
2
(g) F 2+
(h) Ar 2+
2
Determine the bond order of each member of the following groups, and determine which member of each group is predicted by the
molecular orbital model to have the strongest bond.
(a) H2, H , H +
2
−
(b) O2, O 2+
2
,O 2−
2
(c) Li2, Be , Be2 +

2
(d) F2, F , F +
2
−
(e) N2, N , N +
2
−
2
(a) H2 bond order = 1, H bond order = 0.5, H bond order = 0.5, strongest bond is H2; (b) O2 bond order = 2, O bond order =
+
2
−
2
2+
3; O bond order = 1, strongest bond is O ; (c) Li2 bond order = 1, Be bond order = 0.5, Be2 bond order = 0, strongest bond is
2−
2
2+
2
+
Li ;(d) F2 bond order = 1, F bond order = 1.5, F bond order = 0.5, strongest bond is F ; (e) N2 bond order = 3, N bond order
+ − + +
2 2 2 2 2
= 2.5, N bond order = 2.5, strongest bond is N2

−
For the first ionization energy for an N2 molecule, what molecular orbital is the electron removed from?
Compare the atomic and molecular orbital diagrams to identify the member of each of the following pairs that has the highest first
ionization energy (the most tightly bound electron) in the gas phase:
(a) H and H2
(b) N and N2
(c) O and O2
(d) C and C2
(e) B and B2
(a) H2; (b) N2; (c) O; (d) C2; (e) B2
Which of the period 2 homonuclear diatomic molecules are predicted to be paramagnetic?
A friend tells you that the 2s orbital for fluorine starts off at a much lower energy than the 2s orbital for lithium, so the resulting σ2s
molecular orbital in F2 is more stable than in Li2. Do you agree?
Yes, fluorine is a smaller atom than Li, so atoms in the 2s orbital are closer to the nucleus and more stable.
True or false: Boron contains 2s22p1 valence electrons, so only one p orbital is needed to form molecular orbitals.
What charge would be needed on F2 to generate an ion with a bond order of 2?
2+
Predict whether the MO diagram for S2 would show s-p mixing or not.
Explain why N 2+
2
is diamagnetic, while O
4+
2
, which has the same number of valence electrons, is paramagnetic.
N2 has s-p mixing, so the π orbitals are the last filled in N
2+
2
. O2 does not have s-p mixing, so the σp orbital fills before the π
orbitals.
Using the MO diagrams, predict the bond order for the stronger bond in each pair:
(a) B2 or B +
(b) F2 or F +
2
(c) O2 or O 2+
(d) C or C
+
2
−
2

This page titled 5.E: Advanced Theories of Covalent Bonding (Exercises) is shared under a CC BY license and was authored, remixed, and/or

CHAPTER OVERVIEW
6: Composition of Substances and Solutions

General Chemistry
Quantitative aspects of the composition of substances and mixtures are the subject of this chapter.
6.3: Molarity
Contributors
[email protected]).
This page titled 6: Composition of Substances and Solutions is shared under a CC BY license and was authored, remixed, and/or curated by
OpenStax.
1
Calculate formula masses for covalent and ionic compounds
Define the amount unit mole and the related quantity Avogadro’s number
Explain the relation between mass, moles, and numbers of atoms or molecules, and perform calculations deriving these
quantities from one another
We can argue that modern chemical science began when scientists started exploring the quantitative as well as the qualitative
aspects of chemistry. For example, Dalton’s atomic theory was an attempt to explain the results of measurements that allowed him
to calculate the relative masses of elements combined in various compounds. Understanding the relationship between the masses of
atoms and the chemical formulas of compounds allows us to quantitatively describe the composition of substances.
Formula Mass
In an earlier chapter, we described the development of the atomic mass unit, the concept of average atomic masses, and the use of
chemical formulas to represent the elemental makeup of substances. These ideas can be extended to calculate the formula mass of a
substance by summing the average atomic masses of all the atoms represented in the substance’s formula.
Formula Mass for Covalent Substances

For covalent substances, the formula represents the numbers and types of atoms composing a single molecule of the substance;
therefore, the formula mass may be correctly referred to as a molecular mass. Consider chloroform (CHCl3), a covalent compound
once used as a surgical anesthetic and now primarily used in the production of tetrafluoroethylene, the building block for the “anti-
stick” polymer, Teflon. The molecular formula of chloroform indicates that a single molecule contains one carbon atom, one
hydrogen atom, and three chlorine atoms. The average molecular mass of a chloroform molecule is therefore equal to the sum of
the average atomic masses of these atoms. Figure 6.1.1 outlines the calculations used to derive the molecular mass of chloroform,
which is 119.37 amu.
Figure 6.1.1 : The average mass of a chloroform molecule, CHCl3, is 119.37 amu, which is the sum of the average atomic masses of
each of its constituent atoms. The model shows the molecular structure of chloroform.
A table and diagram are shown. The table is made up of six columns and five rows. The header row reads: “Element,” “Quantity,”
a blank space, “Average atomic mass (a m u),” a blank space, and “Subtotal (a m u).” The first column contains the symbols “C,”
“H,” “C l” and a blank, merged cell that runs the width of the first five columns. The second column contains the numbers “1,” “1,”
and “3” as well as the merged cell. The third column contains the multiplication symbol in each cell except for the last, merged
cell. The fourth column contains the numbers “12.01,” “1.008,” and “35.45” as well as the merged cell. The fifth column contains
the symbol “=” in each cell except for the last, merged cell. The sixth column contains the values “12.01,” “1.008,” “106.35,” and
“119.37.” There is a thick black line below the number 106.35. The merged cell under the first five columns reads “Molecular
mass.” To the left of the table is a diagram of a molecule. Three green spheres are attached to a slightly smaller black sphere, which
is also attached to a smaller white sphere. The green spheres lie beneath and to the sides of the black sphere while the white sphere
is located straight up from the black sphere.
Likewise, the molecular mass of an aspirin molecule, C9H8O4, is the sum of the atomic masses of nine carbon atoms, eight
hydrogen atoms, and four oxygen atoms, which amounts to 180.15 amu (Figure 6.1.2).

Figure 6.1.2 : The average mass of an aspirin molecule is 180.15 amu. The model shows the molecular structure of aspirin,
C9H8O4.
A table and diagram are shown. The table is made up of six columns and five rows. The header row reads: “Element,” “Quantity,”
a blank space, “Average atomic mass (a m u),” a blank space, and “Subtotal (a m u).” The first column contains the symbols “C,”
“H,” “O,” and a merged cell. The merged cell runs the length of the first five columns. The second column contains the numbers
“9,” “8,” and “4” as well as the merged, cell. The third column contains the multiplication symbol in each cell except for the last,
merged cell. The fourth column contains the numbers “12.01,” “1.008,” and “16.00” as well as the merged cell. The fifth column
contains the symbol “=” in each cell except for the last, merged cell. The sixth column contains the values: “108.09,” “8.064,”
“64.00,” and “180.15.” There is a thick black line below the number 64.00. The merged cell under the first five columns reads
“Molecular mass.” To the left of the table is a diagram of a molecule. Six black spheres are located in a six-sided ring and
connected by alternating double and single black bonds. Attached to each of the four black spheres is one smaller white sphere.
Attached to the farthest right black sphere is a red sphere, connected to two more black spheres, all in a row. Attached to the last
black sphere of that row are two more white spheres. Attached to the first black sphere of that row is another red sphere. A black
sphere, attached to two red spheres and a white sphere is attached to the black sphere on the top right of the six-sided ring.
 Example 6.1.1: Computing Molecular Mass for a Covalent Compound
Ibuprofen, C13H18O2, is a covalent compound and the active ingredient in several popular nonprescription pain medications,
such as Advil and Motrin. What is the molecular mass (amu) for this compound?
Solution
Molecules of this compound are comprised of 13 carbon atoms, 18 hydrogen atoms, and 2 oxygen atoms. Following the
approach described above, the average molecular mass for this compound is therefore:
 Exercise 6.1.1
Acetaminophen, C8H9NO2, is a covalent compound and the active ingredient in several popular nonprescription pain
medications, such as Tylenol. What is the molecular mass (amu) for this compound?
Answer
151.16 amu
Formula Mass for Ionic Compounds

Ionic compounds are composed of discrete cations and anions combined in ratios to yield electrically neutral bulk matter. The
formula mass for an ionic compound is calculated in the same way as the formula mass for covalent compounds: by summing the
average atomic masses of all the atoms in the compound’s formula. Keep in mind, however, that the formula for an ionic compound
does not represent the composition of a discrete molecule, so it may not correctly be referred to as the “molecular mass.”

As an example, consider sodium chloride, NaCl, the chemical name for common table salt. Sodium chloride is an ionic compound
composed of sodium cations, Na+, and chloride anions, Cl−, combined in a 1:1 ratio. The formula mass for this compound is
computed as 58.44 amu (Figure 6.1.3).
Figure 6.1.3 : Table salt, NaCl, contains an array of sodium and chloride ions combined in a 1:1 ratio. Its formula mass is 58.44
amu.
A table and diagram are shown. The table is made up of six columns and four rows. The header row reads: “Element,” “Quantity,”
a blank space, “Average atomic mass (a m u),” a blank space and “Subtotal (a m u).” The first column contains the symbols “N a”,
“C l,” and a merged cell. The merged cell runs the length of the first five columns. The second column contains the numbers “1”
and “1” as well as the merged cell. The third column contains the multiplication symbol in each cell except for the last, merged
cell. The fourth column contains the numbers “22.99” and “35.45” as well as the merged cell. The fifth column contains the symbol
“=” in each cell except for the last, merged cell. The sixth column contains the values “22.99,” “35.45,” and “58.44.” There is a
thick black line below the number “35.45.” The merged cell under the first five columns reads “Formula mass.” To the left of the
table is a diagram of a chemical structure. The diagram shows green and purple spheres placed in an alternating pattern, making up
the corners of eight stacked cubes to form one larger cube. The green spheres are slightly smaller than the purple spheres.
Note that the average masses of neutral sodium and chlorine atoms were used in this computation, rather than the masses for
sodium cations and chlorine anions. This approach is perfectly acceptable when computing the formula mass of an ionic
compound. Even though a sodium cation has a slightly smaller mass than a sodium atom (since it is missing an electron), this
difference will be offset by the fact that a chloride anion is slightly more massive than a chloride atom (due to the extra electron).
Moreover, the mass of an electron is negligibly small with respect to the mass of a typical atom. Even when calculating the mass of
an isolated ion, the missing or additional electrons can generally be ignored, since their contribution to the overall mass is
negligible, reflected only in the nonsignificant digits that will be lost when the computed mass is properly rounded. The few
exceptions to this guideline are very light ions derived from elements with precisely known atomic masses.
 Example 6.1.2: Computing Formula Mass for an Ionic Compound
Aluminum sulfate, Al2(SO4)3, is an ionic compound that is used in the manufacture of paper and in various water purification
processes. What is the formula mass (amu) of this compound?
Solution
The formula for this compound indicates it contains Al3+ and SO42− ions combined in a 2:3 ratio. For purposes of computing a
formula mass, it is helpful to rewrite the formula in the simpler format, Al2S3O12. Following the approach outlined above, the
formula mass for this compound is calculated as follows:
 Exercise 6.1.2
Calcium phosphate, Ca (PO ) , is an ionic compound and a common anti-caking agent added to food products. What is the
3 4 2
formula mass (amu) of calcium phosphate?
Answer
310.18 amu

The Mole
The identity of a substance is defined not only by the types of atoms or ions it contains, but by the quantity of each type of atom or
ion. For example, water, H O , and hydrogen peroxide, H O , are alike in that their respective molecules are composed of
2 2 2
hydrogen and oxygen atoms. However, because a hydrogen peroxide molecule contains two oxygen atoms, as opposed to the water
molecule, which has only one, the two substances exhibit very different properties. Today, we possess sophisticated instruments
that allow the direct measurement of these defining microscopic traits; however, the same traits were originally derived from the
measurement of macroscopic properties (the masses and volumes of bulk quantities of matter) using relatively simple tools
(balances and volumetric glassware). This experimental approach required the introduction of a new unit for amount of substances,
the mole, which remains indispensable in modern chemical science.
The mole is an amount unit similar to familiar units like pair, dozen, gross, etc. It provides a specific measure of the number of
atoms or molecules in a bulk sample of matter. A mole is defined as the amount of substance containing the same number of
discrete entities (such as atoms, molecules, and ions) as the number of atoms in a sample of pure 12C weighing exactly 12 g. One
Latin connotation for the word “mole” is “large mass” or “bulk,” which is consistent with its use as the name for this unit. The
mole provides a link between an easily measured macroscopic property, bulk mass, and an extremely important fundamental
property, number of atoms, molecules, and so forth.
The number of entities composing a mole has been experimentally determined to be 6.02214179 × 10 , a fundamental constant
23
named Avogadro’s number (N ) or the Avogadro constant in honor of Italian scientist Amedeo Avogadro. This constant is
A
properly reported with an explicit unit of “per mole,” a conveniently rounded version being 6.022 × 10 /mol. 23
Consistent with its definition as an amount unit, 1 mole of any element contains the same number of atoms as 1 mole of any other
element. The masses of 1 mole of different elements, however, are different, since the masses of the individual atoms are drastically
different. The molar mass of an element (or compound) is the mass in grams of 1 mole of that substance, a property expressed in
units of grams per mole (g/mol) (Figure 6.1.4).
Figure 6.1.4 : Each sample contains 6.022 × 10 atoms —1.00 mol of atoms. From left to right (top row): 65.4 g zinc, 12.0 g
23
carbon, 24.3 g magnesium, and 63.5 g copper. From left to right (bottom row): 32.1 g sulfur, 28.1 g silicon, 207 g lead, and 118.7 g
tin. (credit: modification of work by Mark Ott).
This figure contains eight different substances displayed on white circles. The amount of each substance is visibly different.
Because the definitions of both the mole and the atomic mass unit are based on the same reference substance, 12C, the molar mass
of any substance is numerically equivalent to its atomic or formula weight in amu. Per the amu definition, a single 12C atom weighs
12 amu (its atomic mass is 12 amu). According to the definition of the mole, 12 g of 12C contains 1 mole of 12C atoms (its molar
mass is 12 g/mol). This relationship holds for all elements, since their atomic masses are measured relative to that of the amu-
reference substance, 12C. Extending this principle, the molar mass of a compound in grams is likewise numerically equivalent to its
formula mass in amu (Figure 6.1.5).

<div data-mt-source="1"
"This
" height="292" width="437" src="/@api/deki/files/56173/CNX_Chem_03_02_compound.jpg">
Figure 6.1.5 : Each sample contains 6.022 × 10 molecules or formula units—1.00 mol of the compound or element. Clock-wise
23
from the upper left: 130.2 g of C8H17OH (1-octanol, formula mass 130.2 amu), 454.4 g of HgI2 (mercury(II) iodide, formula mass
454.4 amu), 32.0 g of CH3OH (methanol, formula mass 32.0 amu) and 256.5 g of S8 (sulfur, formula mass 256.5 amu). (credit:
Sahar Atwa).
Table 6.1.1 : Mass of one mole of elements
Element Average Atomic Mass (amu) Molar Mass (g/mol) Atoms/Mole
C 12.01 12.01 6.022 × 10

23
H 1.008 1.008 6.022 × 10

23
O 16.00 16.00 6.022 × 10

23
Na 22.99 22.99 6.022 × 10

23
Cl 33.45 35.45 6.022 × 10

23
While atomic mass and molar mass are numerically equivalent, keep in mind that they are vastly different in terms of scale, as
represented by the vast difference in the magnitudes of their respective units (amu versus g). To appreciate the enormity of the
mole, consider a small drop of water after a rainfall. Although this represents just a tiny fraction of 1 mole of water (~18 g), it
contains more water molecules than can be clearly imagined. If the molecules were distributed equally among the roughly seven
billion people on earth, each person would receive more than 100 billion molecules.
How big is a mole? (Not the animal, the …
Video 6.1.1 : The mole is used in chemistry to represent 6.022 × 10 of something, but it can be difficult to conceptualize such a
23
large number. Watch this video and then complete the “Think” questions that follow. Explore more about the mole by reviewing the
information under “Dig Deeper.”
The relationships between formula mass, the mole, and Avogadro’s number can be applied to compute various quantities that
describe the composition of substances and compounds. For example, if we know the mass and chemical composition of a
substance, we can determine the number of moles and calculate number of atoms or molecules in the sample. Likewise, if we know
the number of moles of a substance, we can derive the number of atoms or molecules and calculate the substance’s mass.
 Example 6.1.3: Deriving Moles from Grams for an Element
According to nutritional guidelines from the US Department of Agriculture, the estimated average requirement for dietary
potassium is 4.7 g. What is the estimated average requirement of potassium in moles?
Solution
The mass of K is provided, and the corresponding amount of K in moles is requested. Referring to the periodic table, the
atomic mass of K is 39.10 amu, and so its molar mass is 39.10 g/mol. The given mass of K (4.7 g) is a bit more than one-tenth
the molar mass (39.10 g), so a reasonable “ballpark” estimate of the number of moles would be slightly greater than 0.1 mol.

The molar amount of a substance may be calculated by dividing its mass (g) by its molar mass (g/mol):
The factor-label method supports this mathematical approach since the unit “g” cancels and the answer has units of “mol:”
mol K
4.7 g K( ) = 0.12 mol K
39.10 g
The calculated magnitude (0.12 mol K) is consistent with our ballpark expectation, since it is a bit greater than 0.1 mol.
 Exercise 6.1.3: Beryllium
Beryllium is a light metal used to fabricate transparent X-ray windows for medical imaging instruments. How many moles of
Be are in a thin-foil window weighing 3.24 g?
Answer
0.360 mol
 Example 6.1.4: Deriving Grams from Moles for an Element
A liter of air contains 9.2 × 10

−4
mol argon. What is the mass of Ar in a liter of air?
Solution
The molar amount of Ar is provided and must be used to derive the corresponding mass in grams. Since the amount of Ar is
less than 1 mole, the mass will be less than the mass of 1 mole of Ar, approximately 40 g. The molar amount in question is
approximately one-one thousandth (~10−3) of a mole, and so the corresponding mass should be roughly one-one thousandth of
the molar mass (~0.04 g):
In this case, logic dictates (and the factor-label method supports) multiplying the provided amount (mol) by the molar mass
(g/mol):
39.95 g
−4
9.2 × 10 mol Ar ( ) = 0.037 g Ar
mol Ar
The result is in agreement with our expectations, around 0.04 g Ar.
 Exercise 6.1.4
What is the mass of 2.561 mol of gold?
Answer
504.4 g

 Example 6.1.6: Deriving Number of Atoms from Mass for an Element
Copper is commonly used to fabricate electrical wire (Figure 6.1.6). How many copper atoms are in 5.00 g of copper wire?
Figure 6.1.6 : Copper wire is composed of many, many atoms of Cu. (credit: Emilian Robert Vicol)
Solution
The number of Cu atoms in the wire may be conveniently derived from its mass by a two-step computation: first calculating
the molar amount of Cu, and then using Avogadro’s number (NA) to convert this molar amount to number of Cu atoms:
Considering that the provided sample mass (5.00 g) is a little less than one-tenth the mass of 1 mole of Cu (~64 g), a
reasonable estimate for the number of atoms in the sample would be on the order of one-tenth NA, or approximately 1022 Cu
atoms. Carrying out the two-step computation yields:
23
mol Cu 6.022 × 10 atoms
22
5.00 g Cu ( )( ) = 4.74 × 10 atoms of copper
63.55 g mol
The factor-label method yields the desired cancellation of units, and the computed result is on the order of 1022 as expected.
 Exercise 6.1.6
A prospector panning for gold in a river collects 15.00 g of pure gold. How many Au atoms are in this quantity of gold?
Answer
4.586 × 10
22
Au atoms
 Example 6.1.7: Deriving Moles from Grams for a Compound
Our bodies synthesize protein from amino acids. One of these amino acids is glycine, which has the molecular formula
C2H5O2N. How many moles of glycine molecules are contained in 28.35 g of glycine?
Solution
We can derive the number of moles of a compound from its mass following the same procedure we used for an element in
Example 6.1.6:

The molar mass of glycine is required for this calculation, and it is computed in the same fashion as its molecular mass. One
mole of glycine, C2H5O2N, contains 2 moles of carbon, 5 moles of hydrogen, 2 moles of oxygen, and 1 mole of nitrogen:
A table is shown that is made up of six columns and six rows. The header row reads: “Element,” “Quantity (mol element / mol
compound,” a blank space, “Molar mass (g / mol element),” a blank space, and “Subtotal (a m u).” The first column contains
the symbols “C,” “H,” “O,” “N,” and a merged cell. The merged cell runs the width of the first five columns. The second
column contains the numbers “2,” “5,” “2,” and “1” as well as the merged cell. The third column contains the multiplication
symbol in each cell except for the last, merged cell. The fourth column contains the numbers “12.01,” “1.008,” “16.00,” and
“14.007” as well as the merged cell. The fifth column contains the symbol “=” in each cell except for the last, merged cell. The
sixth column contains the values “24.02,” “5.040,” “32.00,” “14.007,” and “75.07.” There is a thick black line under the
number 14.007. The merged cell under the first five columns reads “Molar mass (g / mol compound). There is a ball-and-stick
drawing to the right of this table. It shows a black sphere that forms a double bond with a slightly smaller red sphere, a single
bond with another red sphere, and a single bond with another black sphere. The red sphere that forms a single bond with the
black sphere also forms a single bond with a smaller, white sphere. The second black sphere forms a single bond with a
smaller, white sphere and a smaller blue sphere. The blue sphere forms a single bond with two smaller, white spheres each.
The provided mass of glycine (~28 g) is a bit more than one-third the molar mass (~75 g/mol), so we would expect the
computed result to be a bit greater than one-third of a mole (~0.33 mol). Dividing the compound’s mass by its molar mass
yields:
mol glycine
28.35 g glycine ( ) = 0.378 mol glycine
75.07 g
This result is consistent with our rough estimate.
 Exercise 6.1.7
How many moles of sucrose, C 12 H22 O11 , are in a 25-g sample of sucrose?
Answer
0.073 mol
 Example 6.1.8: Deriving Grams from Moles for a Compound
Vitamin C is a covalent compound with the molecular formula C6H8O6. The recommended daily dietary allowance of vitamin
C for children aged 4–8 years is 1.42 × 10−4 mol. What is the mass of this allowance in grams?
Solution
As for elements, the mass of a compound can be derived from its molar amount as shown:
The molar mass for this compound is computed to be 176.124 g/mol. The given number of moles is a very small fraction of a
mole (~10−4 or one-ten thousandth); therefore, we would expect the corresponding mass to be about one-ten thousandth of the
molar mass (~0.02 g). Performing the calculation, we get:

176.124 g
−4
1.42 × 10 mol vitamin C ( ) = 0.0250 g vitamin C
mol vitamin C
This is consistent with the anticipated result.
 Exercise 6.1.8
What is the mass of 0.443 mol of hydrazine, N 2 H4 ?
Answer
14.2 g
 Example 6.1.9: Deriving the Number of Molecules from the Compound Mass
A packet of an artificial sweetener contains 40.0 mg of saccharin (C7H5NO3S), which has the structural formula:
Given that saccharin has a molar mass of 183.18 g/mol, how many saccharin molecules are in a 40.0-mg (0.0400-g) sample of
saccharin? How many carbon atoms are in the same sample?
Solution
The number of molecules in a given mass of compound is computed by first deriving the number of moles, as demonstrated in
Example 6.1.8, and then multiplying by Avogadro’s number:
Using the provided mass and molar mass for saccharin yields:
23
mol C H NO S 6.022 × 10 C H NO S molecules
7 5 3 7 5 3
0.0400 g C H NO S ( )( )
7 5 3
183.18 g C H NO S 1 mol C H NO S
7 5 3
7 5 3
20
= 1.31 × 10 C H NO S molecules
7 5 3
The compound’s formula shows that each molecule contains seven carbon atoms, and so the number of C atoms in the
provided sample is:
20
7 C atoms 21
1.31 × 10 C H NO S molecules ( ) = 9.20 × 10 C atoms
7 5 3
1 C H NO S molecule
7 5 3
 Exercise 6.1.9
How many C 4 H10 molecules are contained in 9.213 g of this compound? How many hydrogen atoms?
Answer

22
9.545 × 10 molecules C4 H10
23
9.545 × 10 atoms H
Summary
The formula mass of a substance is the sum of the average atomic masses of each atom represented in the chemical formula and is
expressed in atomic mass units. The formula mass of a covalent compound is also called the molecular mass. A convenient amount
unit for expressing very large numbers of atoms or molecules is the mole. Experimental measurements have determined the number
of entities composing 1 mole of substance to be 6.022 × 1023, a quantity called Avogadro’s number. The mass in grams of 1 mole of
substance is its molar mass. Due to the use of the same reference substance in defining the atomic mass unit and the mole, the
formula mass (amu) and molar mass (g/mol) for any substance are numerically equivalent (for example, one H2O molecule weighs
approximately18 amu and 1 mole of H2O molecules weighs approximately 18 g).
Footnotes
1. 1 Omiatek, Donna M., Amanda J. Bressler, Ann-Sofie Cans, Anne M. Andrews, Michael L. Heien, and Andrew G. Ewing. “The
Real Catecholamine Content of Secretory Vesicles in the CNS Revealed by Electrochemical Cytometry.” Scientific Report 3
(2013): 1447, accessed January 14, 2015, doi:10.1038/srep01447.
Glossary
Avogadro’s number (NA)
experimentally determined value of the number of entities comprising 1 mole of substance, equal to 6.022 × 1023 mol−1
formula mass
sum of the average masses for all atoms represented in a chemical formula; for covalent compounds, this is also the molecular
mass
mole
amount of substance containing the same number of atoms, molecules, ions, or other entities as the number of atoms in exactly
12 grams of 12C
molar mass
mass in grams of 1 mole of a substance
This page titled 6.1: Formula Mass and the Mole Concept is shared under a CC BY license and was authored, remixed, and/or curated by
OpenStax.
3.1: Formula Mass and the Mole Concept is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

Compute the percent composition of a compound
Determine the empirical formula of a compound
Determine the molecular formula of a compound
In the previous section, we discussed the relationship between the bulk mass of a substance and the number of atoms or molecules
it contains (moles). Given the chemical formula of the substance, we were able to determine the amount of the substance (moles)
from its mass, and vice versa. But what if the chemical formula of a substance is unknown? In this section, we will explore how to
apply these very same principles in order to derive the chemical formulas of unknown substances from experimental mass
measurements.
Percent Composition
The elemental makeup of a compound defines its chemical identity, and chemical formulas are the most succinct way of
representing this elemental makeup. When a compound’s formula is unknown, measuring the mass of each of its constituent
elements is often the first step in the process of determining the formula experimentally. The results of these measurements permit
the calculation of the compound’s percent composition, defined as the percentage by mass of each element in the compound. For
example, consider a gaseous compound composed solely of carbon and hydrogen. The percent composition of this compound could
be represented as follows:
mass H
%H = × 100%
mass compound
mass C
%C = × 100%
mass compound
If analysis of a 10.0-g sample of this gas showed it to contain 2.5 g H and 7.5 g C, the percent composition would be calculated to
be 25% H and 75% C:
2.5 g H
%H = × 100% = 25%
10.0 g compound
7.5 g C
%C = × 100% = 75%
10.0 g compound
 Example 6.2.1: Calculation of Percent Composition
Analysis of a 12.04-g sample of a liquid compound composed of carbon, hydrogen, and nitrogen showed it to contain 7.34 g C,
1.85 g H, and 2.85 g N. What is the percent composition of this compound?
Solution
To calculate percent composition, we divide the experimentally derived mass of each element by the overall mass of the
compound, and then convert to a percentage:
7.34 g C
%C = × 100% = 61.0%
12.04 g compound
1.85 g H
%H = × 100% = 15.4%
12.04 g compound
2.85 g N
%N = × 100% = 23.7%
12.04 g compound
The analysis results indicate that the compound is 61.0% C, 15.4% H, and 23.7% N by mass.

 Exercise 6.2.1
A 24.81-g sample of a gaseous compound containing only carbon, oxygen, and chlorine is determined to contain 3.01 g C, 4.00
g O, and 17.81 g Cl. What is this compound’s percent composition?
Answer
12.1% C, 16.1% O, 71.8% Cl
Determining Percent Composition from Formula Mass

Percent composition is also useful for evaluating the relative abundance of a given element in different compounds of known
formulas. As one example, consider the common nitrogen-containing fertilizers ammonia (NH3), ammonium nitrate (NH4NO3),
and urea (CH4N2O). The element nitrogen is the active ingredient for agricultural purposes, so the mass percentage of nitrogen in
the compound is a practical and economic concern for consumers choosing among these fertilizers. For these sorts of applications,
the percent composition of a compound is easily derived from its formula mass and the atomic masses of its constituent elements.
A molecule of NH3 contains one N atom weighing 14.01 amu and three H atoms weighing a total of (3 × 1.008 amu) = 3.024 amu.
The formula mass of ammonia is therefore (14.01 amu + 3.024 amu) = 17.03 amu, and its percent composition is:
14.01 amu N
%N = × 100% = 82.27%
17.03 amu NH3
3.024 amu N
%H = × 100% = 17.76%
17.03 amu NH3
This same approach may be taken considering a pair of molecules, a dozen molecules, or a mole of molecules, etc. The latter
amount is most convenient and would simply involve the use of molar masses instead of atomic and formula masses, as
demonstrated Example 6.2.2. As long as we know the chemical formula of the substance in question, we can easily derive percent
composition from the formula mass or molar mass.
 Example 6.2.2: Determining Percent Composition from a Molecular Formula
Aspirin is a compound with the molecular formula C9H8O4. What is its percent composition?
Solution
To calculate the percent composition, we need to know the masses of C, H, and O in a known mass of C9H8O4. It is convenient
to consider 1 mol of C9H8O4 and use its molar mass (180.159 g/mole, determined from the chemical formula) to calculate the
percentages of each of its elements:
9 mol C × molar mass C 9 × 12.01 g/mol 108.09 g/mol
%C = × 100 = 180.159 g/mol × 100 = × 100
molar mass C H O 180.159 g/mol
9 18 4
%C = 60.00 % C
8 mol H × molar mass H 8 × 1.008 g/mol 8.064 g/mol

%H = × 100 = 180.159 g/mol × 100 = × 100
9 18 4
%H = 4.476 % H
4 mol O × molar mass O 4 × 16.00 g/mol 64.00 g/mol

%O = × 100 = 180.159 g/mol × 100 = × 100
9 18 4
%O = 35.52%
Note that these percentages sum to equal 100.00% when appropriately rounded.

 Exercise 6.2.2
To three significant digits, what is the mass percentage of iron in the compound F e 2 O3 ?
Answer
69.9% Fe
Determination of Empirical Formulas

As previously mentioned, the most common approach to determining a compound’s chemical formula is to first measure the
masses of its constituent elements. However, we must keep in mind that chemical formulas represent the relative numbers, not
masses, of atoms in the substance. Therefore, any experimentally derived data involving mass must be used to derive the
corresponding numbers of atoms in the compound. To accomplish this, we can use molar masses to convert the mass of each
element to a number of moles. We then consider the moles of each element relative to each other, converting these numbers into a
whole-number ratio that can be used to derive the empirical formula of the substance. Consider a sample of compound determined
to contain 1.71 g C and 0.287 g H. The corresponding numbers of atoms (in moles) are:
1 mol C
1.71 g C × = 0.142 mol C
12.01 g C
1 mol H
0.287 g H × = 0.284 mol H
1.008 g H
Thus, we can accurately represent this compound with the formula C0.142H0.284. Of course, per accepted convention, formulas
contain whole-number subscripts, which can be achieved by dividing each subscript by the smaller subscript:
C 0.142 H 0.284 or CH
2
0.142 0.142
(Recall that subscripts of “1” are not written, but rather assumed if no other number is present.)
The empirical formula for this compound is thus CH2. This may or not be the compound’s molecular formula as well; however, we
would need additional information to make that determination (as discussed later in this section).
Consider as another example a sample of compound determined to contain 5.31 g Cl and 8.40 g O. Following the same approach
yields a tentative empirical formula of:
C l0.150O0.525 = C l 0.150 O 0.525 = Cl O3.5

0.150 0.150
In this case, dividing by the smallest subscript still leaves us with a decimal subscript in the empirical formula. To convert this into
a whole number, we must multiply each of the subscripts by two, retaining the same atom ratio and yielding Cl2O7 as the final
empirical formula.
 Procedure
In summary, empirical formulas are derived from experimentally measured element masses by:
1. Deriving the number of moles of each element from its mass
2. Dividing each element’s molar amount by the smallest molar amount to yield subscripts for a tentative empirical formula
3. Multiplying all coefficients by an integer, if necessary, to ensure that the smallest whole-number ratio of subscripts is
obtained
Figure 6.2.1 outlines this procedure in flow chart fashion for a substance containing elements A and X.

Figure 6.2.1 : The empirical formula of a compound can be derived from the masses of all elements in the sample.
A flow chart is shown that is composed of six boxes, two of which are connected together by a right facing arrow and located
above two more that are also connected by a right-facing arrow. These two rows of boxes are connected vertically by a line that
leads to a right-facing arrow and the last two boxes, connected by a final right facing arrow. The first two upper boxes have the
phrases, “Mass of A atoms” and “Moles of A atoms” respectively, while the arrow that connects them has the phrase, “Divide by
molar mass,” written below it. The second two bottom boxes have the phrases, “Mass of X atoms” and “Moles of X atoms”
respectively, while the arrow that connects them has the phrase, “Divide by molar mass” written below it. The arrow that connects
the upper and lower boxes to the last two boxes has the phrase “Divide by lowest number of moles” written below it. The last two
boxes have the phrases, “A to X mole ratio” and “Empirical formula” respectively, while the arrow that connects them has the
phrase, “Convert ratio to lowest whole numbers” written below it.
 Example 6.2.3: Determining an Empirical Formula from Masses of Elements
A sample of the black mineral hematite (Figure 6.2.2), an oxide of iron found in many iron ores, contains 34.97 g of iron and
15.03 g of oxygen. What is the empirical formula of hematite?
Figure 6.2.2 : Hematite is an iron oxide that is used in jewelry. (credit: Mauro Cateb)
Solution
For this problem, we are given the mass in grams of each element. Begin by finding the moles of each:
mol Fe
34.97 g Fe ( ) = 0.6261 mol Fe
55.85 g
mol O
15.03 g O ( ) = 0.9394 mol O
16.00 g
Next, derive the iron-to-oxygen molar ratio by dividing by the lesser number of moles:
0.6261
= 1.000 mol Fe
0.6261
0.9394
= 1.500 mol O
0.6261
The ratio is 1.000 mol of iron to 1.500 mol of oxygen (Fe1O1.5). Finally, multiply the ratio by two to get the smallest possible
whole number subscripts while still maintaining the correct iron-to-oxygen ratio:
2(F e1 O1.5 ) = F e2 O3
The empirical formula is F e 2 O3 .

 Exercise 6.2.3
What is the empirical formula of a compound if a sample contains 0.130 g of nitrogen and 0.370 g of oxygen?
Answer
N2 O5
Calculating Percent Composition and E…

E…
Video 6.2.1 : Additional worked examples illustrating the derivation of empirical formulas are presented in the brief video clip.
Deriving Empirical Formulas from Percent Composition

Finally, with regard to deriving empirical formulas, consider instances in which a compound’s percent composition is available
rather than the absolute masses of the compound’s constituent elements. In such cases, the percent composition can be used to
calculate the masses of elements present in any convenient mass of compound; these masses can then be used to derive the
empirical formula in the usual fashion.
 Example 6.2.4: Determining an Empirical Formula from Percent Composition
The bacterial fermentation of grain to produce ethanol forms a gas with a percent composition of 27.29% C and 72.71% O
(Figure 6.2.3). What is the empirical formula for this gas?
Figure 6.2.3 : An oxide of carbon is removed from these fermentation tanks through the large copper pipes at the top. (credit:
“Dual Freq”/Wikimedia Commons)
A picture is shown of four copper-colored industrial containers with a large pipe connecting to the top of each one.
Solution
Since the scale for percentages is 100, it is most convenient to calculate the mass of elements present in a sample weighing 100
g. The calculation is “most convenient” because, per the definition for percent composition, the mass of a given element in
grams is numerically equivalent to the element’s mass percentage. This numerical equivalence results from the definition of the

“percentage” unit, whose name is derived from the Latin phrase per centum meaning “by the hundred.” Considering this
definition, the mass percentages provided may be more conveniently expressed as fractions:
27.29 g C
27.29 % C =
100 g compound
72.71 g O
72.71 % O =
100 g compound
The molar amounts of carbon and hydrogen in a 100-g sample are calculated by dividing each element’s mass by its molar mass:
mol C
27.29 g C ( ) = 2.272 mol C
12.01 g
mol O
72.71 g O ( ) = 4.544 mol O
16.00 g
Coefficients for the tentative empirical formula are derived by dividing each molar amount by the lesser of the two:
2.272 mol C
=1
2.272
4.544 mol O
=2
2.272
Since the resulting ratio is one carbon to two oxygen atoms, the empirical formula is CO2.
 Exercise 6.2.4
What is the empirical formula of a compound containing 40.0% C, 6.71% H, and 53.28% O?
Answer
C H2 O
Derivation of Molecular Formulas

Recall that empirical formulas are symbols representing the relative numbers of a compound’s elements. Determining the absolute
numbers of atoms that compose a single molecule of a covalent compound requires knowledge of both its empirical formula and its
molecular mass or molar mass. These quantities may be determined experimentally by various measurement techniques. Molecular
mass, for example, is often derived from the mass spectrum of the compound (see discussion of this technique in the previous
chapter on atoms and molecules). Molar mass can be measured by a number of experimental methods, many of which will be
introduced in later chapters of this text.
Molecular formulas are derived by comparing the compound’s molecular or molar mass to its empirical formula mass. As the name
suggests, an empirical formula mass is the sum of the average atomic masses of all the atoms represented in an empirical formula.
If we know the molecular (or molar) mass of the substance, we can divide this by the empirical formula mass in order to identify
the number of empirical formula units per molecule, which we designate as n:
g
molecular or molar mass (amu or )
mol
= n f ormula units/molecule
g
empirical f ormula mass (amu or )
mol
The molecular formula is then obtained by multiplying each subscript in the empirical formula by n, as shown by the generic
empirical formula AxBy:
(Ax By )n = Anx Bnx

For example, consider a covalent compound whose empirical formula is determined to be CH2O. The empirical formula mass for
this compound is approximately 30 amu (the sum of 12 amu for one C atom, 2 amu for two H atoms, and 16 amu for one O atom).
If the compound’s molecular mass is determined to be 180 amu, this indicates that molecules of this compound contain six times
the number of atoms represented in the empirical formula:
180 amu/molecule
= 6 f ormula units/molecule
amu
30
f ormula unit
Molecules of this compound are then represented by molecular formulas whose subscripts are six times greater than those in the
empirical formula:
(CH O) =C H O
2 6 6 12 6
Note that this same approach may be used when the molar mass (g/mol) instead of the molecular mass (amu) is used. In this case,
we are merely considering one mole of empirical formula units and molecules, as opposed to single units and molecules.
 Example 6.2.5: Determination of the Molecular Formula for Nicotine
Nicotine, an alkaloid in the nightshade family of plants that is mainly responsible for the addictive nature of cigarettes,
contains 74.02% C, 8.710% H, and 17.27% N. If 40.57 g of nicotine contains 0.2500 mol nicotine, what is the molecular
formula?
Solution
Determining the molecular formula from the provided data will require comparison of the compound’s empirical formula mass
to its molar mass. As the first step, use the percent composition to derive the compound’s empirical formula. Assuming a
convenient, a 100-g sample of nicotine yields the following molar amounts of its elements:
1 mol C
(74.02 g C) ( ) = 6.163 mol C (6.2.1)
12.01 g C
1 mol H
(8.710 g H) ( ) = 8.624 mol H (6.2.2)
1.01 g H
1 mol N
(17.27 g N) ( ) = 1.233 mol N (6.2.3)
14.01 g N
Next, we calculate the molar ratios of these elements relative to the least abundant element, N .
6.163 mol C / 1.233 mol N = 5
8.264 mol H / 1.233 mol N = 7
1.233 mol N / 1.233 mol N = 1
1.233/1.233 = 1.000 mol N
6.163/1.233 = 4.998 mol C
8.624/1.233 = 6.994 mol H
The C-to-N and H-to-N molar ratios are adequately close to whole numbers, and so the empirical formula is C5H7N. The
empirical formula mass for this compound is therefore 81.13 amu/formula unit, or 81.13 g/mol formula unit.
We calculate the molar mass for nicotine from the given mass and molar amount of compound:
40.57 g nicotine 162.3 g
=
0.2500 mol nicotine mol
Comparing the molar mass and empirical formula mass indicates that each nicotine molecule contains two formula units:
162.3 g/mol
= 2 f ormula units/molecule
g
81.13
f ormula unit

Thus, we can derive the molecular formula for nicotine from the empirical formula by multiplying each subscript by two:
(C H N) =C H N
5 7 2 10 14 2
 Exercise 6.2.5
What is the molecular formula of a compound with a percent composition of 49.47% C, 5.201% H, 28.84% N, and 16.48% O,
and a molecular mass of 194.2 amu?
Answer
C8H10N4O2
Summary
The chemical identity of a substance is defined by the types and relative numbers of atoms composing its fundamental entities
(molecules in the case of covalent compounds, ions in the case of ionic compounds). A compound’s percent composition provides
the mass percentage of each element in the compound, and it is often experimentally determined and used to derive the compound’s
empirical formula. The empirical formula mass of a covalent compound may be compared to the compound’s molecular or molar
mass to derive a molecular formula.
Key Equations
mass X
%X = × 100%
mass compound
g
molecular or molar mass (amu or )
mol
= n f ormula units/molecule
g
empirical f ormula mass (amu or )
mol
(AxBy)n = AnxBny
Glossary
percent composition
percentage by mass of the various elements in a compound
empirical formula mass

sum of average atomic masses for all atoms represented in an empirical formula
This page titled 6.2: Determining Empirical and Molecular Formulas is shared under a CC BY license and was authored, remixed, and/or curated
by OpenStax.
3.2: Determining Empirical and Molecular Formulas is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-
2e.

6.3: Molarity
Describe the fundamental properties of solutions
Calculate solution concentrations using molarity
Perform dilution calculations using the dilution equation
In preceding sections, we focused on the composition of substances: samples of matter that contain only one type of element or
compound. However, mixtures—samples of matter containing two or more substances physically combined—are more commonly
encountered in nature than are pure substances. Similar to a pure substance, the relative composition of a mixture plays an
important role in determining its properties. The relative amount of oxygen in a planet’s atmosphere determines its ability to sustain
aerobic life. The relative amounts of iron, carbon, nickel, and other elements in steel (a mixture known as an “alloy”) determine its
physical strength and resistance to corrosion. The relative amount of the active ingredient in a medicine determines its effectiveness
in achieving the desired pharmacological effect. The relative amount of sugar in a beverage determines its sweetness (Figure
6.3.1). In this section, we will describe one of the most common ways in which the relative compositions of mixtures may be
quantified.
Figure 6.3.1 : Sugar is one of many components in the complex mixture known as coffee. The amount of sugar in a given amount
of coffee is an important determinant of the beverage’s sweetness. (credit: Jane Whitney)
Solutions
We have previously defined solutions as homogeneous mixtures, meaning that the composition of the mixture (and therefore its
properties) is uniform throughout its entire volume. Solutions occur frequently in nature and have also been implemented in many
forms of manmade technology. We will explore a more thorough treatment of solution properties in the chapter on solutions and
colloids, but here we will introduce some of the basic properties of solutions.
The relative amount of a given solution component is known as its concentration. Often, though not always, a solution contains one
component with a concentration that is significantly greater than that of all other components. This component is called the solvent
and may be viewed as the medium in which the other components are dispersed, or dissolved. Solutions in which water is the
solvent are, of course, very common on our planet. A solution in which water is the solvent is called an aqueous solution.
A solute is a component of a solution that is typically present at a much lower concentration than the solvent. Solute concentrations
are often described with qualitative terms such as dilute (of relatively low concentration) and concentrated (of relatively high
concentration).
Concentrations may be quantitatively assessed using a wide variety of measurement units, each convenient for particular
applications. Molarity (M) is a useful concentration unit for many applications in chemistry. Molarity is defined as the number of
moles of solute in exactly 1 liter (1 L) of the solution:
mol solute
M = (6.3.1)
L solution

 Example 6.3.1: Calculating Molar Concentrations
A 355-mL soft drink sample contains 0.133 mol of sucrose (table sugar). What is the molar concentration of sucrose in the
beverage?
Solution
Since the molar amount of solute and the volume of solution are both given, the molarity can be calculated using the definition
of molarity. Per this definition, the solution volume must be converted from mL to L:
mol solute
M =
L solution
0.133 mol
=
1 L
355 mL ×
1000 mL
= 0.375 M
 Exercise 6.3.1
A teaspoon of table sugar contains about 0.01 mol sucrose. What is the molarity of sucrose if a teaspoon of sugar has been
dissolved in a cup of tea with a volume of 200 mL?
Answer
0.05 M
 Example 6.3.2: Deriving Moles and Volumes from Molar Concentrations
How much sugar (mol) is contained in a modest sip (~10 mL) of the soft drink from Example 6.3.1?
Solution
In this case, we can rearrange the definition of molarity to isolate the quantity sought, moles of sugar. We then substitute the
value for molarity that we derived in Example 3.4.2, 0.375 M:
mol solute
M = (6.3.2)
L solution
mol solute = M × L solution
mol sugar 1 L
mol solute = 0.375 × (10 mL × ) = 0.004 mol sugar
L 1000 mL
 Exercise 6.3.2
What volume (mL) of the sweetened tea described in Example 6.3.1 contains the same amount of sugar (mol) as 10 mL of the
soft drink in this example?
Answer
80 mL

 Example 6.3.3: Calculating Molar Concentrations from the Mass of Solute
Distilled white vinegar (Figure 6.3.2) is a solution of acetic acid, C H C O H, in water. A 0.500-L vinegar solution contains
3 2
25.2 g of acetic acid. What is the concentration of the acetic acid solution in units of molarity?
Figure 6.3.3 : Distilled white vinegar is a solution of acetic acid in water.

A label on a container is shown. The label has a picture of a salad with the words “Distilled White Vinegar,” and, “Reduced
with water to 5% acidity,” written above it.
Solution
As in previous examples, the definition of molarity is the primary equation used to calculate the quantity sought. In this case,
the mass of solute is provided instead of its molar amount, so we must use the solute’s molar mass to obtain the amount of
solute in moles:
1 mol CH CO H
3 2
25.2 g CH CO H ×
3 2
mol solute 60.052 g CH CO H
3 2
M = = = 0.839 M (6.3.3)
L solution 0.500 L solution
0.839 mol solute

M =
1.00 L solution
Nov 29, 2019, 5:24 PM

mol solute
M = = 0.839 M (6.3.4)
L solution
 Exercise 6.3.3
Calculate the molarity of 6.52 g of C oC l (128.9 g/mol) dissolved in an aqueous solution with a total volume of 75.0 mL.
2
Answer
0.674 M
 Example 6.3.4: Determining the Mass of Solute in a Given Volume of Solution
How many grams of NaCl are contained in 0.250 L of a 5.30-M solution?
Solution
The volume and molarity of the solution are specified, so the amount (mol) of solute is easily computed as demonstrated in
Example 6.3.3:

mol solute
M = (6.3.5)
L solution
mol solute = M × L solution (6.3.6)
mol NaCl
mol solute = 5.30 × 0.250 L = 1.325 mol NaCl (6.3.7)
L
Finally, this molar amount is used to derive the mass of NaCl:

58.44 g NaCl
1.325 mol NaCl × = 77.4 g NaCl (6.3.8)
mol NaCl
 Exercise 6.3.4
How many grams of C aC l (110.98 g/mol) are contained in 250.0 mL of a 0.200-M solution of calcium chloride?
2
Answer
5.55 g C aC l 2
When performing calculations stepwise, as in Example 6.3.3, it is important to refrain from rounding any intermediate calculation
results, which can lead to rounding errors in the final result. In Example 6.3.4, the molar amount of NaCl computed in the first
step, 1.325 mol, would be properly rounded to 1.32 mol if it were to be reported; however, although the last digit (5) is not
significant, it must be retained as a guard digit in the intermediate calculation. If we had not retained this guard digit, the final
calculation for the mass of NaCl would have been 77.1 g, a difference of 0.3 g.
In addition to retaining a guard digit for intermediate calculations, we can also avoid rounding errors by performing computations
in a single step (Example 6.3.5). This eliminates intermediate steps so that only the final result is rounded.
 Example 6.3.5: Determining the Volume of Solution
In Example 6.3.3 , we found the typical concentration of vinegar to be 0.839 M. What volume of vinegar contains 75.6 g of
acetic acid?
Solution
First, use the molar mass to calculate moles of acetic acid from the given mass:
mol solute
g solute × = mol solute (6.3.9)
g solute
Then, use the molarity of the solution to calculate the volume of solution containing this molar amount of solute:
L solution
mol solute × = L solution (6.3.10)
mol solute
Combining these two steps into one yields:

mol solute L solution
g solute × × = L solution (6.3.11)
g solute mol solute
mol CH CO H L solution
3 2
75.6 g CH CO H ( )( ) = 1.50 L solution (6.3.12)
3 2
60.05 g 0.839 mol CH CO H
3 2
 Exercise 6.3.5:
What volume of a 1.50-M KBr solution contains 66.0 g KBr?
Answer

0.370 L
Dilution of Solutions
Dilution is the process whereby the concentration of a solution is lessened by the addition of solvent. For example, we might say
that a glass of iced tea becomes increasingly diluted as the ice melts. The water from the melting ice increases the volume of the
solvent (water) and the overall volume of the solution (iced tea), thereby reducing the relative concentrations of the solutes that
give the beverage its taste (Figure 6.3.2).
Figure 6.3.2 : Both solutions contain the same mass of copper nitrate. The solution on the right is more dilute because the copper
nitrate is dissolved in more solvent. (credit: Mark Ott).
This figure shows two graduated cylinders side-by-side. The first has about half as much blue liquid as the second. The blue liquid
is darker in the first cylinder than in the second.
Dilution is also a common means of preparing solutions of a desired concentration. By adding solvent to a measured portion of a
more concentrated stock solution, we can achieve a particular concentration. For example, commercial pesticides are typically sold
as solutions in which the active ingredients are far more concentrated than is appropriate for their application. Before they can be
used on crops, the pesticides must be diluted. This is also a very common practice for the preparation of a number of common
laboratory reagents (Figure 6.3.3).
Figure 6.3.3 : A solution of KM nO is prepared by mixing water with 4.74 g of KMnO4 in a flask. (credit: modification of work
4
by Mark Ott)
This figure shows two photos. In the first, there is an empty glass container, 4.75 g of K M n O subscript 4 powder on a white
circle, and a bottle of distilled water. In the second photo the powder and about half the water have been added to the glass
container. The liquid in the glass container is almost black in color.
A simple mathematical relationship can be used to relate the volumes and concentrations of a solution before and after the dilution
process. According to the definition of molarity, the molar amount of solute in a solution is equal to the product of the solution’s
molarity and its volume in liters:
n = ML
Expressions like these may be written for a solution before and after it is diluted:

n1 = M1 L1
n2 = M2 L2
where the subscripts “1” and “2” refer to the solution before and after the dilution, respectively. Since the dilution process does not
change the amount of solute in the solution,n1 = n2. Thus, these two equations may be set equal to one another:
M1 L1 = M2 L2
This relation is commonly referred to as the dilution equation. Although we derived this equation using molarity as the unit of
concentration and liters as the unit of volume, other units of concentration and volume may be used, so long as the units properly
cancel per the factor-label method. Reflecting this versatility, the dilution equation is often written in the more general form:
C1 V1 = C2 V2
where C and V are concentration and volume, respectively.
 Example 6.3.6: Determining the Concentration of a Diluted Solution
If 0.850 L of a 5.00-M solution of copper nitrate, Cu(NO3)2, is diluted to a volume of 1.80 L by the addition of water, what is
the molarity of the diluted solution?
Solution
We are given the volume and concentration of a stock solution, V1 and C1, and the volume of the resultant diluted solution, V2.
We need to find the concentration of the diluted solution, C2. We thus rearrange the dilution equation in order to isolate C2:
C1 V1 = C2 V2
C1 V1
C2 =
V2
Since the stock solution is being diluted by more than two-fold (volume is increased from 0.85 L to 1.80 L), we would expect
the diluted solution’s concentration to be less than one-half 5 M. We will compare this ballpark estimate to the calculated result
to check for any gross errors in computation (for example, such as an improper substitution of the given quantities).
Substituting the given values for the terms on the right side of this equation yields:
mol
0.850 L × 5.00
L
C2 = = 2.36 M
1.80 L
This result compares well to our ballpark estimate (it’s a bit less than one-half the stock concentration, 5 M).
 Exercise 6.3.6
What is the concentration of the solution that results from diluting 25.0 mL of a 2.04-M solution of CH3OH to 500.0 mL?
Answer
0.102 M C H 3 OH
 Example 6.3.7: Volume of a Diluted Solution
What volume of 0.12 M HBr can be prepared from 11 mL (0.011 L) of 0.45 M HBr?
Solution

We are given the volume and concentration of a stock solution, V1 and C1, and the concentration of the resultant diluted
solution, C2. We need to find the volume of the diluted solution, V2. We thus rearrange the dilution equation in order to isolate
V2:
C1 V1 = C2 V2
C1 V1
V2 =
C2
Since the diluted concentration (0.12 M) is slightly more than one-fourth the original concentration (0.45 M), we would expect
the volume of the diluted solution to be roughly four times the original volume, or around 44 mL. Substituting the given values
and solving for the unknown volume yields:
(0.45 M )(0.011 L)
V2 =
(0.12 M )
V2 = 0.041 L
The volume of the 0.12-M solution is 0.041 L (41 mL). The result is reasonable and compares well with our rough estimate.
 Exercise 6.3.7
A laboratory experiment calls for 0.125 M H N O . What volume of 0.125 M H N O can be prepared from 0.250 L of 1.88 M
3 3
HN O ?3
Answer
3.76 L
 Example 6.3.8: Volume of a Concentrated Solution Needed for Dilution
What volume of 1.59 M KOH is required to prepare 5.00 L of 0.100 M KOH?
Solution
We are given the concentration of a stock solution, C1, and the volume and concentration of the resultant diluted solution, V2
and C2. We need to find the volume of the stock solution, V1. We thus rearrange the dilution equation in order to isolate V1:
C1 V1 = C2 V2
C2 V2
V1 =
C1
Since the concentration of the diluted solution 0.100 M is roughly one-sixteenth that of the stock solution (1.59 M), we would
expect the volume of the stock solution to be about one-sixteenth that of the diluted solution, or around 0.3 liters. Substituting
the given values and solving for the unknown volume yields:
(0.100 M )(5.00 L)
V1 =
1.59 M
V1 = 0.314 L
Thus, we would need 0.314 L of the 1.59-M solution to prepare the desired solution. This result is consistent with our rough
estimate.

 Exercise 6.3.8
What volume of a 0.575-M solution of glucose, C6H12O6, can be prepared from 50.00 mL of a 3.00-M glucose solution?
Answer
0.261
Summary
Solutions are homogeneous mixtures. Many solutions contain one component, called the solvent, in which other components,
called solutes, are dissolved. An aqueous solution is one for which the solvent is water. The concentration of a solution is a measure
of the relative amount of solute in a given amount of solution. Concentrations may be measured using various units, with one very
useful unit being molarity, defined as the number of moles of solute per liter of solution. The solute concentration of a solution may
be decreased by adding solvent, a process referred to as dilution. The dilution equation is a simple relation between concentrations
and volumes of a solution before and after dilution.
Key Equations
mol solute
M =
L solution
C1V1 = C2V2
Glossary
aqueous solution
solution for which water is the solvent
concentrated
qualitative term for a solution containing solute at a relatively high concentration
concentration
quantitative measure of the relative amounts of solute and solvent present in a solution
dilute
qualitative term for a solution containing solute at a relatively low concentration
dilution
process of adding solvent to a solution in order to lower the concentration of solutes
dissolved
describes the process by which solute components are dispersed in a solvent
molarity (M)
unit of concentration, defined as the number of moles of solute dissolved in 1 liter of solution
solute
solution component present in a concentration less than that of the solvent
solvent
solution component present in a concentration that is higher relative to other components
This page titled 6.3: Molarity is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
3.3: Molarity is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

Define the concentration units of mass percentage, volume percentage, mass-volume percentage, parts-per-million (ppm),
and parts-per-billion (ppb)
Perform computations relating a solution’s concentration and its components’ volumes and/or masses using these units
In the previous section, we introduced molarity, a very useful measurement unit for evaluating the concentration of solutions.
However, molarity is only one measure of concentration. In this section, we will introduce some other units of concentration that
are commonly used in various applications, either for convenience or by convention.
Mass Percentage
Earlier in this chapter, we introduced percent composition as a measure of the relative amount of a given element in a compound.
Percentages are also commonly used to express the composition of mixtures, including solutions. The mass percentage of a
solution component is defined as the ratio of the component’s mass to the solution’s mass, expressed as a percentage:
mass of component
mass percentage = × 100% (6.4.1)
mass of solution
We are generally most interested in the mass percentages of solutes, but it is also possible to compute the mass percentage of
solvent.
Mass percentage is also referred to by similar names such as percent mass, percent weight, weight/weight percent, and other
variations on this theme. The most common symbol for mass percentage is simply the percent sign, %, although more detailed
symbols are often used including %mass, %weight, and (w/w)%. Use of these more detailed symbols can prevent confusion of
mass percentages with other types of percentages, such as volume percentages (to be discussed later in this section).
Mass percentages are popular concentration units for consumer products. The label of a typical liquid bleach bottle (Figure 6.4.1)
cites the concentration of its active ingredient, sodium hypochlorite (NaOCl), as being 7.4%. A 100.0-g sample of bleach would
therefore contain 7.4 g of NaOCl.
Figure 6.4.1 : Liquid bleach is an aqueous solution of sodium hypochlorite (NaOCl). This brand has a concentration of 7.4%
NaOCl by mass.
The sides of two cylindrical containers are shown. Each container’s label is partially visible. The left container’s label reads
“Bleach.” The right label contains more information about the product including the phrase, “Contains: Sodium hypochlorite 7.4
%.”
 Example 6.4.1: Calculation of Percent by Mass
A 5.0-g sample of spinal fluid contains 3.75 mg (0.00375 g) of glucose. What is the percent by mass of glucose in spinal fluid?
Solution
The spinal fluid sample contains roughly 4 mg of glucose in 5000 mg of fluid, so the mass fraction of glucose should be a bit
less than one part in 1000, or about 0.1%. Substituting the given masses into the equation defining mass percentage yields:

1 g
3.75 mg glucose ×
1000 mg
% glucose = = 0.075%
5.0 g spinal f luid
The computed mass percentage agrees with our rough estimate (it’s a bit less than 0.1%).
Note that while any mass unit may be used to compute a mass percentage (mg, g, kg, oz, and so on), the same unit must be
used for both the solute and the solution so that the mass units cancel, yielding a dimensionless ratio. In this case, we converted
the units of solute in the numerator from mg to g to match the units in the denominator. We could just as easily have converted
the denominator from g to mg instead. As long as identical mass units are used for both solute and solution, the computed mass
percentage will be correct.
 Exercise 6.4.1
A bottle of a tile cleanser contains 135 g of HCl and 775 g of water. What is the percent by mass of HCl in this cleanser?
Answer
14.8%
 Example 6.4.2: Calculations using Mass Percentage
“Concentrated” hydrochloric acid is an aqueous solution of 37.2% HCl that is commonly used as a laboratory reagent. The
density of this solution is 1.19 g/mL. What mass of HCl is contained in 0.500 L of this solution?
Solution
The HCl concentration is near 40%, so a 100-g portion of this solution would contain about 40 g of HCl. Since the solution
density isn’t greatly different from that of water (1 g/mL), a reasonable estimate of the HCl mass in 500 g (0.5 L) of the
solution is about five times greater than that in a 100 g portion, or 5 × 40 = 200 g . To derive the mass of solute in a solution
from its mass percentage, we need to know the corresponding mass of the solution. Using the solution density given, we can
convert the solution’s volume to mass, and then use the given mass percentage to calculate the solute mass. This mathematical
approach is outlined in this flowchart:
A diagram of three boxes connected by a right-facing arrow in between each is shown. The box on the left contains the phrase,
“Volume of solution ( m L ),” the middle box reads, “Mass of solution ( g ),” while the one on the right contains the phrase,
“Mass of H C l ( g ).” There is a phrase under the left arrow that says, “Multiply by density ( g / m L )” and under the right
arrow it states, “Multiply by mass percent as ratio ( g H C l / g solution ).”
For proper unit cancellation, the 0.500-L volume is converted into 500 mL, and the mass percentage is expressed as a ratio,
37.2 g HCl/g solution:
1.19 g solution 37.2 g HCl
500 mL solution ( )( ) = 221 g HCl
mL solution 100 g solution
This mass of HCl is consistent with our rough estimate of approximately 200 g.
 Exercise 6.4.2
What volume of concentrated HCl solution contains 125 g of HCl?
Answer

282 mL
Volume Percentage
Liquid volumes over a wide range of magnitudes are conveniently measured using common and relatively inexpensive laboratory
equipment. The concentration of a solution formed by dissolving a liquid solute in a liquid solvent is therefore often expressed as a
volume percentage, %vol or (v/v)%:
volume solute
volume percentage = × 100% (6.4.2)
volume solution
 Example 6.4.3: Calculations using Volume Percentage
Rubbing alcohol (isopropanol) is usually sold as a 70%vol aqueous solution. If the density of isopropyl alcohol is 0.785 g/mL,
how many grams of isopropyl alcohol are present in a 355 mL bottle of rubbing alcohol?
Solution
Per the definition of volume percentage, the isopropanol volume is 70% of the total solution volume. Multiplying the
isopropanol volume by its density yields the requested mass:
70 mL isopropyl alcohol 0.785 g isopropyl alcohol
355 mL solution( )( ) = 195 g isopropyl alcohol
100 mL solution 1 mL isopropyl alcohol
 Exercise 6.4.3
Wine is approximately 12% ethanol (CH CH OH ) by volume. Ethanol has a molar mass of 46.06 g/mol and a density 0.789
3 2
g/mL. How many moles of ethanol are present in a 750-mL bottle of wine?
Answer
1.5 mol ethanol
Mass-Volume Percentage
“Mixed” percentage units, derived from the mass of solute and the volume of solution, are popular for certain biochemical and
medical applications. A mass-volume percent is a ratio of a solute’s mass to the solution’s volume expressed as a percentage. The
specific units used for solute mass and solution volume may vary, depending on the solution. For example, physiological saline
solution, used to prepare intravenous fluids, has a concentration of 0.9% mass/volume (m/v), indicating that the composition is 0.9
g of solute per 100 mL of solution. The concentration of glucose in blood (commonly referred to as “blood sugar”) is also typically
expressed in terms of a mass-volume ratio. Though not expressed explicitly as a percentage, its concentration is usually given in
milligrams of glucose per deciliter (100 mL) of blood (Figure 6.4.2).

Figure 6.4.2 : “Mixed” mass-volume units are commonly encountered in medical settings. (a) The NaCl concentration of
physiological saline is 0.9% (m/v). (b) This device measures glucose levels in a sample of blood. The normal range for glucose
concentration in blood (fasting) is around 70–100 mg/dL. (credit a: modification of work by “The National Guard”/Flickr; credit b:
modification of work by Biswarup Ganguly).
Two pictures are shown labeled a and b. Picture a depicts a clear, colorless solution in a plastic bag being held in a person’s hand.
Picture b shows a person’s hand holding a detection meter with a digital readout screen while another hand holds someone’s finger
up to the end of the meter. The meter is pressed to the drop of blood that is at the end of the person’s finger.
Parts per Million and Parts per Billion

Very low solute concentrations are often expressed using appropriately small units such as parts per million (ppm) or parts per
billion (ppb). Like percentage (“part per hundred”) units, ppm and ppb may be defined in terms of masses, volumes, or mixed
mass-volume units. There are also ppm and ppb units defined with respect to numbers of atoms and molecules.
The mass-based definitions of ppm and ppb are given here:
mass solute
6
ppm = × 10 ppm (6.4.3)
mass solution
mass solute
9
ppb = × 10 ppb (6.4.4)
mass solution
Both ppm and ppb are convenient units for reporting the concentrations of pollutants and other trace contaminants in water.
Concentrations of these contaminants are typically very low in treated and natural waters, and their levels cannot exceed relatively
low concentration thresholds without causing adverse effects on health and wildlife. For example, the EPA has identified the
maximum safe level of fluoride ion in tap water to be 4 ppm. Inline water filters are designed to reduce the concentration of
fluoride and several other trace-level contaminants in tap water (Figure 6.4.3).
Figure 6.4.3 : (a) In some areas, trace-level concentrations of contaminants can render unfiltered tap water unsafe for drinking and
cooking. (b) Inline water filters reduce the concentration of solutes in tap water. (credit a: modification of work by Jenn Durfey;
credit b: modification of work by “vastateparkstaff”/Wikimedia commons).
Two pictures are shown labeled a and b. Picture a depicts a clear, colorless solution in a plastic bag being held in a person’s hand.
Picture b shows a person’s hand holding a detection meter with a digital readout screen while another hand holds someone’s finger
up to the end of the meter. The meter is pressed to the drop of blood that is at the end of the person’s finger.

 Example 6.4.4: Parts per Million and Parts per Billion Concentrations
According to the EPA, when the concentration of lead in tap water reaches 15 ppb, certain remedial actions must be taken.
What is this concentration in ppm? At this concentration, what mass of lead (μg) would be contained in a typical glass of water
(300 mL)?
Solution
The definitions of the ppm and ppb units may be used to convert the given concentration from ppb to ppm. Comparing these
two unit definitions shows that ppm is 1000 times greater than ppb (1 ppm = 103 ppb). Thus:
1 ppm
15 ppb × = 0.015 ppm
3
10 ppb
The definition of the ppb unit may be used to calculate the requested mass if the mass of the solution is provided. However,
only the volume of solution (300 mL) is given, so we must use the density to derive the corresponding mass. We can assume
the density of tap water to be roughly the same as that of pure water (~1.00 g/mL), since the concentrations of any dissolved
substances should not be very large. Rearranging the equation defining the ppb unit and substituting the given quantities yields:
mass solute
9
ppb = × 10 ppb
mass solution
ppb × mass solution

mass solute =
9
10 ppb
1.00 g
15 ppb × 300 mL ×
mL −6
mass solute = = 4.5 × 10 g
9
10 ppb
Finally, convert this mass to the requested unit of micrograms:

1 μg
−6
4.5 × 10 g× = 4.5 μg
−6
10 g
 Exercise 6.4.4
A 50.0-g sample of industrial wastewater was determined to contain 0.48 mg of mercury. Express the mercury concentration of
the wastewater in ppm and ppb units.
Answer
9.6 ppm, 9600 ppb
Summary
In addition to molarity, a number of other solution concentration units are used in various applications. Percentage concentrations
based on the solution components’ masses, volumes, or both are useful for expressing relatively high concentrations, whereas lower
concentrations are conveniently expressed using ppm or ppb units. These units are popular in environmental, medical, and other
fields where mole-based units such as molarity are not as commonly used.
Glossary
mass percentage
ratio of solute-to-solution mass expressed as a percentage
mass-volume percent

ratio of solute mass to solution volume, expressed as a percentage
parts per billion (ppb)

ratio of solute-to-solution mass multiplied by 109
parts per million (ppm)

ratio of solute-to-solution mass multiplied by 106
volume percentage
ratio of solute-to-solution volume expressed as a percentage
This page titled 6.4: Other Units for Solution Concentrations is shared under a CC BY license and was authored, remixed, and/or curated by
OpenStax.
3.4: Other Units for Solution Concentrations is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

What is the total mass (amu) of carbon in each of the following molecules?
1. (a) CH4
2. (b) CHCl3
3. (c) C12H10O6
4. (d) CH3CH2CH2CH2CH3
(a) 12.01 amu; (b) 12.01 amu; (c) 144.12 amu; (d) 60.05 amu
What is the total mass of hydrogen in each of the molecules?
1. (a) CH4
2. (b) CHCl3
3. (c) C12H10O6
4. (d) CH3CH2CH2CH2CH3
Calculate the molecular or formula mass of each of the following:
(a) P4
(b) H2O
(c) Ca(NO3)2
(d) CH3CO2H (acetic acid)
(e) C12H22O11 (sucrose, cane sugar).
(a) 123.896 amu; (b) 18.015 amu; (c) 164.086 amu; (d) 60.052 amu; (e) 342.297 amu
Determine the molecular mass of the following compounds:
(a)
A structure is shown. A C atom is bonded to two C l atoms and forms a double bond with one O atom.
(b)
A structure is shown. Two C atoms form a triple bond with each other. Each C atom also forms a single bond with on H atom.
(c)
A structure is shown. Two C atoms form double bonds with each other. Each C atom also forms a single bond with an H atom and a B r atom.
(d)
A structure is shown. An S atom forms double bonds with two O atoms. The S atom also forms a single bond with an O atom which forms a single bond with an H atom. The S atom also forms a single bond with
another O atom which forms a single bond with another H atom.
Determine the molecular mass of the following compounds:

(a)
A structure is shown. Two C atoms form double bonds with each other. The C atom on the left forms a single bond with two H atoms each. The C atom on the right forms a single bond with an H atom and with a C H
subscript 2 C H subscript 3 group.
(b)
A structure is shown. There is a C atom which forms single bonds with three H atoms each. This C atom is bonded to another C atom. This second C atom forms a triple bond with another C atom which forms a
single bond with a fourth C atom. The fourth C atom forms single bonds with three H atoms each.
(c)
A structure is shown. An S i atom forms a single bond with a C l atom, a single bond with a C l atom, a single bond with an H atom, and a single bond with another S i atom. The second S i atom froms a single bond
with a C l atom, a single bond with a C l atom, and a single bond with an H atom.
(d)
A structure is shown. A P atom forms a double bond with an O atom. It also forms a single bond with an O atom which forms a single bond with an H atom. It also forms a single bond with another O atom which
forms a single bond with an H atom. It also forms a single bond with another O atom which forms a single bond with an H atom.

1. (a) 56.107 amu;
2. (b) 54.091 amu;
3. (c) 199.9976 amu;
4. (d) 97.9950 amu
Which molecule has a molecular mass of 28.05 amu?
(a)
A structure is shown. A C atom forms a triple bond with another C atom. Each C atom also forms a single bond with an H atom.
(b)
A structure is shown. Two C atoms form a double bond with each other. Each C atom also forms a single bond with two H atoms.
(c)
A structure is shown. A C atom forms a single bond with three H atoms each and with another C atom. The second C atom also forms a single bond with three H atoms each.
Write a sentence that describes how to determine the number of moles of a compound in a known mass of the compound if we
know its molecular formula.
Use the molecular formula to find the molar mass; to obtain the number of moles, divide the mass of compound by the molar mass
of the compound expressed in grams.
Compare 1 mole of H2, 1 mole of O2, and 1 mole of F2.
1. (a) Which has the largest number of molecules? Explain why.
2. (b) Which has the greatest mass? Explain why.
Which contains the greatest mass of oxygen: 0.75 mol of ethanol (C2H5OH), 0.60 mol of formic acid (HCO2H), or 1.0 mol of water
(H2O)? Explain why.
Formic acid. Its formula has twice as many oxygen atoms as the other two compounds (one each). Therefore, 0.60 mol of formic
acid would be equivalent to 1.20 mol of a compound containing a single oxygen atom.
Which contains the greatest number of moles of oxygen atoms: 1 mol of ethanol (C2H5OH), 1 mol of formic acid (HCO2H), or 1
mol of water (H2O)? Explain why.
How are the molecular mass and the molar mass of a compound similar and how are they different?
The two masses have the same numerical value, but the units are different: The molecular mass is the mass of 1 molecule while the
molar mass is the mass of 6.022 × 1023 molecules.
Calculate the molar mass of each of the following compounds:
1. (a) hydrogen fluoride, HF
2. (b) ammonia, NH3
3. (c) nitric acid, HNO3
4. (d) silver sulfate, Ag2SO4
5. (e) boric acid, B(OH)3
Calculate the molar mass of each of the following:
1. (a) S8
2. (b) C5H12
3. (c) Sc2(SO4)3
4. (d) CH3COCH3 (acetone)
5. (e) C6H12O6 (glucose)
(a) 256.528 g/mol; (b) 72.150 g mol−1; (c) 378.103 g mol−1; (d) 58.080 g mol−1; (e) 180.158 g mol−1
Calculate the empirical or molecular formula mass and the molar mass of each of the following minerals:
1. (a) limestone, CaCO3
2. (b) halite, NaCl
3. (c) beryl, Be3Al2Si6O18

4. (d) malachite, Cu2(OH)2CO3
5. (e) turquoise, CuAl6(PO4)4(OH)8(H2O)4
Calculate the molar mass of each of the following:
1. (a) the anesthetic halothane, C2HBrClF3
2. (b) the herbicide paraquat, C12H14N2Cl2
3. (c) caffeine, C8H10N4O2
4. (d) urea, CO(NH2)2
5. (e) a typical soap, C17H35CO2Na
(a) 197.382 g mol−1; (b) 257.163 g mol−1; (c) 194.193 g mol−1; (d) 60.056 g mol−1; (e) 306.464 g mol−1
Determine the number of moles of compound and the number of moles of each type of atom in each of the following:
1. (a) 25.0 g of propylene, C3H6
2. (b) 3.06 × 10−3 g of the amino acid glycine, C2H5NO2
3. (c) 25 lb of the herbicide Treflan, C13H16N2O4F (1 lb = 454 g)
4. (d) 0.125 kg of the insecticide Paris Green, Cu4(AsO3)2(CH3CO2)2
5. (e) 325 mg of aspirin, C6H4(CO2H)(CO2CH3)
Determine the mass of each of the following:
1. (a) 0.0146 mol KOH
2. (b) 10.2 mol ethane, C2H6
3. (c) 1.6 × 10−3 mol Na2 SO4
4. (d) 6.854 × 103 mol glucose, C6 H12 O6
5. (e) 2.86 mol Co(NH3)6Cl3
1. (a) 0.819 g;
2. (b) 307 g;
3. (c) 0.23 g;
4. (d) 1.235 × 106 g (1235 kg);
5. (e) 765 g
Determine the number of moles of the compound and determine the number of moles of each type of atom in each of the following:
1. (a) 2.12 g of potassium bromide, KBr
2. (b) 0.1488 g of phosphoric acid, H3PO4
3. (c) 23 kg of calcium carbonate, CaCO3
4. (d) 78.452 g of aluminum sulfate, Al2(SO4)3
5. (e) 0.1250 mg of caffeine, C8H10N4O2
Determine the mass of each of the following:
1. (a) 2.345 mol LiCl
2. (b) 0.0872 mol acetylene, C2H2
3. (c) 3.3 × 10−2 mol Na2 CO3
4. (d) 1.23 × 103 mol fructose, C6 H12 O6
5. (e) 0.5758 mol FeSO4(H2O)7
1. (a) 99.41 g;
2. (b) 2.27 g;
3. (c) 3.5 g;
4. (d) 222 kg;
5. (e) 160.1 g
The approximate minimum daily dietary requirement of the amino acid leucine, C6H13NO2, is 1.1 g. What is this requirement in
moles?
Determine the mass in grams of each of the following:

1. (a) 0.600 mol of oxygen atoms
2. (b) 0.600 mol of oxygen molecules, O2
3. (c) 0.600 mol of ozone molecules, O3
1.
(a) 9.60 g; (b) 19.2 g; (c) 28.8 g
A 55-kg woman has 7.5 × 10−3 mol of hemoglobin (molar mass = 64,456 g/mol) in her blood. How many hemoglobin molecules is
this? What is this quantity in grams?
Determine the number of atoms and the mass of zirconium, silicon, and oxygen found in 0.3384 mol of zircon, ZrSiO4, a
semiprecious stone.
zirconium: 2.038 × 1023 atoms; 30.87 g; silicon: 2.038 × 1023 atoms; 9.504 g; oxygen: 8.151 × 1023 atoms; 21.66 g
Determine which of the following contains the greatest mass of hydrogen: 1 mol of CH4, 0.6 mol of C6H6, or 0.4 mol of C3H8.
Determine which of the following contains the greatest mass of aluminum: 122 g of AlPO4, 266 g of Al2Cl6, or 225 g of Al2S3.
AlPO4: 1.000 mol
Al2Cl6: 1.994 mol
Al2S3: 3.00 mol
Diamond is one form of elemental carbon. An engagement ring contains a diamond weighing 1.25 carats (1 carat = 200 mg). How
many atoms are present in the diamond?
The Cullinan diamond was the largest natural diamond ever found (January 25, 1905). It weighed 3104 carats (1 carat = 200 mg).
How many carbon atoms were present in the stone?
3.113 × 1025 C atoms
One 55-gram serving of a particular cereal supplies 270 mg of sodium, 11% of the recommended daily allowance. How many
moles and atoms of sodium are in the recommended daily allowance?
A certain nut crunch cereal contains 11.0 grams of sugar (sucrose, C12H22O11) per serving size of 60.0 grams. How many servings
of this cereal must be eaten to consume 0.0278 moles of sugar?
0.865 servings, or about 1 serving.
A tube of toothpaste contains 0.76 g of sodium monofluorophosphate (Na2PO3F) in 100 mL.
a. What mass of fluorine atoms in mg was present?
b. How many fluorine atoms were present?
Which of the following represents the least number of molecules?
a. 20.0 g of H2O (18.02 g/mol)
b. 77.0 g of CH4 (16.06 g/mol)
c. 68.0 g of CaH2 (42.09 g/mol)
d. 100.0 g of N2O (44.02 g/mol)
e. 84.0 g of HF (20.01 g/mol)
20.0 g H2O represents the least number of molecules since it has the least number of moles.

What information do we need to determine the molecular formula of a compound from the empirical formula?
Calculate the following to four significant figures:
a. (a) the percent composition of ammonia, NH3
b. (b) the percent composition of photographic “hypo,” Na2S2O3
c. (c) the percent of calcium ion in Ca3(PO4)2
(a) % N = 82.24%

% H = 17.76%;
(b) % Na = 29.08%
% S = 40.56%
% O = 30.36%;
(c) % Ca2+ = 38.76%
Determine the following to four significant figures:
a. the percent composition of hydrazoic acid, HN3
b. the percent composition of TNT, C6H2(CH3)(NO2)3
c. the percent of SO42– in Al2(SO4)3
Determine the percent ammonia, NH3, in Co(NH3)6Cl3, to three significant figures.
% NH3 = 38.2%
Determine the percent water in CuSO4·5H2O to three significant figures.
Determine the empirical formulas for compounds with the following percent compositions:
(a) 15.8% carbon and 84.2% sulfur
(b) 40.0% carbon, 6.7% hydrogen, and 53.3% oxygen
(a) CS2
(b) CH2O
Determine the empirical formulas for compounds with the following percent compositions:
(a) 43.6% phosphorus and 56.4% oxygen
(b) 28.7% K, 1.5% H, 22.8% P, and 47.0% O
A compound of carbon and hydrogen contains 92.3% C and has a molar mass of 78.1 g/mol. What is its molecular formula?
C6H6
Dichloroethane, a compound that is often used for dry cleaning, contains carbon, hydrogen, and chlorine. It has a molar mass of 99
g/mol. Analysis of a sample shows that it contains 24.3% carbon and 4.1% hydrogen. What is its molecular formula?
Determine the empirical and molecular formula for chrysotile asbestos. Chrysotile has the following percent composition: 28.03%
Mg, 21.60% Si, 1.16% H, and 49.21% O. The molar mass for chrysotile is 520.8 g/mol.
Mg3Si2H3O8 (empirical formula), Mg6Si4H6O16 (molecular formula)
Polymers are large molecules composed of simple units repeated many times. Thus, they often have relatively simple empirical
formulas. Calculate the empirical formulas of the following polymers:
a. Lucite (Plexiglas); 59.9% C, 8.06% H, 32.0% O
b. Saran; 24.8% C, 2.0% H, 73.1% Cl
c. polyethylene; 86% C, 14% H
d. polystyrene; 92.3% C, 7.7% H
e. Orlon; 67.9% C, 5.70% H, 26.4% N
A major textile dye manufacturer developed a new yellow dye. The dye has a percent composition of 75.95% C, 17.72% N, and
6.33% H by mass with a molar mass of about 240 g/mol. Determine the molecular formula of the dye.
C15H15N3
3.3: Molarity
Questions
Explain what changes and what stays the same when 1.00 L of a solution of NaCl is diluted to 1.80 L.
What information do we need to calculate the molarity of a sulfuric acid solution?

We need to know the number of moles of sulfuric acid dissolved in the solution and the volume of the solution.
What does it mean when we say that a 200-mL sample and a 400-mL sample of a solution of salt have the same molarity? In what
ways are the two samples identical? In what ways are these two samples different?
Determine the molarity for each of the following solutions:
a. 0.444 mol of CoCl2 in 0.654 L of solution
b. 98.0 g of phosphoric acid, H3PO4, in 1.00 L of solution
c. 0.2074 g of calcium hydroxide, Ca(OH)2, in 40.00 mL of solution
d. 10.5 kg of Na2SO4·10H2O in 18.60 L of solution
e. 7.0 × 10−3 mol of I2 in 100.0 mL of solution
f. 1.8 × 104 mg of HCl in 0.075 L of solution
a. (a) 0.679 M;
b. (b) 1.00 M;
c. (c) 0.06998 M;
d. (d) 1.75 M;
e. (e) 0.070 M;
f. (f) 6.6 M
Determine the molarity of each of the following solutions:
a. 1.457 mol KCl in 1.500 L of solution
b. 0.515 g of H2SO4 in 1.00 L of solution
c. 20.54 g of Al(NO3)3 in 1575 mL of solution
d. 2.76 kg of CuSO4·5H2O in 1.45 L of solution
e. 0.005653 mol of Br2 in 10.00 mL of solution
f. 0.000889 g of glycine, C2H5NO2, in 1.05 mL of solution
Answers:
a.) 0.9713 M
b.) 5.25x10-3 M
c.) 6.122x10-2 M
d.) 7.62 M
e.) 0.5653 M
f.) 1.13x10-2 M
Consider this question: What is the mass of the solute in 0.500 L of 0.30 M glucose, C6H12O6, used for intravenous injection?
(a) Outline the steps necessary to answer the question.
(b) Answer the question.
(a) determine the number of moles of glucose in 0.500 L of solution; determine the molar mass of glucose; determine the mass of
glucose from the number of moles and its molar mass; (b) 27 g
Consider this question: What is the mass of solute in 200.0 L of a 1.556-M solution of KBr?
1. (a) Outline the steps necessary to answer the question.
2. (b) Answer the question.
Answer:
(a)
1. Calculate to moles of KBr by multiplying the Molarity by the amount of solution (200.0 L)
2. Find the Molar Mass of KBr and convert moles of solute to grams
(b)

1.556 moles KBr
× 200.0 L = 311.2 moles KBr
1 L
119.0 g KBr
311.2 moles KBr × = 37, 030 g
1 mole KBr
37,030g; 37.03 kg
Calculate the number of moles and the mass of the solute in each of the following solutions:
1. (a) 2.00 L of 18.5 M H2SO4, concentrated sulfuric acid
2. (b) 100.0 mL of 3.8 × 10−5 M NaCN, the minimum lethal concentration of sodium cyanide in blood serum
3. (c) 5.50 L of 13.3 M H2CO, the formaldehyde used to “fix” tissue samples
4. (d) 325 mL of 1.8 × 10−6 M FeSO4, the minimum concentration of iron sulfate detectable by taste in drinking water
(a) 37.0 mol H2SO4;
3.63 × 103 g H2SO4;
(b) 3.8 × 10−6 mol NaCN;
1.9 × 10−4 g NaCN;
(c) 73.2 mol H2CO;
2.20 kg H2CO;
(d) 5.9 × 10−7 mol FeSO4;
8.9 × 10−5 g FeSO4
Calculate the number of moles and the mass of the solute in each of the following solutions:
a. 325 mL of 8.23 × 10−5 M KI, a source of iodine in the diet
b. 75.0 mL of 2.2 × 10−5 M H2SO4, a sample of acid rain
c. 0.2500 L of 0.1135 M K2CrO4, an analytical reagent used in iron assays
d. 10.5 L of 3.716 M (NH4)2SO4, a liquid fertilizer
Answers:
a. 2.67x10-5 moles KI; 4.44x10-3g KI
b. 1.7x10-6 moles H2SO4 ; 1.6x10-4 g H2SO4
c. 2.838x10-2 moles K2CrO4 ; 5.510g K2CrO4
d. 39.0 moles (NH4)2SO4 ; 5,160 g (NH4)2SO4
Consider this question: What is the molarity of KMnO4 in a solution of 0.0908 g of KMnO4 in 0.500 L of solution?
(a) Determine the molar mass of KMnO4; determine the number of moles of KMnO4 in the solution; from the number of moles and
the volume of solution, determine the molarity; (b) 1.15 × 10−3 M
Consider this question: What is the molarity of HCl if 35.23 mL of a solution of HCl contain 0.3366 g of HCl?
Answer:
(a)
1. Convert g of HCl to moles of HCl and convert mL of solution to L of solution
2. Divide moles of HCl by L of solution
(b)

1 mole HCl
−3
0.3366 g HCl × = 9.232 × 10 moles HCl
36.46 g HCl
35.23 mL = 0.03523 L
−3
9.232 × 10 moles HCl
= 0.2621 M HCl
0.03523 L
0.2621 M ;
Calculate the molarity of each of the following solutions:
(a) 0.195 g of cholesterol, C27H46O, in 0.100 L of serum, the average concentration of cholesterol in human serum
(b) 4.25 g of NH3 in 0.500 L of solution, the concentration of NH3 in household ammonia
(c) 1.49 kg of isopropyl alcohol, C3H7OH, in 2.50 L of solution, the concentration of isopropyl alcohol in rubbing alcohol
(d) 0.029 g of I2 in 0.100 L of solution, the solubility of I2 in water at 20 °C
(a) 5.04 × 10−3 M;
(b) 0.499 M;
(c) 9.92 M;
(d) 1.1 × 10−3 M
Calculate the molarity of each of the following solutions:
a. 293 g HCl in 666 mL of solution, a concentrated HCl solution
b. 2.026 g FeCl3 in 0.1250 L of a solution used as an unknown in general chemistry laboratories
c. 0.001 mg Cd2+ in 0.100 L, the maximum permissible concentration of cadmium in drinking water
d. 0.0079 g C7H5SNO3 in one ounce (29.6 mL), the concentration of saccharin in a diet soft drink.
There is about 1.0 g of calcium, as Ca2+, in 1.0 L of milk. What is the molarity of Ca2+ in milk?
0.025 M
What volume of a 1.00-M Fe(NO3)3 solution can be diluted to prepare 1.00 L of a solution with a concentration of 0.250 M?
If 0.1718 L of a 0.3556-M C3H7OH solution is diluted to a concentration of 0.1222 M, what is the volume of the resulting solution?
0.5000 L
If 4.12 L of a 0.850 M-H3PO4 solution is be diluted to a volume of 10.00 L, what is the concentration the resulting solution?
What volume of a 0.33-M C12H22O11 solution can be diluted to prepare 25 mL of a solution with a concentration of 0.025 M?
1.9 mL
What is the concentration of the NaCl solution that results when 0.150 L of a 0.556-M solution is allowed to evaporate until the
volume is reduced to 0.105 L?
What is the molarity of the diluted solution when each of the following solutions is diluted to the given final volume?
a. (a) 1.00 L of a 0.250-M solution of Fe(NO3)3 is diluted to a final volume of 2.00 L
b. (b) 0.5000 L of a 0.1222-M solution of C3H7OH is diluted to a final volume of 1.250 L
c. (c) 2.35 L of a 0.350-M solution of H3PO4 is diluted to a final volume of 4.00 L
d. (d) 22.50 mL of a 0.025-M solution of C12H22O11 is diluted to 100.0 mL
1. (a) 0.125 M;
2. (b) 0.04888 M;
3. (c) 0.206 M;
4. (e) 0.0056 M
What is the final concentration of the solution produced when 225.5 mL of a 0.09988-M solution of Na2CO3 is allowed to
evaporate until the solution volume is reduced to 45.00 mL?

A 2.00-L bottle of a solution of concentrated HCl was purchased for the general chemistry laboratory. The solution contained 868.8
g of HCl. What is the molarity of the solution?
11.9 M
An experiment in a general chemistry laboratory calls for a 2.00-M solution of HCl. How many mL of 11.9 M HCl would be
required to make 250 mL of 2.00 M HCl?
What volume of a 0.20-M K2SO4 solution contains 57 g of K2SO4?
1.6 L
The US Environmental Protection Agency (EPA) places limits on the quantities of toxic substances that may be discharged into the
sewer system. Limits have been established for a variety of substances, including hexavalent chromium, which is limited to 0.50
mg/L. If an industry is discharging hexavalent chromium as potassium dichromate (K2Cr2O7), what is the maximum permissible
molarity of that substance?

Questions
1. Consider this question: What mass of a concentrated solution of nitric acid (68.0% HNO3 by mass) is needed to prepare 400.0 g
of a 10.0% solution of HNO3 by mass?
a. Outline the steps necessary to answer the question.
b. Answer the question.
2. What mass of a 4.00% NaOH solution by mass contains 15.0 g of NaOH?
3. What mass of solid NaOH (97.0% NaOH by mass) is required to prepare 1.00 L of a 10.0% solution of NaOH by mass? The
density of the 10.0% solution is 1.109 g/mL.
4. What mass of HCl is contained in 45.0 mL of an aqueous HCl solution that has a density of 1.19 g cm–3 and contains 37.21%
HCl by mass?
5. The hardness of water (hardness count) is usually expressed in parts per million (by mass) of CaCO , which is equivalent to
3
milligrams of CaCO per liter of water. What is the molar concentration of Ca2+ ions in a water sample with a hardness count
3
of 175 mg CaCO3/L?
6. The level of mercury in a stream was suspected to be above the minimum considered safe (1 part per billion by weight). An
analysis indicated that the concentration was 0.68 parts per billion. Assume a density of 1.0 g/mL and calculate the molarity of
mercury in the stream.
7. In Canada and the United Kingdom, devices that measure blood glucose levels provide a reading in millimoles per liter. If a
measurement of 5.3 mM is observed, what is the concentration of glucose (C6H12O6) in mg/dL?
8. A throat spray is 1.40% by mass phenol, C H OH , in water. If the solution has a density of 0.9956 g/mL, calculate the
6 5
molarity of the solution.

9. Copper(I) iodide (CuI) is often added to table salt as a dietary source of iodine. How many moles of CuI are contained in 1.00
lb (454 g) of table salt containing 0.0100% CuI by mass?
10. A cough syrup contains 5.0% ethyl alcohol, C2H5OH, by mass. If the density of the solution is 0.9928 g/mL, determine the
molarity of the alcohol in the cough syrup.
11. D5W is a solution used as an intravenous fluid. It is a 5.0% by mass solution of dextrose (C H O ) in water. If the density of
6 12 6
D5W is 1.029 g/mL, calculate the molarity of dextrose in the solution.

12. Find the molarity of a 40.0% by mass aqueous solution of sulfuric acid, H SO , for which the density is 1.3057 g/mL.
2 4
Solutions
1
(a) The dilution equation can be used, appropriately modified to accommodate mass-based concentration units:
% mass1 × mass1 = % mass2 × mass2 (6.E.1)
This equation can be rearranged to isolate mass and the given quantities substituted into this equation.
1
(b) 58.8 g
3. 114 g 5. 1.75 × 10 −3
M 7 95 mg/dL9 2.38 × 10 −4
mol 11 0.29mol

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CHAPTER OVERVIEW
7: Stoichiometry of Chemical Reactions

General Chemistry
This chapter will describe how to symbolize chemical reactions using chemical equations, how to classify some common chemical
reactions by identifying patterns of reactivity, and how to determine the quantitative relations between the amounts of substances
involved in chemical reactions—that is, the reaction stoichiometry.
Contributors
[email protected]).
This page titled 7: Stoichiometry of Chemical Reactions is shared under a CC BY license and was authored, remixed, and/or curated by
OpenStax.
1
Solid-fuel rockets are a central feature in the world’s space exploration programs, including the new Space Launch System being
developed by the National Aeronautics and Space Administration (NASA) to replace the retired Space Shuttle fleet (Figure 7.1.1).
The engines of these rockets rely on carefully prepared solid mixtures of chemicals combined in precisely measured amounts.
Igniting the mixture initiates a vigorous chemical reaction that rapidly generates large amounts of gaseous products. These gases
are ejected from the rocket engine through its nozzle, providing the thrust needed to propel heavy payloads into space. Both the
nature of this chemical reaction and the relationships between the amounts of the substances being consumed and produced by the
reaction are critically important considerations that determine the success of the technology. This chapter will describe how to
symbolize chemical reactions using chemical equations, how to classify some common chemical reactions by identifying patterns
of reactivity, and how to determine the quantitative relations between the amounts of substances involved in chemical reactions—
that is, the reaction stoichiometry.
Figure 7.1.1 : Many modern rocket fuels are solid mixtures of substances combined in carefully measured amounts and ignited to
yield a thrust-generating chemical reaction. (credit: modification of work by NASA)
An image is shown of a rocket that appears to have just passed through a layer of clouds as it travels skyward. A bright white light
is seen in the upper right corner of the image. To the lower left appears the layer of clouds and the bottom of the rocket with fire
projecting from the fuel cones at its base.
This page titled 7.1: Prelude to Stoichiometry is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
4.0: Prelude to Stoichiometry is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

Derive chemical equations from narrative descriptions of chemical reactions.
Write and balance chemical equations in molecular, total ionic, and net ionic formats.
The preceding chapter introduced the use of element symbols to represent individual atoms. When atoms gain or lose electrons to
yield ions, or combine with other atoms to form molecules, their symbols are modified or combined to generate chemical formulas
that appropriately represent these species. Extending this symbolism to represent both the identities and the relative quantities of
substances undergoing a chemical (or physical) change involves writing and balancing a chemical equation. Consider as an
example the reaction between one methane molecule (CH4) and two diatomic oxygen molecules (O2) to produce one carbon
dioxide molecule (CO2) and two water molecules (H2O). The chemical equation representing this process is provided in the upper
half of Figure 7.2.1, with space-filling molecular models shown in the lower half of the figure.
Figure 7.2.1 : The reaction between methane and oxygen to yield carbon dioxide and water (shown at bottom) may be represented
by a chemical equation using formulas (top).
This figure shows a balanced chemical equation followed below by a representation of the equation using space-filling models. The
equation reads C H subscript 4 plus 2 O subscript 2 arrow C O subscript 2 plus 2 H subscript 2 O. Under the C H subscript 4, the
molecule is shown with a central black sphere, representing a C atom, to which 4 smaller white spheres, representing H atoms, are
distributed evenly around. All four H atoms are bonded to the central black C atom. This is followed by a plus sign. Under the 2 O
subscript 2, two molecules are shown. The molecules are each composed of two red spheres bonded together. The red spheres
represent O atoms. To the right of an arrow and under the C O subscript 2, appears a single molecule with a black central sphere
with two red spheres bonded to the left and right. Following a plus sign and under the 2 H subscript 2 O, are two molecules, each
with a central red sphere and two smaller white spheres attached to the lower right and lower left sides of the central red sphere.
Note that in space filling models of molecules, spheres appear slightly compressed in regions where there is a bond between two
atoms.
This example illustrates the fundamental aspects of any chemical equation:
1. The substances undergoing reaction are called reactants, and their formulas are placed on the left side of the equation.
2. The substances generated by the reaction are called products, and their formulas are placed on the right sight of the equation.
3. Plus signs (+) separate individual reactant and product formulas, and an arrow (⟶) separates the reactant and product (left and
right) sides of the equation.
4. The relative numbers of reactant and product species are represented by coefficients (numbers placed immediately to the left of
each formula). A coefficient of 1 is typically omitted.
It is common practice to use the smallest possible whole-number coefficients in a chemical equation, as is done in this example.
Realize, however, that these coefficients represent the relative numbers of reactants and products, and, therefore, they may be
correctly interpreted as ratios. Methane and oxygen react to yield carbon dioxide and water in a 1:2:1:2 ratio. This ratio is satisfied
if the numbers of these molecules are, respectively, 1-2-1-2, or 2-4-2-4, or 3-6-3-6, and so on (Figure 7.2.2). Likewise, these
coefficients may be interpreted with regard to any amount (number) unit, and so this equation may be correctly read in many ways,
including:
One methane molecule and two oxygen molecules react to yield one carbon dioxide molecule and two water molecules.
One dozen methane molecules and two dozen oxygen molecules react to yield one dozen carbon dioxide molecules and two
dozen water molecules.

One mole of methane molecules and 2 moles of oxygen molecules react to yield 1 mole of carbon dioxide molecules and 2
moles of water molecules.
Figure 7.2.2 : Regardless of the absolute number of molecules involved, the ratios between numbers of molecules of each species
that react (the reactants) and molecules of each species that form (the products) are the same and are given in the chemical
equation.
Balancing Equations
When a chemical equation is balanced it means that equal numbers of atoms for each element involved in the reaction are
represented on the reactant and product sides. This is a requirement the equation must satisfy to be consistent with the law of
conservation of matter. It may be confirmed by simply summing the numbers of atoms on either side of the arrow and comparing
these sums to ensure they are equal. Note that the number of atoms for a given element is calculated by multiplying the coefficient
of any formula containing that element by the element’s subscript in the formula. If an element appears in more than one formula
on a given side of the equation, the number of atoms represented in each must be computed and then added together. For example,
both product species in the example reaction, CO and H O , contain the element oxygen, and so the number of oxygen atoms on
2 2
the product side of the equation is
⎛ 2 O atoms ⎞ ⎛ 1 O atom ⎞
1 CO molecule × + 2 H O molecule × = 4 O atoms
2 2
⎝ CO molecule ⎠ ⎝ H O molecule ⎠
2 2
The equation for the reaction between methane and oxygen to yield carbon dioxide and water is confirmed to be balanced per this
approach, as shown here:
CH +2 O → CO +2 H O
4 2 2 2
Equation for the reaction

CH +2O → CO +2H O
4 2 2 2
Element Reactants Products Balanced?
C 1×1=1 1×1=1 1 = 1, yes
H 4×1=4 2×2=4 4 = 4, yes
O 2×2=4 (1 × 2) + (2 × 1) = 4 4 = 4, yes
A balanced chemical equation often may be derived from a qualitative description of some chemical reaction by a fairly simple
approach known as balancing by inspection. Consider as an example the decomposition of water to yield molecular hydrogen and
oxygen. This process is represented qualitatively by an unbalanced chemical equation:
H O→ H +O (unbalanced)
2 2 2
Comparing the number of H and O atoms on either side of this equation confirms its imbalance:
Comparisons between H and O atoms

H 1×2=2 1×2=2 2 = 2, yes
O 1×1=1 1×2=2 1 ≠ 2, no
The numbers of H atoms on the reactant and product sides of the equation are equal, but the numbers of O atoms are not. To
achieve balance, the coefficients of the equation may be changed as needed. Keep in mind, of course, that the formula subscripts
define, in part, the identity of the substance, and so these cannot be changed without altering the qualitative meaning of the
equation. For example, changing the reactant formula from H2O to H2O2 would yield balance in the number of atoms, but doing so
also changes the reactant’s identity (it’s now hydrogen peroxide and not water). The O atom balance may be achieved by changing
the coefficient for H2O to 2.
2H O→ H +O (unbalanced)
2 2 2
O atom balance may be achieved by changing the coefficient for H2O to 2

H 2×2=4 1×2=2 4 ≠ 2, no
O 2×1=2 1×2=2 2 = 2, yes
The H atom balance was upset by this change, but it is easily reestablished by changing the coefficient for the H2 product to 2.
2H O→ 2H +O (balanced)
2 2 2
H atom balance upset but easily reestablished by changing the coefficient for the H2 product to 2.
H 2×2=4 2×2=2 4 = 4, yes
O 2×1=2 1×2=2 2 = 2, yes
These coefficients yield equal numbers of both H and O atoms on the reactant and product sides, and the balanced equation is,
therefore:
2H O→ 2H +O
2 2 2
 Example 7.2.1: Balancing Chemical Equations
Write a balanced equation for the reaction of molecular nitrogen (N2) and oxygen (O2) to form dinitrogen pentoxide.
Solution
First, write the unbalanced equation.
N +O → N O (unbalanced)
2 2 2 5
Next, count the number of each type of atom present in the unbalanced equation.
Unbalanced Equation
N 1×2=2 1×2=2 2 = 2, yes
O 1×2=2 1×5=5 2 ≠ 5, no
Though nitrogen is balanced, changes in coefficients are needed to balance the number of oxygen atoms. To balance the
number of oxygen atoms, a reasonable first attempt would be to change the coefficients for the O2 and N2O5 to integers that
will yield 10 O atoms (the least common multiple for the O atom subscripts in these two formulas).

N +5 O → 2N O (unbalanced)
2 2 2 5
N +5O → 2N O (unbalanced)
2 2 2 5
N 1×2=2 2×2=4 2 ≠ 4, no
O 5 × 2 = 10 2 × 5 = 10 10 = 10, yes
The N atom balance has been upset by this change; it is restored by changing the coefficient for the reactant N2 to 2.
2N +5 O → 2N O
2 2 2 5
N atom balance upset but restored by changing the coefficient for the reactant N2 to 2.
N 2×2=4 2×2=4 4 = 4, yes
O 5 × 2 = 10 2 × 5 = 10 10 = 10, yes
The numbers of N and O atoms on either side of the equation are now equal, and so the equation is balanced.
 Exercise 7.2.1
Write a balanced equation for the decomposition of ammonium nitrate to form molecular nitrogen, molecular oxygen, and
water. (Hint: Balance oxygen last, since it is present in more than one molecule on the right side of the equation.)
Answer
2 NH NO → 2N +O +4 H O
4 3 2 2 2
Balancing Reactions Which Contain Polyatomics: Balancing Reactions Which Contain

Polyatomics(opens in new window) [youtu.be]
It is sometimes convenient to use fractions instead of integers as intermediate coefficients in the process of balancing a chemical
equation. When balance is achieved, all the equation’s coefficients may then be multiplied by a whole number to convert the
fractional coefficients to integers without upsetting the atom balance. For example, consider the reaction of ethane (C2H6) with
oxygen to yield H2O and CO2, represented by the unbalanced equation:
C H +O → H O + CO (unbalanced)
2 6 2 2 2
Following the usual inspection approach, one might first balance C and H atoms by changing the coefficients for the two product
species, as shown:
C H +O → 3 H O + 2 CO (unbalanced)
2 6 2 2 2
This results in seven O atoms on the product side of the equation, an odd number—no integer coefficient can be used with the O2
reactant to yield an odd number, so a fractional coefficient, , is used instead to yield a provisional balanced equation:
7
7
C H + O → 3 H O + 2 CO
2 6 2 2 2 2
A conventional balanced equation with integer-only coefficients is derived by multiplying each coefficient by 2:
2C H +7 O → 6 H O + 4 CO
2 6 2 2 2
Finally with regard to balanced equations, recall that convention dictates use of the smallest whole-number coefficients. Although
the equation for the reaction between molecular nitrogen and molecular hydrogen to produce ammonia is, indeed, balanced,

3N +9 H → 6 NH
2 2 3
the coefficients are not the smallest possible integers representing the relative numbers of reactant and product molecules. Dividing
each coefficient by the greatest common factor, 3, gives the preferred equation:
N +3 H → 2 NH
2 2 3
 Phet Simulation
Use this interactive tutorial for additional practice balancing equations.
Additional Information in Chemical Equations

The physical states of reactants and products in chemical equations very often are indicated with a parenthetical abbreviation
following the formulas. Common abbreviations include s for solids, l for liquids, g for gases, and aq for substances dissolved in
water (aqueous solutions, as introduced in the preceding chapter). These notations are illustrated in the example equation here:
2 Na(s) + 2 H O(l) → 2 NaOH(aq) + H (g)

2 2
This equation represents the reaction that takes place when sodium metal is placed in water. The solid sodium reacts with liquid
water to produce molecular hydrogen gas and the ionic compound sodium hydroxide (a solid in pure form, but readily dissolved in
water).
Special conditions necessary for a reaction are sometimes designated by writing a word or symbol above or below the equation’s
arrow. For example, a reaction carried out by heating may be indicated by the uppercase Greek letter delta (Δ) over the arrow.
Δ
CaCO (s) −
−→ CaO(s) + CO (g)
3 2
Other examples of these special conditions will be encountered in more depth in later chapters.
Equations for Ionic Reactions

Given the abundance of water on earth, it stands to reason that a great many chemical reactions take place in aqueous media. When
ions are involved in these reactions, the chemical equations may be written with various levels of detail appropriate to their
intended use. To illustrate this, consider a reaction between ionic compounds taking place in an aqueous solution. When aqueous
solutions of CaCl and AgNO are mixed, a reaction takes place producing aqueous Ca(NO ) and solid AgCl:
2 3 3 2
CaCl (aq) + 2 AgNO (aq) → Ca (NO ) (aq) + 2 AgCl(s)

2 3 3 2
This balanced equation, derived in the usual fashion, is called a molecular equation because it doesn’t explicitly represent the ionic
species that are present in solution. When ionic compounds dissolve in water, they may dissociate into their constituent ions, which
are subsequently dispersed homogenously throughout the resulting solution (a thorough discussion of this important process is
provided in the chapter on solutions). Ionic compounds dissolved in water are, therefore, more realistically represented as
dissociated ions, in this case:
2+ −
CaCl (aq) → Ca (aq) + 2 Cl (aq)
2
+ −
2 AgNO (aq) → 2 Ag (aq) + 2 NO (aq)
3 3
2+ −
Ca (NO ) (aq) → Ca (aq) + 2 NO (aq)
3 2 3
Unlike these three ionic compounds, AgCl does not dissolve in water to a significant extent, as signified by its physical state
notation, (s).
Explicitly representing all dissolved ions results in a complete ionic equation. In this particular case, the formulas for the dissolved
ionic compounds are replaced by formulas for their dissociated ions:
2+ − + − 2+ −
Ca (aq) + 2 Cl (aq) + 2 Ag (aq) + 2 NO (aq) → Ca (aq) + 2 NO (aq) + 2 Ag Cl(s)
3 3

Examining this equation shows that two chemical species are present in identical form on both sides of the arrow, Ca (aq) and 2 +
NO (aq) . These spectator ions—ions whose presence is required to maintain charge neutrality—are neither chemically nor
−
3
physically changed by the process, and so they may be eliminated from the equation to yield a more succinct representation called a
net ionic equation:
2+ − + − 2+ −
Ca (aq) + 2 Cl (aq) + 2 Ag (aq) + 2 NO (aq) → Ca (aq) + 2 NO (aq) + 2 AgCl(s)
3 3
− +
2 Cl (aq) + 2 Ag (aq) → 2 AgCl(s)
Following the convention of using the smallest possible integers as coefficients, this equation is then written:
− +
Cl (aq) + Ag (aq) → AgCl(s)
This net ionic equation indicates that solid silver chloride may be produced from dissolved chloride and silver(I) ions, regardless of
the source of these ions. These molecular and complete ionic equations provide additional information, namely, the ionic
compounds used as sources of Cl and Ag .
− +
 Example 7.2.2: Molecular and Ionic Equations
When carbon dioxide is dissolved in an aqueous solution of sodium hydroxide, the mixture reacts to yield aqueous sodium
carbonate and liquid water. Write balanced molecular, complete ionic, and net ionic equations for this process.
Solution
Begin by identifying formulas for the reactants and products and arranging them properly in chemical equation form:
CO (aq) + NaOH(aq) → Na CO (aq) + H O(l) (unbalanced)
2 2 3 2
Balance is achieved easily in this case by changing the coefficient for NaOH to 2, resulting in the molecular equation for this
reaction:
+
CO (aq) NaOH(aq) → Na CO (aq) + H O(l)
2 2 2 3 2
The two dissolved ionic compounds, NaOH and Na2CO3, can be represented as dissociated ions to yield the complete ionic
equation:
+ − + 2 −
CO (aq) + 2 Na (aq) + 2 OH (aq) → 2 Na (aq) + CO3 (aq) + H O(l)
2 2
+
Finally, identify the spectator ion(s), in this case Na (aq), and remove it from each side of the equation to generate the net ionic
equation:
+ − + 2−
CO (aq) + 2 Na (aq) + 2 OH (aq) → 2 Na (aq) + CO (aq) + H O(l)
2 3 2
− 2−
CO (aq) + 2 OH (aq) → CO (aq) + H O(l)
2 3 2
 Exercise 7.2.2
Diatomic chlorine and sodium hydroxide (lye) are commodity chemicals produced in large quantities, along with diatomic
hydrogen, via the electrolysis of brine, according to the following unbalanced equation:
electricity
NaCl(aq) + H O(l) −−−−−→ NaOH(aq) + H (g) + Cl (g)

2 2 2
Write balanced molecular, complete ionic, and net ionic equations for this process.
Answer
Balanced molecular equation:
2 NaCl(aq) + 2 H O(l) ⟶ 2 NaOH(aq) + H (g) + Cl (g)

2 2 2

Balanced ionic equation:
+ − + −
2 Na (aq) + 2 Cl (aq) + 2 H O(l) ⟶ 2 Na (aq) + 2 OH (aq) + H (g) + Cl (g)
2 2 2
Balanced net ionic equation:

− −
2 Cl (aq) + 2 H O(l) ⟶ 2 OH (aq) + H (g) + Cl (g)
2 2 2

Chemical equations are symbolic representations of chemical and physical changes. Formulas for the substances undergoing the
change (reactants) and substances generated by the change (products) are separated by an arrow and preceded by integer
coefficients indicating their relative numbers. Balanced equations are those whose coefficients result in equal numbers of atoms for
each element in the reactants and products. Chemical reactions in aqueous solution that involve ionic reactants or products may be
represented more realistically by complete ionic equations and, more succinctly, by net ionic equations.
Glossary
balanced equation
chemical equation with equal numbers of atoms for each element in the reactant and product
chemical equation
symbolic representation of a chemical reaction
coefficient
number placed in front of symbols or formulas in a chemical equation to indicate their relative amount
complete ionic equation

chemical equation in which all dissolved ionic reactants and products, including spectator ions, are explicitly represented by
formulas for their dissociated ions
molecular equation
chemical equation in which all reactants and products are represented as neutral substances
net ionic equation

chemical equation in which only those dissolved ionic reactants and products that undergo a chemical or physical change are
represented (excludes spectator ions)
product
substance formed by a chemical or physical change; shown on the right side of the arrow in a chemical equation
reactant
substance undergoing a chemical or physical change; shown on the left side of the arrow in a chemical equation
spectator ion
ion that does not undergo a chemical or physical change during a reaction, but its presence is required to maintain charge
neutrality
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OpenStax.
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Define three common types of chemical reactions (precipitation, acid-base, and oxidation-reduction)
Classify chemical reactions as one of these three types given appropriate descriptions or chemical equations
Identify common acids and bases
Predict the solubility of common inorganic compounds by using solubility rules
Compute the oxidation states for elements in compounds
Humans interact with one another in various and complex ways, and we classify these interactions according to common patterns
of behavior. When two humans exchange information, we say they are communicating. When they exchange blows with their fists
or feet, we say they are fighting. Faced with a wide range of varied interactions between chemical substances, scientists have
likewise found it convenient (or even necessary) to classify chemical interactions by identifying common patterns of reactivity.
This module will provide an introduction to three of the most prevalent types of chemical reactions: precipitation, acid-base, and
oxidation-reduction.
Precipitation Reactions and Solubility Rules

A precipitation reaction is one in which dissolved substances react to form one (or more) solid products. Many reactions of this
type involve the exchange of ions between ionic compounds in aqueous solution and are sometimes referred to as double
displacement, double replacement, or metathesis reactions. These reactions are common in nature and are responsible for the
formation of coral reefs in ocean waters and kidney stones in animals. They are used widely in industry for production of a number
of commodity and specialty chemicals. Precipitation reactions also play a central role in many chemical analysis techniques,
including spot tests used to identify metal ions and gravimetric methods for determining the composition of matter (see the last
module of this chapter).
The extent to which a substance may be dissolved in water, or any solvent, is quantitatively expressed as its solubility, defined as
the maximum concentration of a substance that can be achieved under specified conditions. Substances with relatively large
solubilities are said to be soluble. A substance will precipitate when solution conditions are such that its concentration exceeds its
solubility. Substances with relatively low solubilities are said to be insoluble, and these are the substances that readily precipitate
from solution. More information on these important concepts is provided in the text chapter on solutions. For purposes of
predicting the identities of solids formed by precipitation reactions, one may simply refer to patterns of solubility that have been
observed for many ionic compounds (Table 7.3.1).
Table 7.3.1 : Solubilities of Common Ionic Compounds in Water
Soluble compounds contain Exceptions to these solubility rules include
group 1 metal cations (Li+, Na+, K+, Rb+, and Cs+) and ammonium
ion (NH )
+
4
the halide ions (Cl−, Br−, and I−) halides of Ag+, Hg , and Pb2+
2+
2
the acetate (C H O ) , bicarbonate (HCO ) , nitrate (NO ), and

2 3
−
2
−
3
−
3
sulfates of Ag+, Ba2+, Ca2+, Hg , Pb2+, and Sr2+
2+
2
chlorate (ClO ) ions

−
3
the sulfate (SO ) ion

−
4
Insoluble compounds contain Exceptions to these insolubility rules include
carbonate (CO ) , chromate (CrO

2−
3
2−
4
) , phosphate (PO
3−
4
) , and compounds of these anions with group 1 metal cations and
sulfide (S2−) ions ammonium ion
hydroxide ion (OH−) hydroxides of group 1 metal cations and Ba2+
A vivid example of precipitation is observed when solutions of potassium iodide and lead nitrate are mixed, resulting in the
formation of solid lead iodide:
2 KI(aq) + Pb(NO ) (aq) → PbI (s) + 2 KNO (aq)

3 2 2 3
7.3.1 https://chem.libretexts.org/@go/page/207493
This observation is consistent with the solubility guidelines: The only insoluble compound among all those involved is lead iodide,
one of the exceptions to the general solubility of iodide salts.
The net ionic equation representing this reaction is:
2+ −
Pb (aq) + 2 I (aq) → PbI (s)
2
Lead iodide is a bright yellow solid that was formerly used as an artist’s pigment known as iodine yellow (Figure 7.3.1 ). The
properties of pure PbI2 crystals make them useful for fabrication of X-ray and gamma ray detectors.
Figure 7.3.1 : A precipitate of PbI2 forms when solutions containing Pb2+ and I− are mixed. (credit: Der Kreole/Wikimedia
Commons)
A photograph is shown of a yellow green opaque substance swirled through a clear, colorless liquid in a test tube.
The solubility guidelines in Table 7.3.1 may be used to predict whether a precipitation reaction will occur when solutions of
soluble ionic compounds are mixed together. One merely needs to identify all the ions present in the solution and then consider if
possible cation/anion pairing could result in an insoluble compound. For example, mixing solutions of silver nitrate and sodium
fluoride will yield a solution containing Ag+, NO , Na+, and F− ions. Aside from the two ionic compounds originally present in
−
3
the solutions, AgNO3 and NaF, two additional ionic compounds may be derived from this collection of ions: NaNO3 and AgF. The
solubility guidelines indicate all nitrate salts are soluble but that AgF is one of the exceptions to the general solubility of fluoride
salts. A precipitation reaction, therefore, is predicted to occur, as described by the following equations:
NaF(aq) + AgNO (aq) → AgF(s) + NaNO (aq) (molecular)

3 3
+ −
Ag (aq) + F (aq) → AgF(s) (net ionic)
 Example 7.3.1: Predicting Precipitation Reactions

Predict the result of mixing reasonably concentrated solutions of the following ionic compounds. If precipitation is expected,
write a balanced net ionic equation for the reaction.
a. potassium sulfate and barium nitrate
b. lithium chloride and silver acetate
c. lead nitrate and ammonium carbonate
Solution
(a) The two possible products for this combination are KNO3 and BaSO4. The solubility guidelines indicate BaSO4 is
insoluble, and so a precipitation reaction is expected. The net ionic equation for this reaction, derived in the manner detailed in
the previous module, is
2+ 2−
Ba (aq) + SO (aq) → BaSO (s)
4 4
(b) The two possible products for this combination are LiC2H3O2 and AgCl. The solubility guidelines indicate AgCl is
+ −
Ag (aq) + Cl (aq) → AgCl(s)
(c) The two possible products for this combination are PbCO3 and NH4NO3. The solubility guidelines indicate PbCO3 is
2+ 2−
Pb (aq) + CO3 (aq) → PbCO (s)
3
 Exercise 7.3.1
Which solution could be used to precipitate the barium ion, Ba2+, in a water sample: sodium chloride, sodium hydroxide, or
sodium sulfate? What is the formula for the expected precipitate?
Answer
sodium sulfate, BaSO4
Acid-Base Reactions
An acid-base reaction is one in which a hydrogen ion, H+, is transferred from one chemical species to another. Such reactions are of
central importance to numerous natural and technological processes, ranging from the chemical transformations that take place
within cells and the lakes and oceans, to the industrial-scale production of fertilizers, pharmaceuticals, and other substances
essential to society. The subject of acid-base chemistry, therefore, is worthy of thorough discussion, and a full chapter is devoted to
this topic later in the text.
For purposes of this brief introduction, we will consider only the more common types of acid-base reactions that take place in
aqueous solutions. In this context, an acid is a substance that will dissolve in water to yield hydronium ions, H3O+. As an example,
consider the equation shown here:
− +
HCl(aq) + H O(aq) → Cl (aq) + H O (aq)
2 3
The process represented by this equation confirms that hydrogen chloride is an acid. When dissolved in water, H3O+ ions are
produced by a chemical reaction in which H+ ions are transferred from HCl molecules to H2O molecules (Figure 7.3.2).
Figure 7.3.2 : When hydrogen chloride gas dissolves in water, (a) it reacts as an acid, transferring protons to water molecules to
yield (b) hydronium ions (and solvated chloride ions)
This figure shows two flasks, labeled a and b. The flasks are both sealed with stoppers and are nearly three-quarters full of a liquid.
Flask a is labeled H C l followed by g in parentheses. In the liquid there are approximately twenty space-filling molecular models
composed of one red sphere and two smaller attached white spheres. The label H subscript 2 O followed by a q in parentheses is
connected with a line to one of these models. In the space above the liquid in the flask, four space filling molecular models
composed of one larger green sphere to which a smaller white sphere is bonded are shown. To one of these models, the label H C l
followed by g in parentheses is attached with a line segment. An arrow is drawn from the space above the liquid pointing down into
the liquid below. Flask b is labeled H subscript 3 O superscript positive sign followed by a q in parentheses. This is followed by a
plus sign and C l superscript negative sign which is also followed by a q in parentheses. In this flask, no molecules are shown in the
open space above the liquid. A label, C l superscript negative sign followed by a q in parentheses, is connected with a line segment
to a green sphere. This sphere is surrounded by four molecules composed each of one red sphere and two white smaller spheres. A
few of these same molecules appear separate from the green spheres in the liquid. A line segment connects one of them to the label
H subscript 2 O which is followed by l in parentheses. There are a few molecules formed from one central larger red sphere to
which three smaller white spheres are bonded. A line segment is drawn from one of these to the label H subscript 3 O superscript
positive sign, followed by a q in parentheses.
The nature of HCl is such that its reaction with water as just described is essentially 100% efficient: Virtually every HCl molecule
that dissolves in water will undergo this reaction. Acids that completely react in this fashion are called strong acids, and HCl is one
among just a handful of common acid compounds that are classified as strong (Table 7.3.1). A far greater number of compounds
behave as weak acids and only partially react with water, leaving a large majority of dissolved molecules in their original form and
generating a relatively small amount of hydronium ions. Weak acids are commonly encountered in nature, being the substances
partly responsible for the tangy taste of citrus fruits, the stinging sensation of insect bites, and the unpleasant smells associated with
body odor. A familiar example of a weak acid is acetic acid, the main ingredient in food vinegars:
− +
CH CO H(aq) + H O(l) ⇌ CH CO (aq) + H O (aq)
3 2 2 3 2 3
When dissolved in water under typical conditions, only about 1% of acetic acid molecules are present in the ionized form,
CH CO
3
(Figure 7.3.3). (The use of a double-arrow in the equation above denotes the partial reaction aspect of this process, a
−
concept addressed fully in the chapters on chemical equilibrium.)
Figure 7.3.3 : (a) Fruits such as oranges, lemons, and grapefruit contain the weak acid citric acid. (b) Vinegars contain the weak
acid acetic acid. (credit a: modification of work by Scott Bauer; credit b: modification of work by Brücke-Osteuropa/Wikimedia
Commons)
This figure contains two images, each with an associated structural formula provided in the lower left corner of the image. The first
image is a photograph of a variety of thinly sliced, circular cross sections of citrus fruits ranging in color for green to yellow, to
orange and reddish-orange. The slices are closely packed on a white background. The structural formula with this picture shows a
central chain of five C atoms. The leftmost C atom has an O atom double bonded above and to the left and a singly bonded O atom
below and to the left. This single bonded O atom has an H atom indicated in red on its left side which is highlighted in pink. The
second C atom moving to the right has H atoms bonded above and below. The third C atom has a single bonded O atom above
which has an H atom on its right. This third C atom has a C atom bonded below it which has an O atom double bonded below and
to the left and a singly bonded O atom below and to the right. An H atom appears in red and is highlighted in pink to the right of
the singly bonded O atom. The fourth C atom has H atoms bonded above and below. The fifth C atom is at the right end of the
structure. It has an O atom double bonded above and to the right and a singly bonded O atom below and to the right. This single
bonded O atom has a red H atom on its right side which is highlighted in pink. The second image is a photograph of bottles of
vinegar. The bottles are labeled, “Balsamic Vinegar,” and appear to be clear and colorless. The liquid in this bottle appears to be
brown. The structural formula that appears with this image shows a chain of two C atoms. The leftmost C atom has H atoms
bonded above, below, and to the left. The C atom on the right has a doubly bonded O atom above and to the right and a singly
bonded O atom below and to the right. This O atom has an H atom bonded to its right which is highlighted in pink.
Table 7.3.2 : Common Strong Acids
Compound Formula Name in Aqueous Solution
HBr hydrobromic acid
HCl hydrochloric acid
HI hydroiodic acid
HNO3 nitric acid
HClO4 perchloric acid
H2SO4 sulfuric acid
A base is a substance that will dissolve in water to yield hydroxide ions, OH−. The most common bases are ionic compounds
composed of alkali or alkaline earth metal cations (groups 1 and 2) combined with the hydroxide ion—for example, NaOH and
Ca(OH)2. When these compounds dissolve in water, hydroxide ions are released directly into the solution. For example, KOH and
Ba(OH)2 dissolve in water and dissociate completely to produce cations (K+ and Ba2+, respectively) and hydroxide ions, OH−.
These bases, along with other hydroxides that completely dissociate in water, are considered strong bases.
Consider as an example the dissolution of lye (sodium hydroxide) in water:
+ −
NaOH(s) → Na (aq) + OH (aq)
This equation confirms that sodium hydroxide is a base. When dissolved in water, NaOH dissociates to yield Na+ and OH− ions.
This is also true for any other ionic compound containing hydroxide ions. Since the dissociation process is essentially complete
when ionic compounds dissolve in water under typical conditions, NaOH and other ionic hydroxides are all classified as strong
bases.
Unlike ionic hydroxides, some compounds produce hydroxide ions when dissolved by chemically reacting with water molecules. In
all cases, these compounds react only partially and so are classified as weak bases. These types of compounds are also abundant in
nature and important commodities in various technologies. For example, global production of the weak base ammonia is typically
well over 100 metric tons annually, being widely used as an agricultural fertilizer, a raw material for chemical synthesis of other
compounds, and an active ingredient in household cleaners (Figure 7.3.4). When dissolved in water, ammonia reacts partially to
yield hydroxide ions, as shown here:
+ −
NH (aq) + H O(l) ⇌ NH (aq) + OH (aq)
3 2 4
This is, by definition, an acid-base reaction, in this case involving the transfer of H+ ions from water molecules to ammonia
molecules. Under typical conditions, only about 1% of the dissolved ammonia is present as NH ions. +
Figure 7.3.4 : Ammonia is a weak base used in a variety of applications. (a) Pure ammonia is commonly applied as an agricultural
fertilizer. (b) Dilute solutions of ammonia are effective household cleansers. (credit a: modification of work by National Resources
Conservation Service; credit b: modification of work by pat00139)
This photograph shows a large agricultural tractor in a field pulling a field sprayer and a large, white cylindrical tank which is
labeled “Caution Ammonia.”
The chemical reactions described in which acids and bases dissolved in water produce hydronium and hydroxide ions, respectively,
are, by definition, acid-base reactions. In these reactions, water serves as both a solvent and a reactant. A neutralization reaction is
a specific type of acid-base reaction in which the reactants are an acid and a base, the products are often a salt and water, and
neither reactant is the water itself:
acid + base → salt + water
To illustrate a neutralization reaction, consider what happens when a typical antacid such as milk of magnesia (an aqueous
suspension of solid Mg(OH)2) is ingested to ease symptoms associated with excess stomach acid (HCl):
Mg (OH) (s) + 2 HCl(aq) → MgCl (aq) + 2 H O(l).

2 2 2
Note that in addition to water, this reaction produces a salt, magnesium chloride.
 Example 7.3.2: Writing Equations for Acid-Base Reactions

Write balanced chemical equations for the acid-base reactions described here:
a. the weak acid hydrogen hypochlorite reacts with water
b. a solution of barium hydroxide is neutralized with a solution of nitric acid
Solution
(a) The two reactants are provided, HOCl and H2O. Since the substance is reported to be an acid, its reaction with water will
involve the transfer of H+ from HOCl to H2O to generate hydronium ions, H3O+ and hypochlorite ions, OCl−.
− +
HOCl(aq) + H O(l) ⇌ OCl (aq) + H O (aq)
2 3
A double-arrow is appropriate in this equation because it indicates the HOCl is a weak acid that has not reacted completely.
(b) The two reactants are provided, Ba(OH)2 and HNO3. Since this is a neutralization reaction, the two products will be water
and a salt composed of the cation of the ionic hydroxide (Ba2+) and the anion generated when the acid transfers its hydrogen
ion (NO ).
−
3
Ba (OH) (aq) + 2 HNO (aq) → Ba (NO ) (aq) + 2 H O(l)
2 3 3 2 2
 Exercise 7.3.21
Write the net ionic equation representing the neutralization of any strong acid with an ionic hydroxide. (Hint: Consider the ions
produced when a strong acid is dissolved in water.)
Answer
+ −
H O (aq) + OH (aq) → 2 H O(l)
3 2
Explore the microscopic view of strong and weak acids and bases.
Oxidation-Reduction Reactions
Earth’s atmosphere contains about 20% molecular oxygen, O2, a chemically reactive gas that plays an essential role in the
metabolism of aerobic organisms and in many environmental processes that shape the world. The term oxidation was originally
used to describe chemical reactions involving O2, but its meaning has evolved to refer to a broad and important reaction class
known as oxidation-reduction (redox) reactions. A few examples of such reactions will be used to develop a clear picture of this
classification.
Some redox reactions involve the transfer of electrons between reactant species to yield ionic products, such as the reaction
between sodium and chlorine to yield sodium chloride:
2 Na(s) + Cl (g) → 2 NaCl(s)

2
It is helpful to view the process with regard to each individual reactant, that is, to represent the fate of each reactant in the form of
an equation called a half-reaction:
+ −
2 Na(s) → 2 Na (s) + 2 e
− −
Cl (g) + 2 e → 2 Cl (s)
2
These equations show that Na atoms lose electrons while Cl atoms (in the Cl2 molecule) gain electrons, the “s” subscripts for the
resulting ions signifying they are present in the form of a solid ionic compound. For redox reactions of this sort, the loss and gain
of electrons define the complementary processes that occur:
oxidation = loss of electrons (7.3.1)
reduction = gain of electrons (7.3.2)
In this reaction, then, sodium is oxidized and chlorine undergoes reduction. Viewed from a more active perspective, sodium
functions as a reducing agent (reductant), since it provides electrons to (or reduces) chlorine. Likewise, chlorine functions as an
oxidizing agent (oxidant), as it effectively removes electrons from (oxidizes) sodium.
reducing agent = species that is oxidized (7.3.3)
oxidizing agent = species that is reduced (7.3.4)
Some redox processes, however, do not involve the transfer of electrons. Consider, for example, a reaction similar to the one
yielding NaCl:
H (g) + Cl (g) → 2 HCl(g)

2 2
The product of this reaction is a covalent compound, so transfer of electrons in the explicit sense is not involved. To clarify the
similarity of this reaction to the previous one and permit an unambiguous definition of redox reactions, a property called oxidation
number has been defined. The oxidation number (or oxidation state) of an element in a compound is the charge its atoms would
possess if the compound was ionic. The following guidelines are used to assign oxidation numbers to each element in a molecule or
ion.
1. The oxidation number of an atom in an elemental substance is zero.
2. The oxidation number of a monatomic ion is equal to the ion’s charge.
3. Oxidation numbers for common nonmetals are usually assigned as follows:
Hydrogen: +1 when combined with nonmetals, −1 when combined with metals
1
Oxygen: −2 in most compounds, sometimes −1 (so-called peroxides, O 2−
2
), very rarely − (so-called superoxides, O ),
−
2
2
positive values when combined with F (values vary)
Halogens: −1 for F always, −1 for other halogens except when combined with oxygen or other halogens (positive oxidation
numbers in these cases, varying values)
4. The sum of oxidation numbers for all atoms in a molecule or polyatomic ion equals the charge on the molecule or ion.
Note: The proper convention for reporting charge is to write the number first, followed by the sign (e.g., 2+), while oxidation
number is written with the reversed sequence, sign followed by number (e.g., +2). This convention aims to emphasize the
distinction between these two related properties.
 Example 7.3.3: Assigning Oxidation Numbers
Follow the guidelines in this section of the text to assign oxidation numbers to all the elements in the following species:
a. H2S
b. SO 2−
3
c. Na2SO4
Solution
(a) According to guideline 1, the oxidation number for H is +1.
Using this oxidation number and the compound’s formula, guideline 4 may then be used to calculate the oxidation number for
sulfur:
charge on H S = 0 = (2 × +1) + (1 × x)
2
x = 0 − (2 × +1) = −2
(b) Guideline 3 suggests the oxidation number for oxygen is −2.

Using this oxidation number and the ion’s formula, guideline 4 may then be used to calculate the oxidation number for sulfur:
2−
charge on SO = −2 = (3 × −2) + (1 × x)
3
x = −2 − (3 × −2) = +4
(c) For ionic compounds, it’s convenient to assign oxidation numbers for the cation and anion separately.
According to guideline 2, the oxidation number for sodium is +1.
Assuming the usual oxidation number for oxygen (−2 per guideline 3), the oxidation number for sulfur is calculated as directed
by guideline 4:
2−
charge on SO = −2 = (4 × −2) + (1 × x)
4
x = −2 − (4 × −2) = +6
 Exercise 7.3.3
Assign oxidation states to the elements whose atoms are underlined in each of the following compounds or ions:
a. KNO3
b. AlH3
c. –
NH
–
+
4
d. H –
2 PO
– 4
−
Answer a
N, +5
Answer b
Al, +3
Answer c
N, −3
Answer d
P, +5
Using the oxidation number concept, an all-inclusive definition of redox reaction has been established. Oxidation-reduction (redox)
reactions are those in which one or more elements involved undergo a change in oxidation number. While the vast majority of
redox reactions involve changes in oxidation number for two or more elements, a few interesting exceptions to this rule do exist as
shown below\). Definitions for the complementary processes of this reaction class are correspondingly revised as shown here:
oxidation = increase in oxidation number (7.3.5)
reduction = decrease in oxidation number (7.3.6)
Returning to the reactions used to introduce this topic, they may now both be identified as redox processes. In the reaction between
sodium and chlorine to yield sodium chloride, sodium is oxidized (its oxidation number increases from 0 in Na to +1 in NaCl) and
chlorine is reduced (its oxidation number decreases from 0 in Cl2 to −1 in NaCl). In the reaction between molecular hydrogen and
chlorine, hydrogen is oxidized (its oxidation number increases from 0 in H2 to +1 in HCl) and chlorine is reduced (its oxidation
number decreases from 0 in Cl2 to −1 in HCl).
Several subclasses of redox reactions are recognized, including combustion reactions in which the reductant (also called a fuel) and
oxidant (often, but not necessarily, molecular oxygen) react vigorously and produce significant amounts of heat, and often light, in
the form of a flame. Solid rocket-fuel reactions such as the one depicted below are combustion processes. A typical propellant
reaction in which solid aluminum is oxidized by ammonium perchlorate is represented by this equation:
10 Al(s) + 6 NH ClO (s) → 4 Al O (s) + 2 AlCl (s) + 12 H O(g) + 3 N (g)

4 4 2 3 3 2 2
Watch a brief video showing the test firing of a small-scale, prototype, hybrid rocket engine planned for use in the new Space
Launch System being developed by NASA. The first engines firing at 3 s (green flame) use a liquid fuel/oxidant mixture, and
the second, more powerful engines firing at 4 s (yellow flame) use a solid mixture.
NASA Tests Model of Powerful New R…

R…
Single-displacement (replacement) reactions are redox reactions in which an ion in solution is displaced (or replaced) via the
oxidation of a metallic element. One common example of this type of reaction is the acid oxidation of certain metals:
Zn(s) + 2 HCl(aq) → ZnCl (aq) + H (g)

2 2
Metallic elements may also be oxidized by solutions of other metal salts; for example:
Cu(s) + 2 AgNO (aq) → Cu(NO ) (aq) + 2 Ag(s)

3 3 2
This reaction may be observed by placing copper wire in a solution containing a dissolved silver salt. Silver ions in solution are
reduced to elemental silver at the surface of the copper wire, and the resulting Cu2+ ions dissolve in the solution to yield a
characteristic blue color (Figure 7.3.4).
Figure 7.3.4 : (a) A copper wire is shown next to a solution containing silver(I) ions. (b) Displacement of dissolved silver ions by
copper ions results in (c) accumulation of gray-colored silver metal on the wire and development of a blue color in the solution, due
to dissolved copper ions. (credit: modification of work by Mark Ott)
This figure contains three photographs. In a, a coiled copper wire is shown beside a test tube filled with a clear, colorless liquid. In
b, the wire has been inserted into the test tube with the clear, colorless liquid. In c, the test tube contains a light blue liquid and the
coiled wire appears to have a fuzzy silver gray coating.
 Example 7.3.4: Describing Redox Reactions
Identify which equations represent redox reactions, providing a name for the reaction if appropriate. For those reactions
identified as redox, name the oxidant and reductant.
a. ZnCO (s) → ZnO(s) + CO (g)
3 2
b. 2 Ga(l) + 3 Br (l) → 2 GaBr (s)

2 3
c. 2 H O (aq) → 2 H O(l) + O (g)

2 2 2 2
d. BaCl (aq) + K SO (aq) → BaSO (s) + 2 KCl(aq)

2 2 4 4
e. C H (g) + 3 O (g) → 2 CO (g) + 2 H O(l)

2 4 2 2 2
Solution
Redox reactions are identified per definition if one or more elements undergo a change in oxidation number.
a. This is not a redox reaction, since oxidation numbers remain unchanged for all elements.
b. This is a redox reaction. Gallium is oxidized, its oxidation number increasing from 0 in Ga(l) to +3 in GaBr3(s). The
reducing agent is Ga(l). Bromine is reduced, its oxidation number decreasing from 0 in Br2(l) to −1 in GaBr3(s). The
oxidizing agent is Br2(l).
c. This is a redox reaction. It is a particularly interesting process, as it involves the same element, oxygen, undergoing both
oxidation and reduction (a so-called disproportionation reaction). Oxygen is oxidized, its oxidation number increasing from
−1 in H2O2(aq) to 0 in O2(g). Oxygen is also reduced, its oxidation number decreasing from −1 in H2O2(aq) to −2 in
H2O(l). For disproportionation reactions, the same substance functions as an oxidant and a reductant.
d. This is not a redox reaction, since oxidation numbers remain unchanged for all elements.
e. This is a redox reaction (combustion). Carbon is oxidized, its oxidation number increasing from −2 in C2H4(g) to +4 in
CO2(g). The reducing agent (fuel) is C2H4(g). Oxygen is reduced, its oxidation number decreasing from 0 in O2(g) to −2 in
H2O(l). The oxidizing agent is O2(g).
 Exercise 7.3.4
This equation describes the production of tin(II) chloride:
Sn(s) + 2 HCl(g) → SnCl (s) + H (g)

2 2
Is this a redox reaction? If so, provide a more specific name for the reaction if appropriate, and identify the oxidant and
reductant.
Answer
Yes, a single-replacement reaction. Sn(s) is the reductant, HCl(g) is the oxidant.
Balancing Redox Reactions via the Half-Reaction Method

Redox reactions that take place in aqueous media often involve water, hydronium ions, and hydroxide ions as reactants or products.
Although these species are not oxidized or reduced, they do participate in chemical change in other ways (e.g., by providing the
elements required to form oxyanions). Equations representing these reactions are sometimes very difficult to balance by inspection,
so systematic approaches have been developed to assist in the process. One very useful approach is to use the method of half-
reactions, which involves the following steps:
1. Write the two half-reactions representing the redox process.
2. Balance all elements except oxygen and hydrogen.
3. Balance oxygen atoms by adding H2O molecules.
4. Balance hydrogen atoms by adding H+ ions.
5. Balance charge1 by adding electrons.
6. If necessary, multiply each half-reaction’s coefficients by the smallest possible integers to yield equal numbers of electrons in
each.
7. Add the balanced half-reactions together and simplify by removing species that appear on both sides of the equation.
8. For reactions occurring in basic media (excess hydroxide ions), carry out these additional steps:
Add OH− ions to both sides of the equation in numbers equal to the number of H+ ions.
On the side of the equation containing both H+ and OH− ions, combine these ions to yield water molecules.
Simplify the equation by removing any redundant water molecules.
9. Finally, check to see that both the number of atoms and the total charges2 are balanced.
 Example 7.3.5: Balancing Redox Reactions in Acidic Solution
Write a balanced equation for the reaction between dichromate ion and iron(II) to yield iron(III) and chromium(III) in acidic
solution.
2− 2+ 3+ 3+
Cr O + Fe → Cr + Fe
2 7
Solution
Write the two half-reactions.
Each half-reaction will contain one reactant and one product with one element in common.
2+ 3+
Fe → Fe
2− 3+
Cr O → Cr
2 7
Balance all elements except oxygen and hydrogen. The iron half-reaction is already balanced, but the chromium half-reaction
shows two Cr atoms on the left and one Cr atom on the right. Changing the coefficient on the right side of the equation to 2
achieves balance with regard to Cr atoms.
2+ 3+
Fe → Fe
2− 3+
Cr O → 2 Cr
2 7
Balance oxygen atoms by adding H2O molecules. The iron half-reaction does not contain O atoms. The chromium half-reaction
shows seven O atoms on the left and none on the right, so seven water molecules are added to the right side.
2+ 3+
Fe → Fe
2− 3+
Cr O → 2 Cr +7 H O
2 7 2
+
Balance hydrogen atoms by adding H ions. The iron half-reaction does not contain H atoms. The chromium half-reaction shows 14
H atoms on the right and none on the left, so 14 hydrogen ions are added to the left side.
2+ 3+
Fe → Fe
2− + 3+
Cr O + 14 H → 2 Cr +7 H O
2 7 2
Balance charge by adding electrons. The iron half-reaction shows a total charge of 2+ on the left side (1 Fe2+ ion) and 3+ on the
right side (1 Fe3+ ion). Adding one electron to the right side bring that side’s total charge to (3+) + (1−) = 2+, and charge balance is
achieved.
The chromium half-reaction shows a total charge of (1 × 2−) + (14 × 1+) = 12+ on the left side (1 Cr O ion and 14 H+ ions). 2
2−
The total charge on the right side is (2 × 3+) = 6 + (2 Cr3+ ions). Adding six electrons to the left side will bring that side’s total
charge to (12+ + 6−) = 6+, and charge balance is achieved.
2+ 3+ −
Fe → Fe +e
2− + − 3+
Cr O + 14 H +6 e → 2 Cr +7 H O
2 7 2
Multiply the two half-reactions so the number of electrons in one reaction equals the number of electrons in the other reaction. To
be consistent with mass conservation, and the idea that redox reactions involve the transfer (not creation or destruction) of
electrons, the iron half-reaction’s coefficient must be multiplied by 6.
2+ 3+ −
6 Fe → 6 Fe +6 e
2− − + 3+
Cr O +6 e + 14 H → 2 Cr +7 H O
2 7 2
Add the balanced half-reactions and cancel species that appear on both sides of the equation.
2+ 2− − + 3+ − 3+
6 Fe + Cr O +6 e + 14 H → 6 Fe +6 e + 2 Cr +7 H O
2 7 2
Only the six electrons are redundant species. Removing them from each side of the equation yields the simplified, balanced
equation here:
2+ 2− + 3+ 3+
6 Fe + Cr O + 14 H → 6 Fe + 2 Cr +7 H O
2 7 2
A final check of atom and charge balance confirms the equation is balanced.
Final check of atom and charge balance confirms the equation is balanced.
Reactants Products
Fe 6 6
Cr 2 2
O 7 7
H 14 14
charge 24+ 24+
 Exercise 7.3.5
In acidic solution, hydrogen peroxide reacts with Fe2+ to produce Fe3+ and H2O. Write a balanced equation for this reaction.
Answer
+ 2+ 3+
H O (aq) + 2 H (aq) + 2 Fe → 2 H O(l) + 2 Fe
2 2 2
Summary
Chemical reactions are classified according to similar patterns of behavior. A large number of important reactions are included in
three categories: precipitation, acid-base, and oxidation-reduction (redox). Precipitation reactions involve the formation of one or
more insoluble products. Acid-base reactions involve the transfer of hydrogen ions between reactants. Redox reactions involve a
change in oxidation number for one or more reactant elements. Writing balanced equations for some redox reactions that occur in
aqueous solutions is simplified by using a systematic approach called the half-reaction method.
Footnotes
1. 1 The requirement of “charge balance” is just a specific type of “mass balance” in which the species in question are electrons.
An equation must represent equal numbers of electrons on the reactant and product sides, and so both atoms and charges must
be balanced.
2. 2 The requirement of “charge balance” is just a specific type of “mass balance” in which the species in question are electrons.
An equation must represent equal numbers of electrons on the reactant and product sides, and so both atoms and charges must
be balanced.
Glossary
acid
substance that produces H3O+ when dissolved in water
acid-base reaction
reaction involving the transfer of a hydrogen ion between reactant species
base
substance that produces OH− when dissolved in water
combustion reaction
vigorous redox reaction producing significant amounts of energy in the form of heat and, sometimes, light
half-reaction
an equation that shows whether each reactant loses or gains electrons in a reaction.
insoluble
of relatively low solubility; dissolving only to a slight extent
neutralization reaction
reaction between an acid and a base to produce salt and water
oxidation
process in which an element’s oxidation number is increased by loss of electrons
oxidation-reduction reaction
(also, redox reaction) reaction involving a change in oxidation number for one or more reactant elements
oxidation number
(also, oxidation state) the charge each atom of an element would have in a compound if the compound were ionic
oxidizing agent
(also, oxidant) substance that brings about the oxidation of another substance, and in the process becomes reduced
precipitate
insoluble product that forms from reaction of soluble reactants
precipitation reaction
reaction that produces one or more insoluble products; when reactants are ionic compounds, sometimes called double-
displacement or metathesis
reduction
process in which an element’s oxidation number is decreased by gain of electrons
reducing agent
(also, reductant) substance that brings about the reduction of another substance, and in the process becomes oxidized
salt
ionic compound that can be formed by the reaction of an acid with a base that contains a cation and an anion other than
hydroxide or oxide
single-displacement reaction
(also, replacement) redox reaction involving the oxidation of an elemental substance by an ionic species
soluble
of relatively high solubility; dissolving to a relatively large extent
solubility
the extent to which a substance may be dissolved in water, or any solvent
strong acid
acid that reacts completely when dissolved in water to yield hydronium ions
strong base
base that reacts completely when dissolved in water to yield hydroxide ions
weak acid
acid that reacts only to a slight extent when dissolved in water to yield hydronium ions
weak base
base that reacts only to a slight extent when dissolved in water to yield hydroxide ions
7.3: Classifying Chemical Reactions is shared under a CC BY license and was authored, remixed, and/or curated by LibreTexts.
4.2: Classifying Chemical Reactions is licensed CC BY 4.0.
Explain the concept of stoichiometry as it pertains to chemical reactions
Use balanced chemical equations to derive stoichiometric factors relating amounts of reactants and products
Perform stoichiometric calculations involving mass, moles, and solution molarity
A balanced chemical equation provides a great deal of information in a very succinct format. Chemical formulas provide the
identities of the reactants and products involved in the chemical change, allowing classification of the reaction. Coefficients
provide the relative numbers of these chemical species, allowing a quantitative assessment of the relationships between the
amounts of substances consumed and produced by the reaction. These quantitative relationships are known as the reaction’s
stoichiometry, a term derived from the Greek words stoicheion (meaning “element”) and metron (meaning “measure”). In this
module, the use of balanced chemical equations for various stoichiometric applications is explored.
The general approach to using stoichiometric relationships is similar in concept to the way people go about many common
activities. Cooking, for example, offers an appropriate comparison. Suppose a recipe for making eight pancakes calls for 1 cup
3
pancake mix, cup milk, and one egg. The “equation” representing the preparation of pancakes per this recipe is
4
3
1 cup mix + cup milk + 1 egg → 8 pancakes (7.4.1)
4
If two dozen pancakes are needed for a big family breakfast, the ingredient amounts must be increased proportionally according to
the amounts given in the recipe. For example, the number of eggs required to make 24 pancakes is
1 egg
24 pancakes × = 3 eggs (7.4.2)
8 pancakes
Balanced chemical equations are used in much the same fashion to determine the amount of one reactant required to react with a
given amount of another reactant, or to yield a given amount of product, and so forth. The coefficients in the balanced equation are
used to derive stoichiometric factors that permit computation of the desired quantity. To illustrate this idea, consider the production
of ammonia by reaction of hydrogen and nitrogen:
N (g) + 3 H (g) → 2 NH (g) (7.4.3)
2 2 3
This equation shows that ammonia molecules are produced from hydrogen molecules in a 2:3 ratio, and stoichiometric factors may
be derived using any amount (number) unit:
2 NH molecules 2 doz NH molecules 2 mol NH molecules
3 3 3
or or (7.4.4)
3H molecules 3 doz H molecules 3 mol H molecules
2 2 2
These stoichiometric factors can be used to compute the number of ammonia molecules produced from a given number of
hydrogen molecules, or the number of hydrogen molecules required to produce a given number of ammonia molecules. Similar
factors may be derived for any pair of substances in any chemical equation.
 Example 7.4.1: Moles of Reactant Required in a Reaction

How many moles of I2 are required to react with 0.429 mol of Al according to the following equation (see Figure 7.4.2)?
2 Al + 3 I → 2 AlI (7.4.5)
2 3

Figure 7.4.1 : Aluminum and iodine react to produce aluminum iodide. The heat of the reaction vaporizes some of the solid
iodine as a purple vapor. (credit: modification of work by Mark Ott)
Three pictures showing the progression of the reaction between iodine and aluminum. The first diagram shows only a pile of
silver powder while the second diagram shows small amount of vapor forming. The final picture shows a large release of
purple vapor.
Solution
3 mol I
Referring to the balanced chemical equation, the stoichiometric factor relating the two substances of interest is 2
. The
2 mol Al
molar amount of iodine is derived by multiplying the provided molar amount of aluminum by this factor:
3 mol I2
mol I2 = 0.429 mol Al ×
2 mol Al
= 0.644 mol I2
 Exercise 7.4.1
How many moles of Ca(OH)2 are required to react with 1.36 mol of H3PO4 to produce Ca3(PO4)2 according to the equation
3 Ca (OH) + 2 H PO → Ca (PO ) + 6 H O ?
2 3 4 3 4 2 2
Answer
2.04 mol
 Example 7.4.2: Number of Product Molecules Generated by a Reaction
How many carbon dioxide molecules are produced when 0.75 mol of propane is combusted according to this equation?
C H +5 O → 3 CO +4 H O (7.4.6)
3 8 2 2 2
Solution
The approach here is the same as for Example 7.4.1, though the absolute number of molecules is requested, not the number of
moles of molecules. This will simply require use of the moles-to-numbers conversion factor, Avogadro’s number.
The balanced equation shows that carbon dioxide is produced from propane in a 3:1 ratio:
\[\ce{\dfrac{3\: mol\: CO2}{1\: mol\: C3H8}} \label{4.4.7} \]
Using this stoichiometric factor, the provided molar amount of propane, and Avogadro’s number,

3 mol CO2 23
6.022 × 10 C O2 molecules 24
0.75 mol C3 H8 × × = 1.4 × 10 C O2 molecules (7.4.7)
1 mol C3 H8 mol CO2
 Exercise 7.4.1
How many NH3 molecules are produced by the reaction of 4.0 mol of Ca(OH)2 according to the following equation:
(NH ) SO + Ca (OH) → 2 NH + CaSO +2 H O (7.4.8)
4 2 4 2 3 4 2
Answer
4.8 × 1024 NH3 molecules
These examples illustrate the ease with which the amounts of substances involved in a chemical reaction of known stoichiometry
may be related. Directly measuring numbers of atoms and molecules is, however, not an easy task, and the practical application of
stoichiometry requires that we use the more readily measured property of mass.
 Example 7.4.3: Relating Masses of Reactants and Products
What mass of sodium hydroxide, NaOH, would be required to produce 16 g of the antacid milk of magnesia [magnesium
hydroxide, Mg(OH)2] by the following reaction?
MgCl (aq) + 2 NaOH(aq) → Mg (OH) (s) + 2 NaCl(aq)
2 2
Solution
The approach used previously in Examples 7.4.1 and 7.4.2 is likewise used here; that is, we must derive an appropriate
stoichiometric factor from the balanced chemical equation and use it to relate the amounts of the two substances of interest. In this
case, however, masses (not molar amounts) are provided and requested, so additional steps of the sort learned in the previous
chapter are required. The calculations required are outlined in this flowchart:
1 mol Mg(OH)2 2 mol NaOH 40.0 g NaOH

16 g Mg(OH)2 × × × = 22 g NaOH
58.3 g Mg(OH)2 1 mol Mg(OH)2 mol NaOH
 Exercise 7.4.3
What mass of gallium oxide, Ga2O3, can be prepared from 29.0 g of gallium metal? The equation for the reaction is
4 Ga + 3 O → 2 Ga O .
2 2 3
Answer
39.0 g

 Example 7.4.4: Relating Masses of Reactants
What mass of oxygen gas, O2, from the air is consumed in the combustion of 702 g of octane, C8H18, one of the principal
components of gasoline?
2C H + 25 O → 16 CO + 18 H O
8 18 2 2 2
Solution
The approach required here is the same as for the Example 7.4.3, differing only in that the provided and requested masses are
both for reactant species.
1 mol C H 25 mol O
8 18 2 32.00 g O
2 3
702 g C H × × × = 2.46 × 10 g O
8 18 2
114.23 g C H 2 mol C H mol O
8 18 8 18 2
 Exercise 7.4.4
What mass of CO is required to react with 25.13 g of Fe2O3 according to the equation Fe 2
O
3
+ 3 CO → 2 Fe + 3 CO
2
?
Answer
13.22 g
These examples illustrate just a few instances of reaction stoichiometry calculations. Numerous variations on the beginning and
ending computational steps are possible depending upon what particular quantities are provided and sought (volumes, solution
concentrations, and so forth). Regardless of the details, all these calculations share a common essential component: the use of
stoichiometric factors derived from balanced chemical equations. Figure 7.4.2 provides a general outline of the various
computational steps associated with many reaction stoichiometry calculations.

Figure 7.4.2 : The flowchart depicts the various computational steps involved in most reaction stoichiometry calculations.
Schematic flowchart showing how density is used for converting volume of pure substance to mass, molar mass for mass and
moles, molarity for moles and volume of solution, Avogadro's number for moles and number of particles, and stoichiometric factor
for relating moles of one substance to another.
 Airbags
Airbags (Figure 7.4.3) are a safety feature provided in most automobiles since the 1990s. The effective operation of an airbag
requires that it be rapidly inflated with an appropriate amount (volume) of gas when the vehicle is involved in a collision. This
requirement is satisfied in many automotive airbag systems through use of explosive chemical reactions, one common choice
being the decomposition of sodium azide, NaN3. When sensors in the vehicle detect a collision, an electrical current is passed
through a carefully measured amount of NaN3 to initiate its decomposition:
2 NaN (s) → 3 N (g) + 2 Na(s)

3 2
This reaction is very rapid, generating gaseous nitrogen that can deploy and fully inflate a typical airbag in a fraction of a second
(~0.03–0.1 s). Among many engineering considerations, the amount of sodium azide used must be appropriate for generating
enough nitrogen gas to fully inflate the air bag and ensure its proper function. For example, a small mass (~100 g) of NaN3 will
generate approximately 50 L of N2.

Figure 7.4.3 : Airbags deploy upon impact to minimize serious injuries to passengers. (credit: Jon Seidman)
Summary
A balanced chemical equation may be used to describe a reaction’s stoichiometry (the relationships between amounts of reactants
and products). Coefficients from the equation are used to derive stoichiometric factors that subsequently may be used for
computations relating reactant and product masses, molar amounts, and other quantitative properties.
Glossary
stoichiometric factor
ratio of coefficients in a balanced chemical equation, used in computations relating amounts of reactants and products
stoichiometry
relationships between the amounts of reactants and products of a chemical reaction
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4.3: Reaction Stoichiometry is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

Explain the concepts of theoretical yield and limiting reactants/reagents.
Derive the theoretical yield for a reaction under specified conditions.
Calculate the percent yield for a reaction.
The relative amounts of reactants and products represented in a balanced chemical equation are often referred to as stoichiometric
amounts. All the exercises of the preceding module involved stoichiometric amounts of reactants. For example, when calculating
the amount of product generated from a given amount of reactant, it was assumed that any other reactants required were available
in stoichiometric amounts (or greater). In this module, more realistic situations are considered, in which reactants are not present in
stoichiometric amounts.
Limiting Reactant
Consider another food analogy, making grilled cheese sandwiches (Figure 7.5.1):
1 slice of cheese + 2 slices of bread → 1 sandwich (7.5.1)
Stoichiometric amounts of sandwich ingredients for this recipe are bread and cheese slices in a 2:1 ratio. Provided with 28 slices of
bread and 11 slices of cheese, one may prepare 11 sandwiches per the provided recipe, using all the provided cheese and having six
slices of bread left over. In this scenario, the number of sandwiches prepared has been limited by the number of cheese slices, and
the bread slices have been provided in excess.
Figure 7.5.1 : Sandwich making can illustrate the concepts of limiting and excess reactants.
This figure has three rows showing the ingredients needed to make a sandwich. The first row reads, “1 sandwich = 2 slices of bread
+ 1 slice of cheese.” Two slices of bread and one slice of cheese are shown. The second row reads, “Provided with: 28 slices of
bread + 11 slices of cheese.” There are 28 slices of bread and 11 slices of cheese shown. The third row reads, “We can make: 11
sandwiches + 6 slices of bread left over.” 11 sandwiches are shown with six extra slices of bread.
Consider this concept now with regard to a chemical process, the reaction of hydrogen with chlorine to yield hydrogen chloride:
H (g) + Cl (g) → 2 HCl(g)

2 2
The balanced equation shows the hydrogen and chlorine react in a 1:1 stoichiometric ratio. If these reactants are provided in any
other amounts, one of the reactants will nearly always be entirely consumed, thus limiting the amount of product that may be
generated. This substance is the limiting reactant, and the other substance is the excess reactant. Identifying the limiting and excess
reactants for a given situation requires computing the molar amounts of each reactant provided and comparing them to the
stoichiometric amounts represented in the balanced chemical equation.
For example, imagine combining 6 moles of H2 and 4 moles of Cl2. Identifying the limiting reactant involves comparing the
amount of product expected for the complete reaction of each reactant. Each reactant amount is used to separately calculate the

amount of product that would be formed per the reaction’s stoichiometry. The reactant yielding the lesser amount of product is the
limiting reactant.
For the example in the previous paragraph, the complete reaction of the hydrogen would yield
2 mol HCl
mol HCl produced = 6 mol H2 × = 12 mol HCl
1 mol H2
The complete reaction of the provided chlorine would produce

2 mol HCl
mol HCl produced = 4 mol C l2 × = 8 mol HCl
1 mol Cl2
The chlorine will be completely consumed once 8 moles of HCl have been produced. Since enough hydrogen was provided to yield
12 moles of HCl, there will be non-reacted hydrogen remaining once this reaction is complete. Chlorine, therefore, is the limiting
reactant and hydrogen is the excess reactant (Figure 7.5.2). To determine the amount of excess reactant that remains, the amount
of hydrogen consumed in the reaction can be subtracted from the starting quantity of hydrogen.
The amount of hydrogen consumed is
1 mol H2
mol H2 produced = 8 mol HCl × = 4 mol H2
2 mol HCl
Subtract the hydrogen consumed from the starting quantity
mole of excess H2 = 6 mol H2 starting − 4 mol H2 consumed = 2 mol H2 excess
Figure 7.5.2 : When H2 and Cl2 are combined in nonstoichiometric amounts, one of these reactants will limit the amount of HCl
that can be produced. This illustration shows a reaction in which hydrogen is present in excess and chlorine is the limiting reactant.
The figure shows a space-filling molecular models reacting. There is a reaction arrow pointing to the right in the middle. To the left
of the reaction arrow there are three molecules each consisting of two green spheres bonded together. There are also five molecules
each consisting of two smaller, white spheres bonded together. Above these molecules is the label, “Before reaction,” and below
these molecules is the label, “6 H subscript 2 and 4 C l subscript 2.” To the right of the reaction arrow, there are eight molecules
each consisting of one green sphere bonded to a smaller white sphere. There are also two molecules each consisting of two white
spheres bonded together. Above these molecules is the label, “After reaction,” and below these molecules is the label, “8 H C l and
2 H subscript 2.”
 Example 7.5.1: Identifying the Limiting Reactant

Silicon nitride is a very hard, high-temperature-resistant ceramic used as a component of turbine blades in jet engines. It is
prepared according to the following equation:
3 Si(s) + 2 N (g) → Si N (s)

2 3 4
Which is the limiting reactant when 2.00 g of Si and 1.50 g of N2 react?
Solution

Compute the provided molar amounts of reactants, and then compare these amounts to the balanced equation to identify the
limiting reactant.
1 mol Si
mol Si = 2.00 g Si × = 0.0712 mol Si
28.09 g Si
1 mol N2
mol N2 = 1.50 g N2 × = 0.0535 mol N2
28.02 g N2
The provided Si:N2 molar ratio is:

0.0712 mol Si 1.33 mol Si
=
0.0535 mol N2 1 mol N2
The stoichiometric Si:N2 ratio is:

3 mol Si 1.5 mol Si
=
2 mol N2 1 mol N2
Comparing these ratios shows that Si is provided in a less-than-stoichiometric amount, and so is the limiting reactant.
Alternatively, compute the amount of product expected for complete reaction of each of the provided reactants. The 0.0712
moles of silicon would yield
1 mol Si3 N4
mol Si3 N4 produced = 0.0712 mol Si × = 0.0237 mol Si3 N4
3 mol Si
while the 0.0535 moles of nitrogen would produce

1 mol Si3 N4
mol Si3 N4 produced = 0.0535 mol N2 × = 0.0268 mol Si3 N4
2 mol N2
Since silicon yields the lesser amount of product, it is the limiting reactant.
 Exercise 7.5.1
Which is the limiting reactant when 5.00 g of H2 and 10.0 g of O2 react and form water?
Answer
O2
Percent Yield
The amount of product that may be produced by a reaction under specified conditions, as calculated per the stoichiometry of an
appropriate balanced chemical equation, is called the theoretical yield of the reaction. In practice, the amount of product obtained is
called the actual yield, and it is often less than the theoretical yield for a number of reasons. Some reactions are inherently
inefficient, being accompanied by side reactions that generate other products. Others are, by nature, incomplete (consider the
partial reactions of weak acids and bases discussed earlier in this text). Some products are difficult to collect without some loss, and
so less than perfect recovery will reduce the actual yield. The extent to which a reaction’s theoretical yield is achieved is commonly
expressed as its percent yield:
actual yield
percent yield = × 100%
theoretical yield
Actual and theoretical yields may be expressed as masses or molar amounts (or any other appropriate property; e.g., volume, if the
product is a gas). As long as both yields are expressed using the same units, these units will cancel when percent yield is calculated.

 Example 7.5.2: Calculation of Percent Yield
Upon reaction of 1.274 g of copper sulfate with excess zinc metal, 0.392 g copper metal was obtained according to the
equation:
CuSO (aq) + Zn(s) → Cu(s) + ZnSO (aq)

4 4
What is the percent yield?
Solution
The provided information identifies copper sulfate as the limiting reactant, and so the theoretical yield is found by the approach
illustrated in the previous module, as shown here:
1 mol CuSO4 1 mol Cu 63.55 g Cu

1.274 g CuS O4 × × × = 0.5072 g Cu
159.62 g CuSO4 1 mol CuSO4 1 mol Cu
Using this theoretical yield and the provided value for actual yield, the percent yield is calculated to be
actual yield
percent yield = ( ) × 100
theoretical yield
0.392 g Cu
0.5072 g Cu
= 77.3%
 Exercise 7.5.2
What is the percent yield of a reaction that produces 12.5 g of the gas Freon CF2Cl2 from 32.9 g of CCl4 and excess HF?
CCl + 2 HF → CF Cl + 2 HCl
4 2 2
Answer
48.3%
 Green Chemistry and Atom Economy

The purposeful design of chemical products and processes that minimize the use of environmentally hazardous substances and
the generation of waste is known as green chemistry. Green chemistry is a philosophical approach that is being applied to many
areas of science and technology, and its practice is summarized by guidelines known as the “Twelve Principles of Green
Chemistry”. One of the 12 principles is aimed specifically at maximizing the efficiency of processes for synthesizing chemical
products. The atom economy of a process is a measure of this efficiency, defined as the percentage by mass of the final product
of a synthesis relative to the masses of all the reactants used:
mass of product
atom economy = × 100%
mass of reactants
Though the definition of atom economy at first glance appears very similar to that for percent yield, be aware that this property
represents a difference in the theoretical efficiencies of different chemical processes. The percent yield of a given chemical
process, on the other hand, evaluates the efficiency of a process by comparing the yield of product actually obtained to the
maximum yield predicted by stoichiometry.
The synthesis of the common nonprescription pain medication, ibuprofen, nicely illustrates the success of a green chemistry
approach (Figure 7.5.3). First marketed in the early 1960s, ibuprofen was produced using a six-step synthesis that required 514
g of reactants to generate each mole (206 g) of ibuprofen, an atom economy of 40%. In the 1990s, an alternative process was

developed by the BHC Company (now BASF Corporation) that requires only three steps and has an atom economy of ~80%,
nearly twice that of the original process. The BHC process generates significantly less chemical waste; uses less-hazardous and
recyclable materials; and provides significant cost-savings to the manufacturer (and, subsequently, the consumer). In
recognition of the positive environmental impact of the BHC process, the company received the Environmental Protection
Agency’s Greener Synthetic Pathways Award in 1997.
Figure 7.5.3 : (a) Ibuprofen is a popular nonprescription pain medication commonly sold as 200 mg tablets. (b) The BHC
process for synthesizing ibuprofen requires only three steps and exhibits an impressive atom economy. (credit a: modification
of work by Derrick Coetzee)
Summary
When reactions are carried out using less-than-stoichiometric quantities of reactants, the amount of product generated will be
determined by the limiting reactant. The amount of product generated by a chemical reaction is its actual yield. This yield is often
less than the amount of product predicted by the stoichiometry of the balanced chemical equation representing the reaction (its
theoretical yield). The extent to which a reaction generates the theoretical amount of product is expressed as its percent yield.
Key Equations
actual yield
theoretical yield
Glossary
actual yield
amount of product formed in a reaction
excess reactant
reactant present in an amount greater than required by the reaction stoichiometry
limiting reactant
reactant present in an amount lower than required by the reaction stoichiometry, thus limiting the amount of product generated
percent yield
measure of the efficiency of a reaction, expressed as a percentage of the theoretical yield
theoretical yield
amount of product that may be produced from a given amount of reactant(s) according to the reaction stoichiometry
This page titled 7.5: Reaction Yields is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
4.4: Reaction Yields is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

Describe the fundamental aspects of titrations and gravimetric analysis.
Perform stoichiometric calculations using typical titration and gravimetric data.
In the 18th century, the strength (actually the concentration) of vinegar samples was determined by noting the amount of potassium
carbonate, K2CO3, which had to be added, a little at a time, before bubbling ceased. The greater the weight of potassium carbonate
added to reach the point where the bubbling ended, the more concentrated the vinegar.
We now know that the effervescence that occurred during this process was due to reaction with acetic acid, CH3CO2H, the
compound primarily responsible for the odor and taste of vinegar. Acetic acid reacts with potassium carbonate according to the
following equation:
2 CH CO H(aq) + K CO (s) → 2 KCH CO (aq) + CO (g) + H O(l)

3 2 2 3 3 3 2 2
The bubbling was due to the production of CO2.

The test of vinegar with potassium carbonate is one type of quantitative analysis—the determination of the amount or concentration
of a substance in a sample. In the analysis of vinegar, the concentration of the solute (acetic acid) was determined from the amount
of reactant that combined with the solute present in a known volume of the solution. In other types of chemical analyses, the
amount of a substance present in a sample is determined by measuring the amount of product that results.
Titration
The described approach to measuring vinegar strength was an early version of the analytical technique known as titration analysis.
A typical titration analysis involves the use of a buret (Figure 7.6.1) to make incremental additions of a solution containing a
known concentration of some substance (the titrant) to a sample solution containing the substance whose concentration is to be
measured (the analyte). The titrant and analyte undergo a chemical reaction of known stoichiometry, and so measuring the volume
of titrant solution required for complete reaction with the analyte (the equivalence point of the titration) allows calculation of the
analyte concentration. The equivalence point of a titration may be detected visually if a distinct change in the appearance of the
sample solution accompanies the completion of the reaction. The halt of bubble formation in the classic vinegar analysis is one
such example, though, more commonly, special dyes called indicators are added to the sample solutions to impart a change in color
at or very near the equivalence point of the titration. Equivalence points may also be detected by measuring some solution property
that changes in a predictable way during the course of the titration. Regardless of the approach taken to detect a titration’s
equivalence point, the volume of titrant actually measured is called the end point. Properly designed titration methods typically
ensure that the difference between the equivalence and end points is negligible. Though any type of chemical reaction may serve as
the basis for a titration analysis, the three described in this chapter (precipitation, acid-base, and redox) are most common.
Additional details regarding titration analysis are provided in the chapter on acid-base equilibria.

Figure 7.6.1 : (a) A student fills a buret in preparation for a titration analysis. (b) A typical buret permits volume measurements to
the nearest 0.1 mL. (credit a: modification of work by Mark Blaser and Matt Evans; credit b: modification of work by Mark Blaser
and Matt Evans)
Two pictures are shown. In a, a person is shown pouring a liquid from a small beaker into a buret. The person is wearing goggles
and gloves as she transfers the solution into the buret. In b, a close up view of the markings on the side of the buret is shown. The
markings for 10, 15, and 20 are clearly shown with horizontal rings printed on the buret. Between each of these whole number
markings, half markings are also clearly shown with horizontal line segment markings.
 Example 7.6.1: Titration Analysis
The end point in a titration of a 50.00-mL sample of aqueous HCl was reached by addition of 35.23 mL of 0.250 M NaOH
titrant. The titration reaction is:
HCl(aq) + NaOH(aq) → NaCl(aq) + H O(l)
2
What is the molarity of the HCl?
Solution
As for all reaction stoichiometry calculations, the key issue is the relation between the molar amounts of the chemical species
of interest as depicted in the balanced chemical equation. The approach outlined in previous modules of this chapter is
followed, with additional considerations required, since the amounts of reactants provided and requested are expressed as
solution concentrations.
For this exercise, the calculation will follow the following outlined steps:

This figure shows four rectangles. The first is shaded lavender and is labeled, “Volume of N a O H.” This rectangle is followed
by an arrow pointing right which is labeled, “Molar concentration,” to a second rectangle. This second rectangle is shaded pink
and is labeled, “Moles of N a O H.” This rectangle is followed by an arrow pointing right which is labeled, “Stoichiometric
factor,” to a third rectangle which is shaded pink and is labeled, “Moles of H C l.” This rectangle is followed by an arrow
labeled, “Solution volume,” which points right to a fourth rectangle. This fourth rectangle is shaded lavender and is labeled,
“Concentration of H C l.”
The molar amount of HCl is calculated to be:
1 L 0.250 mol NaOH 1 mol HCl −3

35.23 mL NaOH × × × = 8.81 × 10 mol HCl
1000 mL 1 L 1 mol NaOH
Using the provided volume of HCl solution and the definition of molarity, the HCl concentration is:
mol HCl
M =
L solution
−3
8.81 × 10 mol HCl
M =
1 L
50.00 mL ×
1000 mL
M = 0.176 M
Note: For these types of titration calculations, it is convenient to recognize that solution molarity is also equal to the number of
millimoles of solute per milliliter of solution:
3
10 mmol
mol solute mol mmol solute

M = × =
3
L solution 10 mL mL solution
Using this version of the molarity unit will shorten the calculation by eliminating two conversion factors:
0.250 mmol NaOH 1 mmol HCl
35.23 mL NaOH × ×
mL NaOH 1 mmol NaOH
= 0.176 M HCl
50.00 mL solution
 Exercise 7.6.1
A 20.00-mL sample of aqueous oxalic acid, H2C2O4, was titrated with a 0.09113-M solution of potassium permanganate,
KMnO4.
− + 2+
2 MnO (aq) + 5 H C O (aq) + 6 H (aq) → 10 CO (g) + 2 Mn (aq) + 8 H O(l)
4 2 2 4 2 2
A volume of 23.24 mL was required to reach the end point. What is the oxalic acid molarity?
Answer
0.2648 M

Gravimetric Analysis
A gravimetric analysis is one in which a sample is subjected to some treatment that causes a change in the physical state of the
analyte that permits its separation from the other components of the sample. Mass measurements of the sample, the isolated
analyte, or some other component of the analysis system, used along with the known stoichiometry of the compounds involved,
permit calculation of the analyte concentration. Gravimetric methods were the first techniques used for quantitative chemical
analysis, and they remain important tools in the modern chemistry laboratory.
The required change of state in a gravimetric analysis may be achieved by various physical and chemical processes. For example,
the moisture (water) content of a sample is routinely determined by measuring the mass of a sample before and after it is subjected
to a controlled heating process that evaporates the water. Also common are gravimetric techniques in which the analyte is subjected
to a precipitation reaction of the sort described earlier in this chapter. The precipitate is typically isolated from the reaction mixture
by filtration, carefully dried, and then weighed (Figure 7.6.2). The mass of the precipitate may then be used, along with relevant
stoichiometric relationships, to calculate analyte concentration.
Figure 7.6.2 : Precipitate may be removed from a reaction mixture by filtration.

"A photo is shown of a flask and funnel used for filtration. The flask contains a slightly opaque liquid filtrate with a slight yellow
tint. A funnel, which contains a bright yellow and orange material, sits atop the flask. The flask is held in place by a clamp and is
connected to a vacuum line. The connection between the funnel and flask is sealed with a rubber bung or gasket."
 Example 7.6.2: Gravimetric Analysis
A 0.4550-g solid mixture containing MgSO4 is dissolved in water and treated with an excess of Ba(NO3)2, resulting in the
precipitation of 0.6168 g of BaSO4.
MgSO (aq) + Ba (NO ) (aq) → BaSO (s) + Mg (NO ) (aq)

4 3 2 4 3 2
What is the concentration (percent) of MgSO4 in the mixture?
Solution
The plan for this calculation is similar to others used in stoichiometric calculations, the central step being the connection
between the moles of BaSO4 and MgSO4 through their stoichiometric factor. Once the mass of MgSO4 is computed, it may be
used along with the mass of the sample mixture to calculate the requested percentage concentration.

"This figure shows five rectangles. The first is shaded yellow and is labeled “Mass of B a S O subscript 4.” This rectangle is
followed by an arrow pointing right to a second rectangle. The arrow is labeled, “Molar mass.” The second rectangle is shaded
pink and is labeled, “Moles of B a S O subscript 4.” This rectangle is followed by an arrow pointing right to a third rectangle.
The arrow is labeled, “Stoichiometric factor.” This third rectangle is shaded pink and is labeled, “Moles of M g S O subscript
4.” This rectangle is followed by an arrow labeled, “Molar mass,” which points downward to a fourth rectangle. This fourth
rectangle is shaded yellow and is labeled, “Mass of M g S O subscript 4.” This rectangle is followed by an arrow labeled,
“Sample mass,” which points left to a fifth rectangle. This fifth rectangle is shaded lavender and is labeled, “Percent M g S O
subscript 4."
The mass of MgSO4 that would yield the provided precipitate mass is
1 mol BaSO4 1 mol MgSO4 120.37 g MgSO4

0.6168 g BaSO4 × × × = 0.3181 g MgSO4
233.43 g BaSO4 1 mol BaSO4 1 mol MgSO4
The concentration of MgSO4 in the sample mixture is then calculated to be

mass MgSO
4
percent MgSO = × 100%
4
mass sample
0.3181 g
× 100% = 69.91%
0.4550 g
 Exercise 7.6.2
What is the percent of chloride ion in a sample if 1.1324 g of the sample produces 1.0881 g of AgCl when treated with excess
Ag+?
+ −
Ag (aq) + Cl (aq) → AgCl(s)
Answer
23.76%
Combustion Analysis
The elemental composition of hydrocarbons and related compounds may be determined via a gravimetric method known as
combustion analysis. In a combustion analysis, a weighed sample of the compound is heated to a high temperature under a stream
of oxygen gas, resulting in its complete combustion to yield gaseous products of known identities. The complete combustion of
hydrocarbons, for example, will yield carbon dioxide and water as the only products. The gaseous combustion products are swept
through separate, preweighed collection devices containing compounds that selectively absorb each product (Figure 7.6.3). The
mass increase of each device corresponds to the mass of the absorbed product and may be used in an appropriate stoichiometric
calculation to derive the mass of the relevant element.

Figure 7.6.3 : This schematic diagram illustrates the basic components of a combustion analysis device for determining the carbon
and hydrogen content of a sample.
This diagram shows an arrow pointing from O subscript 2 into a tube that leads into a vessel containing a red material, labeled
“Sample.” This vessel is inside a blue container with a red inner lining which is labeled “Furnace.” An arrow points from the tube
to the right into the vessel above the red sample material. An arrow leads out of this vessel through a tube into a second vessel
outside the furnace. An line points from this tube to a label above the diagram that reads “C O subscript 2, H subscript 2 O, O
subscript 2, and other gases.” Many small green spheres are visible in the second vessel which is labeled below, “H subscript 2 O
absorber such as M g ( C l O subscript 4 ) subscript 2.” An arrow points to the right through the vessel, and another arrow points
right heading out of the vessel through a tube into a third vessel. The third vessel contains many small blue spheres. It is labeled “C
O subscript 2 absorber such as N a O H.” An arrow points right through this vessel, and a final arrow points out of a tube at the
right end of the vessel. Outside the end of this tube at the end of the arrow is the label, “O subscript 2 and other gases.”
 Example 7.6.3: Combustion Analysis
Polyethylene is a hydrocarbon polymer used to produce food-storage bags and many other flexible plastic items. A combustion
analysis of a 0.00126-g sample of polyethylene yields 0.00394 g of CO2 and 0.00161 g of H2O. What is the empirical formula
of polyethylene?
Solution
The primary assumption in this exercise is that all the carbon in the sample combusted is converted to carbon dioxide, and all
the hydrogen in the sample is converted to water:
y
Cx Hy (s) + excess O (g) → x CO (g) + H O(g)
2 2 2
2
Note that a balanced equation is not necessary for the task at hand. To derive the empirical formula of the compound, only the
subscripts x and y are needed.
First, calculate the molar amounts of carbon and hydrogen in the sample, using the provided masses of the carbon dioxide and
water, respectively. With these molar amounts, the empirical formula for the compound may be written as described in the
previous chapter of this text. An outline of this approach is given in the following flow chart:

This figure shows two flowcharts. The first row is a single flow chart. In this row, a rectangle at the left is shaded yellow and is
labeled, “Mass of C O subscript 2.” This rectangle is followed by an arrow pointing right to a second rectangle. The arrow is
labeled, “Molar mass.” The second rectangle is shaded pink and is labeled, “Moles of C O subscript 2.” This rectangle is
followed by an arrow pointing right to a third rectangle. The arrow is labeled, “Stoichiometric factor.” The third rectangle is
shaded pink and is labeled, “Moles of C.” This rectangle is followed by an arrow labeled “Molar mass” which points right to a
fourth rectangle. The fourth rectangle is shaded yellow and is labeled “Mass of C.” Below, is a second flowchart. It begins with
a yellow shaded rectangle on the left which is labeled, “Mass of H subscript 2 O.” This rectangle is followed by an arrow
labeled, “Molar mass,” which points right to a second rectangle. The second rectangle is shaded pink and is labeled, “Moles of
H subscript 2 O.” This rectangle is followed by an arrow pointing right to a third rectangle. The arrow is labeled,
“Stoichiometric factor.” The third rectangle is shaded pink and is labeled “Moles of H.” This rectangle is followed to the right
by an arrow labeled, “Molar mass,” which points to a fourth rectangle. The fourth rectangle is shaded yellow and is labeled
“Mass of H.” An arrow labeled, “Sample mass” points down beneath this rectangle to a green shaded rectangle. This rectangle
is labeled, “Percent composition.” An arrow extends beneath the pink rectangle labeled, “Moles of H,” to a green shaded
rectangle labeled, “C to H mole ratio.” Beneath this rectangle, an arrow extends to a second green shaded rectangle which is
labeled, “Empirical formula.”
1 mol CO2 1 mol C −5
mol C = 0.00394 g C O2 × × = 8.95 × 10 mol C
44.01 g/mol 1 mol CO2
1 mol H2 O 2 mol H
−4
mol H = 0.00161 g H2 O × × = 1.79 × 10 mol H
18.02 g/mol 1 mol H2 O
The empirical formula for the compound is then derived by identifying the smallest whole-number multiples for these molar
amounts. The H-to-C molar ratio is
−4
mol H 1.79 × 10 mol H 2 mol H
= =
−5
mol C 8.95 × 10 mol C 1 mol C
and the empirical formula for polyethylene is CH2.
 Exercise 7.6.3
A 0.00215-g sample of polystyrene, a polymer composed of carbon and hydrogen, produced 0.00726 g of CO2 and 0.00148 g
of H2O in a combustion analysis. What is the empirical formula for polystyrene?
Answer
CH

Summary
The stoichiometry of chemical reactions may serve as the basis for quantitative chemical analysis methods. Titrations involve
measuring the volume of a titrant solution required to completely react with a sample solution. This volume is then used to
calculate the concentration of analyte in the sample using the stoichiometry of the titration reaction. Gravimetric analysis involves
separating the analyte from the sample by a physical or chemical process, determining its mass, and then calculating its
concentration in the sample based on the stoichiometry of the relevant process. Combustion analysis is a gravimetric method used
to determine the elemental composition of a compound by collecting and weighing the gaseous products of its combustion.
Glossary
analyte
chemical species of interest
buret
device used for the precise delivery of variable liquid volumes, such as in a titration analysis
combustion analysis
gravimetric technique used to determine the elemental composition of a compound via the collection and weighing of its
gaseous combustion products
end point
measured volume of titrant solution that yields the change in sample solution appearance or other property expected for
stoichiometric equivalence (see equivalence point)
equivalence point
volume of titrant solution required to react completely with the analyte in a titration analysis; provides a stoichiometric amount
of titrant for the sample’s analyte according to the titration reaction
gravimetric analysis
quantitative chemical analysis method involving the separation of an analyte from a sample by a physical or chemical process
and subsequent mass measurements of the analyte, reaction product, and/or sample
indicator
substance added to the sample in a titration analysis to permit visual detection of the end point
quantitative analysis
the determination of the amount or concentration of a substance in a sample
titrant
solution containing a known concentration of substance that will react with the analyte in a titration analysis
titration analysis
quantitative chemical analysis method that involves measuring the volume of a reactant solution required to completely react
with the analyte in a sample
This page titled 7.6: Quantitative Chemical Analysis is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
4.5: Quantitative Chemical Analysis is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

Q4.1.1
What does it mean to say an equation is balanced? Why is it important for an equation to be balanced?
S4.1.1
An equation is balanced when the same number of each element is represented on the reactant and product sides. Equations must be
balanced to accurately reflect the law of conservation of matter.
Q4.1.2
Consider molecular, complete ionic, and net ionic equations.
a. What is the difference between these types of equations?
b. In what circumstance would the complete and net ionic equations for a reaction be identical?
Q4.1.3
Balance the following equations:
a. PCl (s) + H O(l) → POCl (l) + HCl(aq)
5 2 3
b. Cu(s) + HNO (aq) → Cu(NO ) (aq) + H O(l) + NO(g)

3 3 2 2
c. H (g) + I (s) → HI(s)

2 2
d. Fe(s) + O (g) → Fe O (s) 2 2 3
e. Na(s) + H O(l) → NaOH(aq) + H (g)

2 2
f. (NH ) Cr O (s) → Cr O (s) + N (g) + H O(g)

4 2 2 7 2 3 2 2
g. P (s) + Cl (g) → PCl (l)

4 2 3
h. PtCl (s) → Pt(s) + Cl (g)

4 2
S4.1.3
a. PCl (s) + H O(l) → POCl (l) + 2 HCl(aq) ;
5 2 3
b. 3 Cu(s) + 8 HNO (aq) → 3 Cu(NO ) (aq) + 4 H O(l) + 2 NO(g) ;

3 3 2 2
c. H (g) + I (s) → 2 HI(s) ;

2 2
d. 4 Fe(s) + 3 O (g) → 2 Fe O (s) ; 2 2 3
e. 2 Na(s) + 2 H O(l) → 2 NaOH(aq) + H (g) ;

2 2
f. (NH ) Cr O (s) → Cr O (s) + N (g) + 4 H O(g) ;

4 2 52 7 2 3 2 2
g. P (s) + 6 Cl (g) → 4 PCl (l) ;

4 2 3
h. PtCl (s) → Pt(s) + 2 Cl (g)

4 2
Q4.1.4
Balance the following equations:
a. Ag(s) + H S(g) + O (g) → Ag S(s) + H O(l)
2 2 2 2
b. P (s) + O (g) → P O (s)

4 2 4 10
c. Pb(s) + H O(l) + O (g) → Pb(OH) (s)

2 2 2
d. Fe(s) + H O(l) → Fe O (s) + H (g)

2 3 4 2
e. Sc O (s) + SO (l) → Sc (SO ) (s)

2 3 3 2 4 3
f. Ca (PO ) (aq) + H PO (aq) → Ca(H PO )

3 4 2 3 4 2 4 2
(aq)
g. Al(s) + H SO (aq) → Al (SO ) (s) + H (g)

2 4 2 4 3 2
h. TiCl (s) + H O(g) → TiO (s) + HCl(g)

4 2 2
S4.1.4
a. 4 Ag(s) + 2 H S(g) + O (g) → 2 Ag S(s) + 2 H
2 2 2 2
O(l)
b. P (s) + 5 O (g) → P O (s)

4 2 4 10
c. 2 Pb(s) + 2 H O(l) + O (g) → 2 Pb(OH) (s)

2 2 2
d. 3 Fe(s) + 4 H O(l) → Fe O (s) + 4 H (g)

2 3 4 2

e. Sc O (s) + 3 SO (l) → Sc (SO ) (s)
2 3 3 2 4 3
f. Ca (PO ) (aq) + 4 H PO (aq) → 3 Ca(H PO ) (aq)

3 4 2 3 4 2 4 2
g. 2 Al(s) + 3 H SO (aq) → Al (SO ) (s) + 3 H (g)

2 4 2 4 3 2
h. TiCl (s) + 2 H O(g) → TiO (s) + 4 HCl(g)

4 2 2
Q4.1.5
Write a balanced molecular equation describing each of the following chemical reactions.
a. Solid calcium carbonate is heated and decomposes to solid calcium oxide and carbon dioxide gas.
b. Gaseous butane, C4H10, reacts with diatomic oxygen gas to yield gaseous carbon dioxide and water vapor.
c. Aqueous solutions of magnesium chloride and sodium hydroxide react to produce solid magnesium hydroxide and aqueous sodium
chloride.
d. Water vapor reacts with sodium metal to produce solid sodium hydroxide and hydrogen gas.
S4.1.5
a. CaCO (s) → CaO(s) + CO (g) ;
3 2
b. 2 C H (g) + 13 O (g) → 8 CO (g) + 10 H O(g) ;

4 10 2 2 2
c. MgCl (aq) + 2 NaOH(aq) → Mg(OH) (s) + 2 NaCl(aq) ;

2 2
d. 2 H O(g) + 2 Na(s) → 2 NaOH(s) + H (g)

2 2
Q4.1.6
Write a balanced equation describing each of the following chemical reactions.
a. Solid potassium chlorate, KClO3, decomposes to form solid potassium chloride and diatomic oxygen gas.
b. Solid aluminum metal reacts with solid diatomic iodine to form solid Al2I6.
c. When solid sodium chloride is added to aqueous sulfuric acid, hydrogen chloride gas and aqueous sodium sulfate are produced.
d. Aqueous solutions of phosphoric acid and potassium hydroxide react to produce aqueous potassium dihydrogen phosphate and
liquid water.
Q4.1.7
Colorful fireworks often involve the decomposition of barium nitrate and potassium chlorate and the reaction of the metals
magnesium, aluminum, and iron with oxygen.
a. Write the formulas of barium nitrate and potassium chlorate.
b. The decomposition of solid potassium chlorate leads to the formation of solid potassium chloride and diatomic oxygen gas. Write
an equation for the reaction.
c. The decomposition of solid barium nitrate leads to the formation of solid barium oxide, diatomic nitrogen gas, and diatomic
oxygen gas. Write an equation for the reaction.
d. Write separate equations for the reactions of the solid metals magnesium, aluminum, and iron with diatomic oxygen gas to yield
the corresponding metal oxides. (Assume the iron oxide contains Fe3+ ions.)
Q4.1.7
a. Ba(NO3)2, KClO3;
b. 2 KClO (s) → 2 KCl(s) + 3 O (g) ;
3 2
c. 2 Ba(NO ) (s) → 2 BaO(s) + 2 N (g) + 5 O (g) ;

3 2 2 2
d. 2 Mg(s) + O (g) → 2 MgO(s) ; 4 Al(s) + 3 O (g) → 2 Al

2 2 2
O (g)
3
; 4 Fe(s) + 3 O
2
(g) → 2 Fe O (s)
2 3
Q4.1.8
Fill in the blank with a single chemical formula for a covalent compound that will balance the equation:

Q4.1.9
Aqueous hydrogen fluoride (hydrofluoric acid) is used to etch glass and to analyze minerals for their silicon content. Hydrogen
fluoride will also react with sand (silicon dioxide).
a. Write an equation for the reaction of solid silicon dioxide with hydrofluoric acid to yield gaseous silicon tetrafluoride and liquid
water.
b. The mineral fluorite (calcium fluoride) occurs extensively in Illinois. Solid calcium fluoride can also be prepared by the reaction of
aqueous solutions of calcium chloride and sodium fluoride, yielding aqueous sodium chloride as the other product. Write complete
and net ionic equations for this reaction.
S4.1.9
a. 4 HF(aq) + SiO (s) → SiF (g) + 2 H O(l) ;
2 4 2
b. complete ionic equation: 2 Na (aq) + 2 F (aq) + Ca + − 2+

(aq) + 2 Cl
−
(aq) → CaF (s) + 2 Na
2
+
(aq) + 2 Cl
−
(aq) , net ionic
equation: 2 F (aq) + Ca (aq) → CaF (s)
− 2+
Q4.1.10
A novel process for obtaining magnesium from sea water involves several reactions. Write a balanced chemical equation for each step
of the process.
a. The first step is the decomposition of solid calcium carbonate from seashells to form solid calcium oxide and gaseous carbon
dioxide.
b. The second step is the formation of solid calcium hydroxide as the only product from the reaction of the solid calcium oxide with
liquid water.
c. Solid calcium hydroxide is then added to the seawater, reacting with dissolved magnesium chloride to yield solid magnesium
hydroxide and aqueous calcium chloride.
d. The solid magnesium hydroxide is added to a hydrochloric acid solution, producing dissolved magnesium chloride and liquid
water.
e. Finally, the magnesium chloride is melted and electrolyzed to yield liquid magnesium metal and diatomic chlorine gas.
Q4.1.11
From the balanced molecular equations, write the complete ionic and net ionic equations for the following:
a. K C O (aq) + Ba(OH) (aq) → 2 KOH(aq) + BaC O (s)
2 2 4 2 2 2
b. Pb(NO ) (aq) + H SO (aq) → PbSO (s) + 2 HNO (aq)

3 2 2 4 4 3
c. CaCO (s) + H SO (aq) → CaSO (s) + CO (g) + H O(l)

3 2 4 4 2 2
S4.1.11
a. 2K
+
(aq) + C O
2
2−
4
(aq) + Ba
2+
(aq) + 2 OH
−
(aq) → 2 K
+
(aq) + 2 OH
−
(aq) + BaC O (s)
2 4
(complete) (7.E.1)
2+ 2−
Ba (aq) + C O (aq) → BaC O (s) (net) (7.E.2)
2 4 2 4
b. Pb
2+
(aq) + 2 NO3 (aq) + 2 H
− +
(aq) + SO
2−
4
(aq) → PbSO (s) + 2 H
4
+
(aq) + 2 NO3 (aq)
−
(complete) (7.E.3)
2+ 2−
Pb (aq) + SO (aq) → PbSO (s) (net) (7.E.4)
4 4
c. CaCO (s) + 2 H
3
+
(aq) + SO
2−
4
(aq) → CaSO (s) + CO (g) + H O(l)
4 2 2
(complete) (7.E.5)
+ 2−
CaCO (s) + 2 H (aq) + SO 4 (aq) → CaSO (s) + CO (g) + H O(l) (net) (7.E.6)
3 4 2 2

Q4.2.1
Use the following equations to answer the next five questions:
i. H O(s) → H O(l)
2 2
ii. Na (aq) + Cl (aq)Ag (aq) + NO

+ − + −
3
(aq) → AgCl(s) + Na
+
(aq) + NO
−
3
(aq)
iii. CH OH(g) + O (g) → CO (g) + H

3 2 2 2
O(g)
iv. 2 H O(l) → 2 H (g) + O (g)

2 2 2
v. H (aq) + OH (aq) → H O(l)

+ −

a. Which equation describes a physical change?
b. Which equation identifies the reactants and products of a combustion reaction?
c. Which equation is not balanced?
d. Which is a net ionic equation?
S4.2.1
a.) i. H 2 O(solid) → H2 O(liquid)
b.) iii.
c.) iii. 2 CH 3
OH(g) + 3 O (g) → 2 CO (g) + 4 H O(g)
2 2 2
d.) v.
Q4.2.2
Indicate what type, or types, of reaction each of the following represents:
a. Ca(s) + Br (l) → CaBr (s) 2 2
b. Ca(OH) (aq) + 2 HBr(aq) → CaBr (aq) + 2 H

2 2 2
O(l)
c. C H (l) + 9 O (g) → 6 CO (g) + 6 H O(g)

6 12 2 2 2
S4.2.2
oxidation-reduction (addition); acid-base (neutralization); oxidation-reduction (combustion)
<
Q4.2.3
Indicate what type, or types, of reaction each of the following represents:
a. H O(g) + C(s) → CO(g) + H (g)
2 2
b. 2 KClO (s) → 2 KCl(s) + 3 O (g)

3 2
c. Al(OH) (aq) + 3 HCl(aq) → AlBr (aq) + 3 H O(l)

3 3 2
d. Pb(NO ) (aq) + H SO (aq) → PbSO (s) + 2 HNO

3 2 2 4 4 3
(aq)
Q4.2.4
Silver can be separated from gold because silver dissolves in nitric acid while gold does not. Is the dissolution of silver in nitric acid
an acid-base reaction or an oxidation-reduction reaction? Explain your answer.
S4.2.4
It is an oxidation-reduction reaction because the oxidation state of the silver changes during the reaction.
Q4.2.5
Determine the oxidation states of the elements in the following compounds:
a. NaI
b. GdCl3
c. LiNO3
d. H2Se
e. Mg2Si
f. RbO2, rubidium superoxide
g. HF
Q4.2.6
Determine the oxidation states of the elements in the compounds listed. None of the oxygen-containing compounds are peroxides or
superoxides.
a. H3PO4
b. Al(OH)3
c. SeO2
d. KNO2

e. In2S3
f. P4O6
S4.2.6
H +1, P +5, O −2; Al +3, H +1, O −2; Se +4, O −2; K +1, N +3, O −2; In +3, S −2; P +3, O −2
Q4.2.7
Determine the oxidation states of the elements in the compounds listed. None of the oxygen-containing compounds are peroxides or
superoxides.
a. H2SO4
b. Ca(OH)2
c. BrOH
d. ClNO2
e. TiCl4
f. NaH
S4.2.7
a. H1+, O2-, S6+
b. H1+, O2-, Ca+2
c. H1+, O2-, Br1+
d. O2-, Cl1-, N5+
e. Cl1-, Ti4+
f. H1+, Na1-
Q4.2.8
Classify the following as acid-base reactions or oxidation-reduction reactions:
a. Na S(aq) + 2 HCl(aq) → 2 NaCl(aq) + H S(g)
2 2
b. 2 Na(s) + 2 HCl(aq) → 2 NaCl(aq) + H (g) 2
c. Mg(s) + Cl (g) → MgCl (s)2 2
d. MgO(s) + 2 HCl(aq) → MgCl (aq) + H O(l) 2 2
e. K P(s) + 2 O (g) → K PO (s)

3 2 3 4
f. 3 KOH(aq) + H PO (aq) → K PO (aq) + 3 H 3 4 3 4 2

O(l)
S4.2.9
acid-base; oxidation-reduction: Na is oxidized, H+ is reduced; oxidation-reduction: Mg is oxidized, Cl2 is reduced; acid-base;
oxidation-reduction: P3− is oxidized, O2 is reduced; acid-base
Q4.2.10
Identify the atoms that are oxidized and reduced, the change in oxidation state for each, and the oxidizing and reducing agents in each
of the following equations:
a. Mg(s) + NiCl (aq) → MgCl (aq) + Ni(s)
2 2
b. PCl (l) + Cl (g) → PCl (s)

3 2 5
c. C H (g) + 3 O (g) → 2 CO (g) + 2 H O(g)

2 4 2 2 2
d. Zn(s) + H SO (aq) → ZnSO (aq) + H (g)

2 4 4 2
e. 2 K S O (s) + I (s) → K S O (s) + 2 KI(s)

2 2 3 2 2 4 6
f. 3 Cu(s) + 8 HNO (aq) → 3 Cu(NO ) (aq) + 2 NO(g) + 4 H

3 3 2 2
O(l)
Q4.2.11
Complete and balance the following acid-base equations:
a. HCl gas reacts with solid Ca(OH)2(s).
b. A solution of Sr(OH)2 is added to a solution of HNO3.

S4.2.11
a. 2 HCl(g) + Ca(OH) (s) → CaCl (s) + 2 H O(l) ;
2 2 2
b. Sr(OH) (aq) + 2 HNO (aq) → Sr(NO ) (aq) + 2 H

2 3 3 2 2
O(l)
Q4.2.12
Complete and balance the following acid-base equations:
a. A solution of HClO4 is added to a solution of LiOH.
b. Aqueous H2SO4 reacts with NaOH.
c. Ba(OH)2 reacts with HF gas.
Q4.2.13
Complete and balance the following oxidation-reduction reactions, which give the highest possible oxidation state for the oxidized
atoms.
a. Al(s) + F (g) →
2
b. Al(s) + CuBr (aq) → (single displacement)

2
c. P (s) + O (g) →
4 2
d. Ca(s) + H O(l) → (products are a strong base and a diatomic gas)

2
S4.2.13
a. 2 Al(s) + 3 F (g) → 2 AlF (s) ;
2 3
b. 2 Al(s) + 3 CuBr (aq) → 3 Cu(s) + 2 AlBr

2 3
(aq) ;
c. P (s) + 5 O (g) → P O (s) ; Ca(s) + 2 H
4 2 4 10 2
O(l) → Ca (OH) (aq) + H (g)
2 2
Q4.2.14
Complete and balance the following oxidation-reduction reactions, which give the highest possible oxidation state for the oxidized
atoms.
a. K(s) + H O(l) →
2
b. Ba(s) + HBr(aq) →
c. Sn(s) + I (s) →
2
Q4.2.15
Complete and balance the equations for the following acid-base neutralization reactions. If water is used as a solvent, write the
reactants and products as aqueous ions. In some cases, there may be more than one correct answer, depending on the amounts of
reactants used.
a. Mg(OH) (s) + HClO (aq) →
2 4
b. SO (g) + H O(l) → (assume an excess of water and that the product dissolves)
3 2
c. SrO(s) + H SO (l) → 2 4
S4.2.15
a. Mg(OH) (s) + 2 HClO (aq) → Mg (aq) + 2 ClO (aq) + 2 H O(l) ;
2 4
2+ −
4 2
b. SO (g) + 2 H O(l) → H O (aq) + HSO (aq) , (a solution of H2SO4);

3 2 3
+ −
4
c. SrO(s) + H SO (l) → SrSO (s) + H O

2 4 4 2
Q4.2.16
When heated to 700–800 °C, diamonds, which are pure carbon, are oxidized by atmospheric oxygen. (They burn!) Write the balanced
equation for this reaction.
Q4.2.17
The military has experimented with lasers that produce very intense light when fluorine combines explosively with hydrogen. What is
the balanced equation for this reaction?

S4.2.17
H (g) + F (g) → 2 HF(g)
2 2
Q4.2.18
Write the molecular, total ionic, and net ionic equations for the following reactions:
a. Ca(OH) (aq) + HC H O (aq) →
2 2 3 2
b. H PO (aq) + CaCl (aq) →

3 4 2
Q4.2.19
Great Lakes Chemical Company produces bromine, Br2, from bromide salts such as NaBr, in Arkansas brine by treating the brine with
chlorine gas. Write a balanced equation for the reaction of NaBr with Cl2.
S4.2.19
2 NaBr(aq) + Cl (g) → 2 NaCl(aq) + Br (l)
2 2
Q4.2.20
In a common experiment in the general chemistry laboratory, magnesium metal is heated in air to produce MgO. MgO is a white solid,
but in these experiments it often looks gray, due to small amounts of Mg3N2, a compound formed as some of the magnesium reacts
with nitrogen. Write a balanced equation for each reaction.
Q4.2.21
Lithium hydroxide may be used to absorb carbon dioxide in enclosed environments, such as manned spacecraft and submarines. Write
an equation for the reaction that involves 2 mol of LiOH per 1 mol of CO2. (Hint: Water is one of the products.)
S4.2.21
2 LiOH(aq) + CO (g) → Li CO (aq) + H O(l)
2 2 3 2
Q4.2.22
Calcium propionate is sometimes added to bread to retard spoilage. This compound can be prepared by the reaction of calcium
carbonate, CaCO3, with propionic acid, C2H5CO2H, which has properties similar to those of acetic acid. Write the balanced equation
for the formation of calcium propionate.
Q4.2.23
Complete and balance the equations of the following reactions, each of which could be used to remove hydrogen sulfide from natural
gas:
a. Ca(OH) (s) + H 2 2
S(g) →
b. Na CO (aq) + H
2 3 2
S(g) →
S4.2.23
a. Ca(OH) (s) + H 2 2
S(g) → CaS(s) + 2 H O(l)
2
;
b. Na CO (aq) + H
2 3 2
S(g) → Na S(aq) + CO (g) + H O(l)
2 2 2
Q4.2.24
Copper(II) sulfide is oxidized by molecular oxygen to produce gaseous sulfur trioxide and solid copper(II) oxide. The gaseous product
then reacts with liquid water to produce liquid hydrogen sulfate as the only product. Write the two equations which represent these
reactions.
Q4.2.25
Write balanced chemical equations for the reactions used to prepare each of the following compounds from the given starting
material(s). In some cases, additional reactants may be required.
a. solid ammonium nitrate from gaseous molecular nitrogen via a two-step process (first reduce the nitrogen to ammonia, then
neutralize the ammonia with an appropriate acid)
b. gaseous hydrogen bromide from liquid molecular bromine via a one-step redox reaction

c. gaseous H2S from solid Zn and S via a two-step process (first a redox reaction between the starting materials, then reaction of the
product with a strong acid)
S4.2.25
a. step 1: N (g) + 3 H (g) → 2 NH (g) , step 2: NH (g) + HNO (aq) → NH
2 2 3 3 3 4
NO (aq) → NH NO (s)(after drying)
3 4 3
;
b. H (g) + Br (l) → 2 HBr(g) ;
2 2
c. Zn(s) + S(s) → ZnS(s) and ZnS(s) + 2 HCl(aq) → ZnCl (aq) + H S(g) 2 2
Q4.2.26
Calcium cyclamate Ca(C6H11NHSO3)2 is an artificial sweetener used in many countries around the world but is banned in the United
States. It can be purified industrially by converting it to the barium salt through reaction of the acid C6H11NHSO3H with barium
carbonate, treatment with sulfuric acid (barium sulfate is very insoluble), and then neutralization with calcium hydroxide. Write the
balanced equations for these reactions.
Q4.2.27
Complete and balance each of the following half-reactions (steps 2–5 in half-reaction method):
a. Sn (aq) → Sn (aq)
4+ 2+
+
b. [Ag(NH ) ] (aq) → Ag(s) + NH (aq)
3 2 3
c. Hg Cl (s) → Hg(l) + Cl (aq)

2 2
−
d. H O(l) → O (g) (in acidic solution)

2 2
e. IO (aq) → I (s)
−
3 2
f. SO (aq) → SO (aq) (in acidic solution)

2−
3
2−
4
g. MnO (aq) → Mn (aq) (in acidic solution)

−
4
2+
h. Cl (aq) → ClO (aq) (in basic solution)

− −
3
S4.2.27
a. Sn (aq) + 2 e → Sn (aq) ,
4+ − 2+
b. [Ag(NH ) ] (aq) + e → Ag(s) + 2 NH (aq) ;

3 2
+ −
3
c. Hg Cl (s) + 2 e → 2 Hg(l) + 2 Cl (aq) ;

2 2
− −
d. 2 H O(l) → O (g) + 4 H (aq) + 4 e ;

2 2
+ −
e. 6 H O(l) + 2 IO (aq) + 10 e → I (s) + 12 OH (aq) ;

2
−
3
−
2
−
f. H O(l) + SO (aq) → SO (aq) + 2 H (aq) + 2 e ;

2
2−
3
2−
4
+ −
g. (g) 8 H (aq) + MnO (aq) + 5 e → Mn (aq) + 4 H O(l) ;

+ −
4
− 2+
h. (h) Cl (aq) + 6 OH (aq) → ClO (aq) + 3 H O(l) + 6 e

− − −
3 2
−
Q4.2.28
Complete and balance each of the following half-reactions (steps 2–5 in half-reaction method):
a. Cr (aq) → Cr (aq)
2+ 3+
b. Hg(l) + Br (aq) → HgBr (aq)

− 2−
4
c. ZnS(s) → Zn(s) + S (aq) 2−
d. H (g) → H O(l) (in basic solution)

2 2
e. H (g) → H O (aq) (in acidic solution)

2 3
+
f. NO (aq) → HNO (aq) (in acidic solution)

−
3 2
g. MnO (s) → MnO (aq) (in basic solution)

2
−
h. Cl (aq) → ClO (aq) (in acidic solution)

− −
3
Q4.2.29
Balance each of the following equations according to the half-reaction method:
a. Sn (aq) + Cu (aq) → Sn (aq) + Cu (aq)
2+ 2+ 4+ +
b. H S(g) + Hg (aq) → Hg(l) + S(s) (in acid)

2
2+
2
c. CN (aq) + ClO (aq) → CNO (aq) + Cl (aq) (in acid)

−
2
− −
d. Fe (aq) + Ce (aq) → Fe (aq) + Ce (aq)

2+ 4+ 3+ 3+
e. HBrO(aq) → Br (aq) + O (g) (in acid) −

2

S4.2.29
a. Sn (aq) + 2 Cu (aq) → Sn (aq) + 2 Cu (aq) ;
2+ 2+ 4+ +
b. H S(g) + Hg (aq) + 2 H O(l) → 2 Hg(l) + S(s) + 2 H O (aq) ;

2
2+
2 2 3
+
c. 5 CN (aq) + 2 ClO (aq) + 3 H O(l) → 5 CNO (aq) + 2 Cl (aq) + 2 H

−
2 2
− −
3
O
+
(aq) ;
d. Fe (aq) + Ce (aq) → Fe (aq) + Ce (aq) ;
2+ 4+ 3+ 3+
e. 2 HBrO(aq) + 2 H O(l) → 2 H O (aq) + 2 Br (aq) + O (g)

2 3
+ −
2
Q4.2.30
a. Zn(s) + NO (aq) → Zn (aq) + N (g) (in acid)
−
3
2+
b. Zn(s) + NO (aq) → Zn (aq) + NH (aq) (in base)

−
3
2+
3
c. CuS(s) + NO (aq) → Cu (aq) + S(s) + NO(g) (in acid)

−
3
2+
d. NH (aq) + O (g) → NO (g) (gas phase)

3 2 2
e. Cl (g) + OH (aq) → Cl (aq) + ClO (aq) (in base)

2
− − −
f. H O (aq) + MnO (aq) → Mn (aq) + O (g) (in acid)

2 2
−
4
2+
2
g. NO (g) → NO (aq) + NO (aq) (in base)

2
−
3
−
2
h. Fe (aq) + I (aq) → Fe (aq) + I (aq)

3+ − 2+
Q4.2.31
a. MnO (aq) + NO (aq) → MnO (s) + NO (aq) (in base)
−
4
−
2 2
−
b. MnO (aq) → MnO (aq) + MnO (s) (in base)

2−
4
−
4 2
c. Br (l) + SO (g) → Br (aq) + SO (aq) (in acid)

2 2
− 2−
4
S4.2.31
a. 2 MnO (aq) + 3 NO (aq) + H O(l) → 2 MnO (s) + 3 NO (aq) + 2 OH (aq) ;
−
4
−
2 2 2
−
3
−
b. 3 MnO (aq) + 2 H O(l) → 2 MnO (aq) + 4 OH (aq) + MnO (s) (in base) ;
2−
4 2
−
4
−
2
c. Br (l) + SO (g) + 2 H O(l) → 4 H (aq) + 2 Br (aq) + SO (aq)

2 2 2
+ − 2−

Q4.3.1
Write the balanced equation, then outline the steps necessary to determine the information requested in each of the following:
a. The number of moles and the mass of chlorine, Cl2, required to react with 10.0 g of sodium metal, Na, to produce sodium chloride,
NaCl.
b. The number of moles and the mass of oxygen formed by the decomposition of 1.252 g of mercury(II) oxide.
c. The number of moles and the mass of sodium nitrate, NaNO3, required to produce 128 g of oxygen. (NaNO2 is the other product.)
d. The number of moles and the mass of carbon dioxide formed by the combustion of 20.0 kg of carbon in an excess of oxygen.
e. The number of moles and the mass of copper(II) carbonate needed to produce 1.500 kg of copper(II) oxide. (CO2 is the other
product.)
f.
Q4.3.2
Determine the number of moles and the mass requested for each reaction in Exercise.
S4.3.2
0.435 mol Na, 0.217 mol Cl2, 15.4 g Cl2; 0.005780 mol HgO, 2.890 × 10−3 mol O2, 9.248 × 10−2 g O2; 8.00 mol NaNO3, 6.8 × 102 g
NaNO3; 1665 mol CO2, 73.3 kg CO2; 18.86 mol CuO, 2.330 kg CuCO3; 0.4580 mol C2H4Br2, 86.05 g C2H4Br2

Q4.3.3
Write the balanced equation, then outline the steps necessary to determine the information requested in each of the following:
a. The number of moles and the mass of Mg required to react with 5.00 g of HCl and produce MgCl2 and H2.
b. The number of moles and the mass of oxygen formed by the decomposition of 1.252 g of silver(I) oxide.
c. The number of moles and the mass of magnesium carbonate, MgCO3, required to produce 283 g of carbon dioxide. (MgO is the
other product.)
d. The number of moles and the mass of water formed by the combustion of 20.0 kg of acetylene, C2H2, in an excess of oxygen.
e. The number of moles and the mass of barium peroxide, BaO2, needed to produce 2.500 kg of barium oxide, BaO (O2 is the other
product.)
This figure includes two structural formulas. It reads, “The number of moles and the mass of,” which is followed by a structure with two C atoms connected with a horizontal double bond at the center. The C atom to
the left has H atoms bonded above and to the left and below and to the left. The C atom to the right has H atoms bonded above and to the right and below and to the right. Following this structure, the figure reads,
“required to react with H subscript 2 O to produce 9.55 g of,” which is followed by a structure with two C atoms connected with a horizontal single bond. The C atom to the left has H atoms bonded above, to the left,
f. and below. The C atom to the right has H atoms bonded above and below. To the right, an O atom forms a single bond with the C atom. A single H atom is bonded to the right side of the O atom.
Q4.3.4
Determine the number of moles and the mass requested for each reaction in Exercise.
S4.3.4
0.0686 mol Mg, 1.67 g Mg; 2.701 × 10−3 mol O2, 0.08644 g O2; 6.43 mol MgCO3, 542 g MgCO3 713 mol H2O, 12.8 kg H2O; 16.31
mol BaO2, 2762 g BaO2; 0.207 mol C2H4, 5.81 g C2H4
Q4.3.5
H2 is produced by the reaction of 118.5 mL of a 0.8775-M solution of H3PO4 according to the following equation:
2 Cr + 2 H PO → 3 H + 2 CrPO .
3 4 2 4
a. Outline the steps necessary to determine the number of moles and mass of H2.
b. Perform the calculations outlined.
S4.3.5
a.)
1. Convert mL to L
2. Multiply L by the molarity to determine moles of H3PO4
3. Convert moles of H3PO4 to moles of H2
4. Multiply moles of H2 by the molar mass of H2 to get the answer in grams
b.)
1 L
1. 118.5 mL × = 0.1185 L
1000 mL
0.8775 moles H PO
3 4
2. 0.1185 L × = 0.1040 moles H PO
3 4
1 L
3 moles H
3. 0.1040 moles H 3
PO
4
×
2
= 0.1560 moles H
2
2 moles H PO
3 4
2.02g
4. 0.1560 moles H 2
× = 0.3151g H
2
1 mole
Q4.3.6
Gallium chloride is formed by the reaction of 2.6 L of a 1.44 M solution of HCl according to the following equation:
2 Ga + 6 HCl → 2 GaCl + 3 H .
3 2
a. Outline the steps necessary to determine the number of moles and mass of gallium chloride.
b. Perform the calculations outlined.
S4.3.6
volume HCl solution → mol HCl → mol GaCl3 ; 1.25 mol GaCl3, 2.2 × 102 g GaCl3

Q4.3.7
I2 is produced by the reaction of 0.4235 mol of CuCl2 according to the following equation: 2 CuCl 2
+ 4 KI → 2 CuI + 4 KCl + I
2
.
a. How many molecules of I2 are produced?
b. What mass of I2 is produced?
Q4.3.8
Silver is often extracted from ores as K[Ag(CN)2] and then recovered by the reaction
2 K[Ag (CN) ](aq) + Zn(s) → 2 Ag(s) + Zn(CN) (aq) + 2 KCN(aq)
2 2
a. How many molecules of Zn(CN)2 are produced by the reaction of 35.27 g of K[Ag(CN)2]?
b. What mass of Zn(CN)2 is produced?
S4.3.8
5.337 × 1022 molecules; 10.41 g Zn(CN)2
Q4.3.9
What mass of silver oxide, Ag2O, is required to produce 25.0 g of silver sulfadiazine, AgC10H9N4SO2, from the reaction of silver
oxide and sulfadiazine?
2C H N SO + Ag O → 2 AgC H N SO +H O
10 10 4 2 2 10 9 4 2 2
Q4.3.10
Carborundum is silicon carbide, SiC, a very hard material used as an abrasive on sandpaper and in other applications. It is prepared by
the reaction of pure sand, SiO2, with carbon at high temperature. Carbon monoxide, CO, is the other product of this reaction. Write the
balanced equation for the reaction, and calculate how much SiO2 is required to produce 3.00 kg of SiC.
S4.3.10
SiO
2
+ 3 C → SiC + 2 CO , 4.50 kg SiO2
Q4.3.11
Automotive air bags inflate when a sample of sodium azide, NaN3, is very rapidly decomposed.
2 NaN (s) → 2 Na(s) + 3 N (g)
3 2
What mass of sodium azide is required to produce 2.6 ft3 (73.6 L) of nitrogen gas with a density of 1.25 g/L?
S4.3.11
142g NaN3
Q4.3.12
Urea, CO(NH2)2, is manufactured on a large scale for use in producing urea-formaldehyde plastics and as a fertilizer. What is the
maximum mass of urea that can be manufactured from the CO2 produced by combustion of 1.00×103 kg of carbon followed by the
reaction?
CO (g) + 2 NH (g) → CO(NH ) (s) + H O(l) (7.E.7)
2 3 2 2 2
S4.3.12
5.00 × 103 kg
Q4.3.13
In an accident, a solution containing 2.5 kg of nitric acid was spilled. Two kilograms of Na2CO3 was quickly spread on the area and
CO2 was released by the reaction. Was sufficient Na2CO3 used to neutralize all of the acid?
Q4.3.14
A compact car gets 37.5 miles per gallon on the highway. If gasoline contains 84.2% carbon by mass and has a density of 0.8205
g/mL, determine the mass of carbon dioxide produced during a 500-mile trip (3.785 liters per gallon).

S4.3.14
1.28 × 105 g CO2
Q4.3.15
What volume of a 0.750 M solution of hydrochloric acid, a solution of HCl, can be prepared from the HCl produced by the reaction of
25.0 g of NaCl with an excess of sulfuric acid?
NaCl(s) + H SO (l) → HCl(g) + NaHSO (s) (7.E.8)

2 4 4
Q4.3.16
What volume of a 0.2089 M KI solution contains enough KI to react exactly with the Cu(NO3)2 in 43.88 mL of a 0.3842 M solution of
Cu(NO3)2?
2 Cu(NO ) + 4 KI → 2 CuI + I + 4 KNO (7.E.9)
3 2 2 3
S4.3.16
161.40 mL KI solution
Q4.3.17
A mordant is a substance that combines with a dye to produce a stable fixed color in a dyed fabric. Calcium acetate is used as a
mordant. It is prepared by the reaction of acetic acid with calcium hydroxide.
2 CH CO H + Ca (OH) → Ca (CH CO ) +2 H O (7.E.10)

3 2 2 3 2 2 2
What mass of Ca(OH)2 is required to react with the acetic acid in 25.0 mL of a solution having a density of 1.065 g/mL and containing
58.0% acetic acid by mass?
Q4.3.18
The toxic pigment called white lead, Pb3(OH)2(CO3)2, has been replaced in white paints by rutile, TiO2. How much rutile (g) can be
prepared from 379 g of an ore that contains 88.3% ilmenite (FeTiO3) by mass?
2 FeTiO + 4 HCl + Cl → 2 FeCl + 2 TiO +2 H O (7.E.11)
3 2 3 2 2
S4.3.18
176 g TiO2

Q4.4.1
The following quantities are placed in a container: 1.5 × 1024 atoms of hydrogen, 1.0 mol of sulfur, and 88.0 g of diatomic oxygen.
a. What is the total mass in grams for the collection of all three elements?
b. What is the total number of moles of atoms for the three elements?
c. If the mixture of the three elements formed a compound with molecules that contain two hydrogen atoms, one sulfur atom, and
four oxygen atoms, which substance is consumed first?
d. How many atoms of each remaining element would remain unreacted in the change described in ?
Q4.4.2
What is the limiting reactant in a reaction that produces sodium chloride from 8 g of sodium and 8 g of diatomic chlorine?
S4.4.2
The limiting reactant is Cl2.
Q4.4.3
Which of the postulates of Dalton's atomic theory explains why we can calculate a theoretical yield for a chemical reaction?

Q4.4.4
A student isolated 25 g of a compound following a procedure that would theoretically yield 81 g. What was his percent yield?
S4.4.4
Percent yield = 31%
Q4.4.5
A sample of 0.53 g of carbon dioxide was obtained by heating 1.31 g of calcium carbonate. What is the percent yield for this reaction?
CaCO (s) → CaO(s) + CO (s) (7.E.12)
3 2
Q4.4.6
Freon-12, CCl2F2, is prepared from CCl4 by reaction with HF. The other product of this reaction is HCl. Outline the steps needed to
determine the percent yield of a reaction that produces 12.5 g of CCl2F2 from 32.9 g of CCl4. Freon-12 has been banned and is no
longer used as a refrigerant because it catalyzes the decomposition of ozone and has a very long lifetime in the atmosphere. Determine
the percent yield.
S4.4.6
g CCl → mol CCl → mol CCl F → g CCl F , percent yield = 48.3%
4 4 2 2 2 2
Q4.4.7
Citric acid, C6H8O7, a component of jams, jellies, and fruity soft drinks, is prepared industrially via fermentation of sucrose by the
mold Aspergillus niger. The equation representing this reaction is
C H O +H O+3 O → 2C H O +4 H O (7.E.13)
12 22 11 2 2 6 8 7 2
3
What mass of citric acid is produced from exactly 1 metric ton (1.000 × 10 kg) of sucrose if the yield is 92.30%?
Q4.4.8
Toluene, C6H5CH3, is oxidized by air under carefully controlled conditions to benzoic acid, C6H5CO2H, which is used to prepare the
food preservative sodium benzoate, C6H5CO2Na. What is the percent yield of a reaction that converts 1.000 kg of toluene to 1.21 kg
of benzoic acid?
2 C H CH +3 O → 2 C H CO H + 2 H O (7.E.14)
6 5 3 2 6 5 2 2
S4.4.8
percent yield = 91.3%
Q4.4.9
In a laboratory experiment, the reaction of 3.0 mol of H2 with 2.0 mol of I2 produced 1.0 mol of HI. Determine the theoretical yield in
grams and the percent yield for this reaction.
Q4.4.10
Outline the steps needed to solve the following problem, then do the calculations. Ether, (C2H5)2O, which was originally used as an
anesthetic but has been replaced by safer and more effective medications, is prepared by the reaction of ethanol with sulfuric acid.
2C2H5OH + H2SO4 ⟶ (C2H5)2 + H2SO4·H2O
Q4.4.11
What is the percent yield of ether if 1.17 L (d = 0.7134 g/mL) is isolated from the reaction of 1.500 L of C2H5OH (d = 0.7894 g/mL)?
S4.4.11
Convert mass of ethanol to moles of ethanol; relate the moles of ethanol to the moles of ether produced using the stoichiometry of the
balanced equation. Convert moles of ether to grams; divide the actual grams of ether (determined through the density) by the
theoretical mass to determine the percent yield; 87.6%

Q4.4.12
Outline the steps needed to determine the limiting reactant when 30.0 g of propane, C3H8, is burned with 75.0 g of oxygen.
0.8347 g
percent yield = × 100% = 87.6% (7.E.15)
0.9525 g
Determine the limiting reactant.
Q4.4.13
Outline the steps needed to determine the limiting reactant when 0.50 g of Cr and 0.75 g of H3PO4 react according to the following
chemical equation?
2 Cr + 2 H PO → 2 CrPO +3 H (7.E.16)
3 4 4 2
Determine the limiting reactant.
S4.4.13
The conversion needed is mol Cr → mol H PO
2 4
. Then compare the amount of Cr to the amount of acid present. Cr is the limiting
reactant.
Q4.4.14
What is the limiting reactant when 1.50 g of lithium and 1.50 g of nitrogen combine to form lithium nitride, a component of advanced
batteries, according to the following unbalanced equation?
Li + N → Li N (7.E.17)
2 3
S4.4.14
6 Li + N → 2 Li N (7.E.18)
2 3
1 mole Li 2 mole Li N
3
1.50g Li × × = 0.0720 moles Li N (7.E.19)
3
6.94g Li 6 mole Li
1 mole N 2 mole Li N
2 3
1.50g N × × = 0.107 moles Li N (7.E.20)
2 3
28.02g N 1 mole N
2 2
Li is the limiting reactant
Q4.4.15
Uranium can be isolated from its ores by dissolving it as UO2(NO3)2, then separating it as solid UO2(C2O4)·3H2O. Addition of 0.4031
g of sodium oxalate, Na2C2O4, to a solution containing 1.481 g of uranyl nitrate, UO2(NO2)2, yields 1.073 g of solid
UO2(C2O4)·3H2O.
Na C O + UO (NO ) + 3 H O ⟶ UO (C O ) ⋅ 3 H O + 2 NaNO (7.E.21)

2 2 4 2 3 2 2 2 2 4 2 3
Determine the limiting reactant and the percent yield of this reaction.
S4.4.15
Na2C2O4 is the limiting reactant. percent yield = 86.6%
Q4.4.16
How many molecules of C2H4Cl2 can be prepared from 15 C2H4 molecules and 8 Cl2 molecules?
Q4.4.17
How many molecules of the sweetener saccharin can be prepared from 30 C atoms, 25 H atoms, 12 O atoms, 8 S atoms, and 14 N
atoms?

S4.4.17
Only four molecules can be made.
Q4.4.18
The phosphorus pentoxide used to produce phosphoric acid for cola soft drinks is prepared by burning phosphorus in oxygen.
a. What is the limiting reactant when 0.200 mol of P4 and 0.200 mol of O2 react according to
P +5 O → P O (7.E.22)
4 2 4 10
b. Calculate the percent yield if 10.0 g of P4O10 is isolated from the reaction.
Q4.4.19
Would you agree to buy 1 trillion (1,000,000,000,000) gold atoms for $5? Explain why or why not. Find the current price of gold at
http://money.cnn.com/data/commodities/ (1 troy ounce = 31.1 g)
S4.4.19
This amount cannot be weighted by ordinary balances and is worthless.

Q4.5.1
What volume of 0.0105-M HBr solution is be required to titrate 125 mL of a 0.0100-M Ca(OH)2 solution?
Ca (OH) (aq) + 2 HBr(aq) → CaBr (aq) + 2 H O(l) (7.E.23)
2 2 2
Q4.5.2
Titration of a 20.0-mL sample of acid rain required 1.7 mL of 0.0811 M NaOH to reach the end point. If we assume that the acidity of
the rain is due to the presence of sulfuric acid, what was the concentration of sulfuric acid in this sample of rain?
S4.5.2
3.4 × 10−3 M H2SO4
Q4.5.3
What is the concentration of NaCl in a solution if titration of 15.00 mL of the solution with 0.2503 M AgNO3 requires 20.22 mL of the
AgNO3 solution to reach the end point?
AgNO (aq) + NaCl(aq) → AgCl(s) + NaNO (aq) (7.E.24)
3 3
Q4.5.4
In a common medical laboratory determination of the concentration of free chloride ion in blood serum, a serum sample is titrated
with a Hg(NO3)2 solution.
− −
2 Cl (aq) + Hg (NO ) (aq) → 2 NO3 (aq) + HgCl (s) (7.E.25)
3 2 2
What is the Cl− concentration in a 0.25-mL sample of normal serum that requires 1.46 mL of 5.25 × 10−4 M Hg(NO3)2(aq) to reach
the end point?
S4.5.4
9.6 × 10−3 M Cl−

Q4.5.5
Potatoes can be peeled commercially by soaking them in a 3-M to 6-M solution of sodium hydroxide, then removing the loosened
skins by spraying them with water. Does a sodium hydroxide solution have a suitable concentration if titration of 12.00 mL of the
solution requires 30.6 mL of 1.65 M HCI to reach the end point?
Q4.5.6
A sample of gallium bromide, GaBr2, weighing 0.165 g was dissolved in water and treated with silver nitrate, AgNO3, resulting in the
precipitation of 0.299 g AgBr. Use these data to compute the %Ga (by mass) GaBr2.
S4.5.6
22.4%
Q4.5.7
The principal component of mothballs is naphthalene, a compound with a molecular mass of about 130 amu, containing only carbon
and hydrogen. A 3.000-mg sample of naphthalene burns to give 10.3 mg of CO2. Determine its empirical and molecular formulas.
Q4.5.8
A 0.025-g sample of a compound composed of boron and hydrogen, with a molecular mass of ~28 amu, burns spontaneously when
exposed to air, producing 0.063 g of B2O3. What are the empirical and molecular formulas of the compound.
S4.5.8
The empirical formula is BH3. The molecular formula is B2H6.
Q4.5.9
Sodium bicarbonate (baking soda), NaHCO3, can be purified by dissolving it in hot water (60 °C), filtering to remove insoluble
impurities, cooling to 0 °C to precipitate solid NaHCO3, and then filtering to remove the solid, leaving soluble impurities in solution.
Any NaHCO3 that remains in solution is not recovered. The solubility of NaHCO3 in hot water of 60 °C is 164 g L. Its solubility in
cold water of 0 °C is 69 g/L. What is the percent yield of NaHCO3 when it is purified by this method?
Q4.5.10
What volume of 0.600 M HCl is required to react completely with 2.50 g of sodium hydrogen carbonate?
NaHCO (aq) + HCl(aq) → NaCl(aq) + CO (g) + H O(l) (7.E.26)
3 2 2
S4.5.10
49.6 mL
Q4.5.11
What volume of 0.08892 M HNO3 is required to react completely with 0.2352 g of potassium hydrogen phosphate?
2 HNO (aq) + K HPO (aq) → H PO (aq) + 2 KNO (aq) (7.E.27)

3 2 4 2 4 3
Q4.5.12
What volume of a 0.3300-M solution of sodium hydroxide would be required to titrate 15.00 mL of 0.1500 M oxalic acid?
C O H (aq) + 2 NaOH(aq) → Na C O (aq) + 2 H O(l) (7.E.28)
2 4 2 2 2 4 2
S4.5.12
13.64 mL
Q4.5.13
What volume of a 0.00945-M solution of potassium hydroxide would be required to titrate 50.00 mL of a sample of acid rain with a
H2SO4 concentration of 1.23 × 10−4 M.
H SO (aq) + 2 KOH(aq) → K SO (aq) + 2 H O(l) (7.E.29)
2 4 2 4 2

S4.5.13
1.30 mL
Q4.5.14
A sample of solid calcium hydroxide, Ca(OH)2, is allowed to stand in water until a saturated solution is formed. A titration of 75.00
mL of this solution with 5.00 × 10−2 M HCl requires 36.6 mL of the acid to reach the end point.
Ca (OH) (aq) + 2 HCl(aq) → CaCl (aq) + 2 H O(l) (7.E.30)

2 2 2
What is the molarity?
S4.5.14
1.22 M
Q4.5.15
What mass of Ca(OH)2 will react with 25.0 g of propionic acid to form the preservative calcium propionate according to the equation?
Q4.5.16
How many milliliters of a 0.1500-M solution of KOH will be required to titrate 40.00 mL of a 0.0656-M solution of H3PO4?
H PO (aq) + 2 KOH(aq) → K HPO (aq) + 2 H O(l) (7.E.31)
3 4 2 4 2
S4.5.16
34.99 mL KOH
Q4.5.17
Potassium acid phthalate, KHC6H4O4, or KHP, is used in many laboratories, including general chemistry laboratories, to standardize
solutions of base. KHP is one of only a few stable solid acids that can be dried by warming and weighed. A 0.3420-g sample of
KHC6H4O4 reacts with 35.73 mL of a NaOH solution in a titration. What is the molar concentration of the NaOH?
KHC H O (aq) + NaOH(aq) → KNaC H O (aq) + H O(aq) (7.E.32)

6 4 4 6 4 4 2
Q4.5.18
The reaction of WCl6 with Al at ~400 °C gives black crystals of a compound containing only tungsten and chlorine. A sample of this
compound, when reduced with hydrogen, gives 0.2232 g of tungsten metal and hydrogen chloride, which is absorbed in water.
Titration of the hydrochloric acid thus produced requires 46.2 mL of 0.1051 M NaOH to reach the end point. What is the empirical
formula of the black tungsten chloride?
S4.5.19
The empirical formula is WCl4.
This page titled 7.E: Stoichiometry of Chemical Reactions (Exercises) is shared under a CC BY license and was authored, remixed, and/or curated by
OpenStax.

CHAPTER OVERVIEW
8: Gases

General Chemistry
In this chapter, we examine the relationships between gas temperature, pressure, amount, and volume. We will study a simple
theoretical model and use it to analyze the experimental behavior of gases. The results of these analyses will show us the
limitations of the theory and how to improve on it.
8.1: Gas Pressure
Contributors
[email protected]).
This page titled 8: Gases is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
1
8.1: Gas Pressure
Define the property of pressure
Define and convert among the units of pressure measurements
Describe the operation of common tools for measuring gas pressure
Calculate pressure from manometer data
The earth’s atmosphere exerts a pressure, as does any other gas. Although we do not normally notice atmospheric pressure, we are
sensitive to pressure changes—for example, when your ears “pop” during take-off and landing while flying, or when you dive
underwater. Gas pressure is caused by the force exerted by gas molecules colliding with the surfaces of objects (Figure 8.1.1).
Although the force of each collision is very small, any surface of appreciable area experiences a large number of collisions in a
short time, which can result in a high pressure. In fact, normal air pressure is strong enough to crush a metal container when not
balanced by equal pressure from inside the container.
Figure 8.1.1 : The atmosphere above us exerts a large pressure on objects at the surface of the earth, roughly equal to the weight of
a bowling ball pressing on an area the size of a human thumbnail.
Diagram of Earth with a square inch column of air molecules extending to the atmosphere. This column points to an arrow pointing
down on a bowling ball resting on a human thumbnail placed on top of a table.
Atmospheric pressure is caused by the weight of the column of air molecules in the atmosphere above an object, such as the tanker
car. At sea level, this pressure is roughly the same as that exerted by a full-grown African elephant standing on a doormat, or a
typical bowling ball resting on your thumbnail. These may seem like huge amounts, and they are, but life on earth has evolved
under such atmospheric pressure. If you actually perch a bowling ball on your thumbnail, the pressure experienced is twice the
usual pressure, and the sensation is unpleasant.
A dramatic illustration of atmospheric pressure is provided in this brief video, which shows a railway tanker car imploding when
its internal pressure is decreased.
Pressure is defined as the force exerted on a given area:
F
P = (8.1.1)
A

Since pressure is directly proportional to force and inversely proportional to area (Equation 8.1.1), pressure can be increased
either by either increasing the amount of force or by decreasing the area over which it is applied. Correspondingly, pressure
can be decreased by either decreasing the force or increasing the area.
Let’s apply the definition of pressure (Equation 8.1.1 ) to determine which would be more likely to fall through thin ice in Figure
8.1.2.—the elephant or the figure skater?
Figure 8.1.2 : Although (a) an elephant’s weight is large, creating a very large force on the ground, (b) the figure skater exerts a
much higher pressure on the ice due to the small surface area of her skates. (credit a: modification of work by Guido da Rozze;
credit b: modification of work by Ryosuke Yagi).
Figure a is a photo of a large gray elephant on grassy, beige terrain. Figure b is a photo of a figure skater with her right skate on the
ice, upper torso lowered, arms extended upward behind her chest, and left leg extended upward behind her.
A large African elephant can weigh 7 tons, supported on four feet, each with a diameter of about 1.5 ft (footprint area of 250 in2),
so the pressure exerted by each foot is about 14 lb/in2:
lb 1 elephant 1 f oot
2
pressure per elephant f oot = 14, 000 × × = 14 lb/i n (8.1.2)
2
elephant 4 f eet 250 in
The figure skater weighs about 120 lbs, supported on two skate blades, each with an area of about 2 in2, so the pressure exerted by
each blade is about 30 lb/in2:
lb 1 skater 1 blade 2
pressure per skate blade = 120 × × = 30 lb/i n (8.1.3)
2
skater 2 blades 2 in
Even though the elephant is more than one hundred times heavier than the skater, it exerts less than one-half of the pressure and
would therefore be less likely to fall through thin ice. On the other hand, if the skater removes her skates and stands with bare feet
(or regular footwear) on the ice, the larger area over which her weight is applied greatly reduces the pressure exerted:
lb 1 skater 1 f oot
2
pressure per human f oot = 120 × × = 2 lb/i n (8.1.4)
2
skater 2 f eet 30 in
The SI unit of pressure is the pascal (Pa), with 1 Pa = 1 N/m2, where N is the newton, a unit of force defined as 1 kg m/s2. One
pascal is a small pressure; in many cases, it is more convenient to use units of kilopascal (1 kPa = 1000 Pa) or bar (1 bar = 100,000
Pa). In the United States, pressure is often measured in pounds of force on an area of one square inch—pounds per square inch (psi)
—for example, in car tires. Pressure can also be measured using the unit atmosphere (atm), which originally represented the
average sea level air pressure at the approximate latitude of Paris (45°). Table 8.1.1 provides some information on these and a few
other common units for pressure measurements
Table 8.1.1 : Pressure Units
Unit Name and Abbreviation Definition or Relation to Other Unit Comment
pascal (Pa) 1 Pa = 1 N/m2 recommended IUPAC unit
kilopascal (kPa) 1 kPa = 1000 Pa
pounds per square inch (psi) air pressure at sea level is ~14.7 psi
atmosphere (atm) 1 atm = 101,325 Pa air pressure at sea level is ~1 atm
bar (bar, or b) 1 bar = 100,000 Pa (exactly) commonly used in meteorology

Unit Name and Abbreviation Definition or Relation to Other Unit Comment
millibar (mbar, or mb) 1000 mbar = 1 bar
used by aviation industry, also some weather

inches of mercury (in. Hg) 1 in. Hg = 3386 Pa
reports
1 named after Evangelista Torricelli, inventor of
torr 1 torr = atm
760 the barometer
millimeters of mercury (mm Hg) 1 mm Hg ~1 torr
 Example 8.1.1: Conversion of Pressure Units
The United States National Weather Service reports pressure in both inches of Hg and millibars. Convert a pressure of 29.2 in.
Hg into:
a. torr
b. atm
c. kPa
d. mbar
Solution
This is a unit conversion problem. The relationships between the various pressure units are given in Table 9.2.1.
25.4 mm 1 torr
a. 29.2 in Hg × × = 742 torr
1 in 1 mm Hg
1 atm
b. 742 torr × = 0.976 atm
760 torr
101.325 kPa
c. 742 torr × = 98.9 kPa
760 torr
1000 Pa 1 bar 1000 mbar

d. 98.9 kPa × × × = 989 mbar
1 kPa 100, 000 Pa 1 bar
 Exercise 8.1.1
A typical barometric pressure in Kansas City is 740 torr. What is this pressure in atmospheres, in millimeters of mercury, in
kilopascals, and in bar?
Answer
0.974 atm; 740 mm Hg; 98.7 kPa; 0.987 bar
We can measure atmospheric pressure, the force exerted by the atmosphere on the earth’s surface, with a barometer (Figure 8.1.3).
A barometer is a glass tube that is closed at one end, filled with a nonvolatile liquid such as mercury, and then inverted and
immersed in a container of that liquid. The atmosphere exerts pressure on the liquid outside the tube, the column of liquid exerts
pressure inside the tube, and the pressure at the liquid surface is the same inside and outside the tube. The height of the liquid in the
tube is therefore proportional to the pressure exerted by the atmosphere.

Figure 8.1.3 : In a barometer, the height, h, of the column of liquid is used as a measurement of the air pressure. Using very dense
liquid mercury (left) permits the construction of reasonably sized barometers, whereas using water (right) would require a
barometer more than 30 feet tall.
Two barometers are in vacuum. One utilizes mercury while the other uses water in the capillary tube. Both barometers are exposed
to atmospheric pressure. The barometer with mercury shows mercury levels of 2.49 feet. The barometer with water has a much
greater level of 33.9 feet.
If the liquid is water, normal atmospheric pressure will support a column of water over 10 meters high, which is rather inconvenient
for making (and reading) a barometer. Because mercury (Hg) is about 13.6-times denser than water, a mercury barometer only
1
needs to be as tall as a water barometer—a more suitable size. Standard atmospheric pressure of 1 atm at sea level (101,325
13.6
Pa) corresponds to a column of mercury that is about 760 mm (29.92 in.) high. The torr was originally intended to be a unit equal
to one millimeter of mercury, but it no longer corresponds exactly. The pressure exerted by a fluid due to gravity is known as
hydrostatic pressure, p:
p = hρg (8.1.5)
where
h is the height of the fluid,
ρ is the density of the fluid, and
g is acceleration due to gravity.
 Example 8.1.2: Calculation of Barometric Pressure
Show the calculation supporting the claim that atmospheric pressure near sea level corresponds to the pressure exerted by a
column of mercury that is about 760 mm high. The density of mercury = 13.6 g/cm . 3
Solution
The hydrostatic pressure is given by Equation 8.1.5, with h = 760 mm, ρ = 13.6 g/cm , and g = 9.81 m/s . Plugging these
3 2
values into the Equation 8.1.5 and doing the necessary unit conversions will give us the value we seek. (Note: We are
expecting to find a pressure of ~101,325 Pa:)
2
kg ⋅ m/s kg
2
101, 325 N/ m = 101, 325 = 101, 325
2 2
m m⋅s

3
1 m 13.6 g 1 kg (100 cm) 9.81 m
p = (760 mm × ) ×( × × ) ×( )
3 3 2
1000 mm 1 cm 1000 g (1 m) 1 s
3 2 5 2 5 2
= (0.760 m)(13, 600 kg/ m )(9.81 m/ s ) = 1.01 × 10 kg/ms = 1.01 × 10 N/ m
5
= 1.01 × 10 Pa
 Exercise 8.1.2
Calculate the height of a column of water at 25 °C that corresponds to normal atmospheric pressure. The density of water at
this temperature is 1.0 g/cm3.
Answer
10.3 m
A manometer is a device similar to a barometer that can be used to measure the pressure of a gas trapped in a container. A closed-
end manometer is a U-shaped tube with one closed arm, one arm that connects to the gas to be measured, and a nonvolatile liquid
(usually mercury) in between. As with a barometer, the distance between the liquid levels in the two arms of the tube (h in the
diagram) is proportional to the pressure of the gas in the container. An open-end manometer (Figure 8.1.3) is the same as a closed-
end manometer, but one of its arms is open to the atmosphere. In this case, the distance between the liquid levels corresponds to the
difference in pressure between the gas in the container and the atmosphere.
Figure 8.1.4 : A manometer can be used to measure the pressure of a gas. The (difference in) height between the liquid levels (h) is
a measure of the pressure. Mercury is usually used because of its large density.
The first manometer is closed end. The gas in the bulb exerts a certain pressure on the liquid in the tube so that the height, h,
between the two levels of liquid on both sides of the U tube is proportional to the pressure. The equation is P subscript gas equals to
h rho g. The second manometer has an open end. The equation for P subscript gas is equals to P subscript atm minus h rho g. The
final manometer is also open ended and has equation of P subscript gas equals to P subscript atm plus h rho g for cases where
pressure of the gas is greater than atmospheric pressure.
 Example 8.1.3: Calculation of Pressure Using an Open-End Manometer
The pressure of a sample of gas is measured at sea level with an open-end Hg (mercury) manometer, as shown below.
Determine the pressure of the gas in:
a. mm Hg
b. atm
c. kPa

The height is the difference between the two levels of mercury on each side of the U tube and has a value of 13.7 centimeters.
The level on the right side is higher than the left.
Solution
The pressure of the gas equals the hydrostatic pressure due to a column of mercury of height 13.7 cm plus the pressure of the
atmosphere at sea level. (The pressure at the bottom horizontal line is equal on both sides of the tube. The pressure on the left
is due to the gas and the pressure on the right is due to 13.7 cm of Hg plus atmospheric pressure.)
a. In mm Hg, this is: 137 mm Hg + 760 mm Hg = 897 mm Hg
1 atm
b. 897 mmHg × = 1.18 atm
760 mmHg
101.325 kPa
c. 1.18 atm × = 1.20 × 10
2
kPa
1 atm
 Exercise 8.1.3
The pressure of a sample of gas is measured at sea level with an open-end Hg manometer, as shown below Determine the
pressure of the gas in:
a. mm Hg
b. atm
c. kPa
The height is the difference between the two levels of mercury on each side of the U tube and has a value of 4.63 inches. The
level on the left side is higher than the right.
Answer a
642 mm Hg

Answer b
0.845 atm
Answer c
85.6 kPa
 Application: Measuring Blood Pressure
Blood pressure is measured using a device called a sphygmomanometer (Greek sphygmos = “pulse”). It consists of an
inflatable cuff to restrict blood flow, a manometer to measure the pressure, and a method of determining when blood flow
begins and when it becomes impeded (Figure 8.1.5). Since its invention in 1881, it has been an essential medical device. There
are many types of sphygmomanometers: manual ones that require a stethoscope and are used by medical professionals;
mercury ones, used when the most accuracy is required; less accurate mechanical ones; and digital ones that can be used with
little training but that have limitations. When using a sphygmomanometer, the cuff is placed around the upper arm and inflated
until blood flow is completely blocked, then slowly released. As the heart beats, blood forced through the arteries causes a rise
in pressure. This rise in pressure at which blood flow begins is the systolic pressure—the peak pressure in the cardiac cycle.
When the cuff’s pressure equals the arterial systolic pressure, blood flows past the cuff, creating audible sounds that can be
heard using a stethoscope. This is followed by a decrease in pressure as the heart’s ventricles prepare for another beat. As cuff
pressure continues to decrease, eventually sound is no longer heard; this is the diastolic pressure—the lowest pressure (resting
phase) in the cardiac cycle. Blood pressure units from a sphygmomanometer are in terms of millimeters of mercury (mm Hg).
Figure 8.1.5 : (a) A medical technician prepares to measure a patient’s blood pressure with a sphygmomanometer. (b) A typical
sphygmomanometer uses a valved rubber bulb to inflate the cuff and a diaphragm gauge to measure pressure. (credit a:
modification of work by Master Sgt. Jeffrey Allen)
Meteorology, Climatology, and Atmospheric Science

Throughout the ages, people have observed clouds, winds, and precipitation, trying to discern patterns and make predictions: when
it is best to plant and harvest; whether it is safe to set out on a sea voyage; and much more. We now face complex weather and
atmosphere-related challenges that will have a major impact on our civilization and the ecosystem. Several different scientific
disciplines use chemical principles to help us better understand weather, the atmosphere, and climate. These are meteorology,
climatology, and atmospheric science. Meteorology is the study of the atmosphere, atmospheric phenomena, and atmospheric
effects on earth’s weather. Meteorologists seek to understand and predict the weather in the short term, which can save lives and
benefit the economy. Weather forecasts (Figure 8.1.5) are the result of thousands of measurements of air pressure, temperature, and
the like, which are compiled, modeled, and analyzed in weather centers worldwide.

Figure 8.1.6 : Meteorologists use weather maps to describe and predict weather. Regions of high (H) and low (L) pressure have
large effects on weather conditions. The gray lines represent locations of constant pressure known as isobars. (credit: modification
of work by National Oceanic and Atmospheric Administration)
A weather map of the United States is shown which points out areas of high and low pressure with the letters H in blue and L in
red. There are curved grey lines throughout the United States region as well as beyond it around area of Canada and the oceans.
In terms of weather, low-pressure systems occur when the earth’s surface atmospheric pressure is lower than the surrounding
environment: Moist air rises and condenses, producing clouds. Movement of moisture and air within various weather fronts
instigates most weather events.
The atmosphere is the gaseous layer that surrounds a planet. Earth’s atmosphere, which is roughly 100–125 km thick, consists of
roughly 78.1% nitrogen and 21.0% oxygen, and can be subdivided further into the regions shown in Figure 8.1.7: the exosphere
(furthest from earth, > 700 km above sea level), the thermosphere (80–700 km), the mesosphere (50–80 km), the stratosphere
(second lowest level of our atmosphere, 12–50 km above sea level), and the troposphere (up to 12 km above sea level, roughly 80%
of the earth’s atmosphere by mass and the layer where most weather events originate). As you go higher in the troposphere, air
density and temperature both decrease.
Figure 8.1.7 : Earth’s atmosphere has five layers: the troposphere, the stratosphere, the mesosphere, the thermosphere, and the
exosphere.
The different layers of the atmosphere is illustrated as a cross sectional slice of the Earth's atmosphere. The different thickness of
each layer is shown. The thermosphere has the largest portion, followed by the exosphere, stratosphere, mesosphere, and
troposphere.
Climatology is the study of the climate, averaged weather conditions over long time periods, using atmospheric data. However,
climatologists study patterns and effects that occur over decades, centuries, and millennia, rather than shorter time frames of hours,
days, and weeks like meteorologists. Atmospheric science is an even broader field, combining meteorology, climatology, and other
scientific disciplines that study the atmosphere.
Summary
Gases exert pressure, which is force per unit area. The pressure of a gas may be expressed in the SI unit of pascal or kilopascal, as
well as in many other units including torr, atmosphere, and bar. Atmospheric pressure is measured using a barometer; other gas
pressures can be measured using one of several types of manometers.

Key Equations
F
P =
A
p = hρg
Glossary
atmosphere (atm)
unit of pressure; 1 atm = 101,325 Pa
bar
(bar or b) unit of pressure; 1 bar = 100,000 Pa
barometer
device used to measure atmospheric pressure
hydrostatic pressure
pressure exerted by a fluid due to gravity
manometer
device used to measure the pressure of a gas trapped in a container
pascal (Pa)
SI unit of pressure; 1 Pa = 1 N/m2
pounds per square inch (psi)

unit of pressure common in the US
pressure
force exerted per unit area
torr
1
unit of pressure; 1 torr = atm
760
This page titled 8.1: Gas Pressure is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
9.1: Gas Pressure is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

Identify the mathematical relationships between the various properties of gases
Use the ideal gas law, and related gas laws, to compute the values of various gas properties under specified conditions
During the seventeenth and especially eighteenth centuries, driven both by a desire to understand nature and a quest to make balloons in which they could fly (Figure 8.2.1), a number of scientists
established the relationships between the macroscopic physical properties of gases, that is, pressure, volume, temperature, and amount of gas. Although their measurements were not precise by
today’s standards, they were able to determine the mathematical relationships between pairs of these variables (e.g., pressure and temperature, pressure and volume) that hold for an ideal gas—a
hypothetical construct that real gases approximate under certain conditions. Eventually, these individual laws were combined into a single equation—the ideal gas law—that relates gas quantities
for gases and is quite accurate for low pressures and moderate temperatures. We will consider the key developments in individual relationships (for pedagogical reasons not quite in historical order),
then put them together in the ideal gas law.
Figure 8.2.1 : In 1783, the first (a) hydrogen-filled balloon flight, (b) manned hot air balloon flight, and (c) manned hydrogen-filled balloon flight occurred. When the hydrogen-filled balloon
depicted in (a) landed, the frightened villagers of Gonesse reportedly destroyed it with pitchforks and knives. The launch of the latter was reportedly viewed by 400,000 people in Paris.
This figure includes three images. Image a is a black and white image of a hydrogen balloon apparently being deflated by a mob of people. In image b, a blue, gold, and red balloon is being held to
the ground with ropes while positioned above a platform from which smoke is rising beneath the balloon. In c, an image is shown in grey on a peach-colored background of an inflated balloon with
vertical striping in the air. It appears to have a basket attached to its lower side. A large stately building appears in the background.
Pressure and Temperature: Amontons’s Law

Imagine filling a rigid container attached to a pressure gauge with gas and then sealing the container so that no gas may escape. If the container is cooled, the gas inside likewise gets colder and its
pressure is observed to decrease. Since the container is rigid and tightly sealed, both the volume and number of moles of gas remain constant. If we heat the sphere, the gas inside gets hotter (Figure
8.2.2) and the pressure increases.
Figure 8.2.2 : The effect of temperature on gas pressure: When the hot plate is off, the pressure of the gas in the sphere is relatively low. As the gas is heated, the pressure of the gas in the sphere
increases.
This figure includes three similar diagrams. In the first diagram to the left, a rigid spherical container of a gas to which a pressure gauge is attached at the top is placed in a large beaker of water,
indicated in light blue, atop a hot plate. The needle on the pressure gauge points to the far left on the gauge. The diagram is labeled “low P” above and “hot plate off” below. The second similar
diagram also has the rigid spherical container of gas placed in a large beaker from which light blue wavy line segments extend from the top of the liquid in the beaker. The beaker is situated on top
of a slightly reddened circular area. The needle on the pressure gauge points straight up, or to the middle on the gauge. The diagram is labeled “medium P” above and “hot plate on medium” below.
The third diagram also has the rigid spherical container of gas placed in a large beaker in which bubbles appear near the liquid surface and several wavy light blue line segments extend from the
surface out of the beaker. The beaker is situated on top of a bright red circular area. The needle on the pressure gauge points to the far right on the gauge. The diagram is labeled “high P” above and
“hot plate on high” below.
This relationship between temperature and pressure is observed for any sample of gas confined to a constant volume. An example of experimental pressure-temperature data is shown for a sample
of air under these conditions in Figure 8.2.3. We find that temperature and pressure are linearly related, and if the temperature is on the kelvin scale, then P and T are directly proportional (again,
when volume and moles of gas are held constant); if the temperature on the kelvin scale increases by a certain factor, the gas pressure increases by the same factor.
Figure 8.2.3 : For a constant volume and amount of air, the pressure and temperature are directly proportional, provided the temperature is in kelvin. (Measurements cannot be made at lower
temperatures because of the condensation of the gas.) When this line is extrapolated to lower pressures, it reaches a pressure of 0 at –273 °C, which is 0 on the kelvin scale and the lowest possible
temperature, called absolute zero.
This figure includes a table and a graph. The table has 3 columns and 7 rows. The first row is a header, which labels the columns “Temperature, degrees C,” “Temperature, K,” and “Pressure, k P a.”
The first column contains the values from top to bottom negative 150, negative 100, negative 50, 0, 50, and 100. The second column contains the values from top to bottom 173, 223, 273, 323, 373,
and 423. The third column contains the values 36.0, 46.4, 56.7, 67.1, 77.5, and 88.0. A graph appears to the right of the table. The horizontal axis is labeled “Temperature ( K ).” with markings and
labels provided for multiples of 100 beginning at 0 and ending at 500. The vertical axis is labeled “Pressure ( k P a )” with markings and labels provided for multiples of 10, beginning at 0 and
ending at 100. Six data points from the table are plotted on the graph with black dots. These dots are connected with a solid black line. A dashed line extends from the data point furthest to the left
to the origin. The graph shows a positive linear trend.
Guillaume Amontons was the first to empirically establish the relationship between the pressure and the temperature of a gas (~1700), and Joseph Louis Gay-Lussac determined the relationship
more precisely (~1800). Because of this, the P-T relationship for gases is known as either Amontons’s law or Gay-Lussac’s law. Under either name, it states that the pressure of a given amount of
gas is directly proportional to its temperature on the kelvin scale when the volume is held constant. Mathematically, this can be written:

P ∝ T or P = constant × T or P = k × T
where ∝ means “is proportional to,” and k is a proportionality constant that depends on the identity, amount, and volume of the gas.
P P
For a confined, constant volume of gas, the ratio is therefore constant (i.e., =k ). If the gas is initially in “Condition 1” (with P = P1 and T = T1), and then changes to “Condition 2” (with P =
T T
P1 P2 P1 P2
P2 and T = T2), we have that =k and =k , which reduces to = . This equation is useful for pressure-temperature calculations for a confined gas at constant volume. Note that
T1 T2 T1 T2
temperatures must be on the kelvin scale for any gas law calculations (0 on the kelvin scale and the lowest possible temperature is called absolute zero). (Also note that there are at least three ways
we can describe how the pressure of a gas changes as its temperature changes: We can use a table of values, a graph, or a mathematical equation.)
 Example 8.2.1: Predicting Change in Pressure with Temperature
A can of hair spray is used until it is empty except for the propellant, isobutane gas.
a. On the can is the warning “Store only at temperatures below 120 °F (48.8 °C). Do not incinerate.” Why?
b. The gas in the can is initially at 24 °C and 360 kPa, and the can has a volume of 350 mL. If the can is left in a car that reaches 50 °C on a hot day, what is the new pressure in the can?
Solution
a. The can contains an amount of isobutane gas at a constant volume, so if the temperature is increased by heating, the pressure will increase proportionately. High temperature could lead to
high pressure, causing the can to burst. (Also, isobutane is combustible, so incineration could cause the can to explode.)
b. We are looking for a pressure change due to a temperature change at constant volume, so we will use Amontons’s/Gay-Lussac’s law. Taking P1 and T1 as the initial values, T2 as the
temperature where the pressure is unknown and P2 as the unknown pressure, and converting °C to K, we have:
P1 P2 360 kPa P2
= which means that =
T1 T2 297 K 323 K
Rearranging and solving gives:

360 kPa × 323 K
P2 = = 390 kPa
297 K
 Exercise 8.2.1
A sample of nitrogen, N2, occupies 45.0 mL at 27 °C and 600 torr. What pressure will it have if cooled to –73 °C while the volume remains constant?
Answer
400 torr
Volume and Temperature: Charles’s Law

If we fill a balloon with air and seal it, the balloon contains a specific amount of air at atmospheric pressure, let’s say 1 atm. If we put the balloon in a refrigerator, the gas inside gets cold and the
balloon shrinks (although both the amount of gas and its pressure remain constant). If we make the balloon very cold, it will shrink a great deal, and it expands again when it warms up.
Liquid Nitrogen Experiments: The Balloon
Video 8.2.1 : This video shows how cooling and heating a gas causes its volume to decrease or increase, respectively.
These examples of the effect of temperature on the volume of a given amount of a confined gas at constant pressure are true in general: The volume increases as the temperature increases, and
decreases as the temperature decreases. Volume-temperature data for a 1-mole sample of methane gas at 1 atm are listed and graphed in Figure 8.2.2.

Figuire 8.2.4 : The volume and temperature are linearly related for 1 mole of methane gas at a constant pressure of 1 atm. If the temperature is in kelvin, volume and temperature are directly
proportional. The line stops at 111 K because methane liquefies at this temperature; when extrapolated, it intersects the graph’s origin, representing a temperature of absolute zero.
This figure includes a table and a graph. The table has 3 columns and 6 rows. The first row is a header, which labels the columns “Temperature, degrees C,” “Temperature, K,” and “Pressure, k P a.”
The first column contains the values from top to bottom negative 100, negative 50, 0, 100, and 200. The second column contains the values from top to bottom 173, 223, 273, 373, and 473. The
third column contains the values 14.10, 18.26, 22.40, 30.65, and 38.88. A graph appears to the right of the table. The horizontal axis is labeled “Temperature ( K ).” with markings and labels
provided for multiples of 100 beginning at 0 and ending at 300. The vertical axis is labeled “Volume ( L )” with marking and labels provided for multiples of 10, beginning at 0 and ending at 30.
Five data points from the table are plotted on the graph with black dots. These dots are connected with a solid black line. The graph shows a positive linear trend.
The relationship between the volume and temperature of a given amount of gas at constant pressure is known as Charles’s law in recognition of the French scientist and balloon flight pioneer
Jacques Alexandre César Charles. Charles’s law states that the volume of a given amount of gas is directly proportional to its temperature on the kelvin scale when the pressure is held constant.
Mathematically, this can be written as:
V αT or V = constant ⋅ T or V = k ⋅ T
with k being a proportionality constant that depends on the amount and pressure of the gas.
V V1 V2
For a confined, constant pressure gas sample, is constant (i.e., the ratio = k), and as seen with the P-T relationship, this leads to another form of Charles’s law: = .
T T1 T2
 Example 8.2.2: Predicting Change in Volume with Temperature
A sample of carbon dioxide, CO2, occupies 0.300 L at 10 °C and 750 torr. What volume will the gas have at 30 °C and 750 torr?
Solution
Because we are looking for the volume change caused by a temperature change at constant pressure, this is a job for Charles’s law. Taking V1 and T1 as the initial values, T2 as the temperature at
which the volume is unknown and V2 as the unknown volume, and converting °C into K we have:
V1 V2 0.300 L V2
T1 T2 283 K 303 K
0.300 L × 303 K
Rearranging and solving gives: V 2 = = 0.321 L
283 K
This answer supports our expectation from Charles’s law, namely, that raising the gas temperature (from 283 K to 303 K) at a constant pressure will yield an increase in its volume (from 0.300 L to
0.321 L).
 Exercise 8.2.2
A sample of oxygen, O2, occupies 32.2 mL at 30 °C and 452 torr. What volume will it occupy at –70 °C and the same pressure?
Answer
21.6 mL
 Example 8.2.3: Measuring Temperature with a Volume
Change Temperature is sometimes measured with a gas thermometer by observing the change in the volume of the gas as the temperature changes at constant pressure. The hydrogen in a
particular hydrogen gas thermometer has a volume of 150.0 cm3 when immersed in a mixture of ice and water (0.00 °C). When immersed in boiling liquid ammonia, the volume of the
hydrogen, at the same pressure, is 131.7 cm3. Find the temperature of boiling ammonia on the kelvin and Celsius scales.
Solution
A volume change caused by a temperature change at constant pressure means we should use Charles’s law. Taking V1 and T1 as the initial values, T2 as the temperature at which the volume is
unknown and V2 as the unknown volume, and converting °C into K we have:
3 3
V1 V2 150.0 cm 131.7 cm
T1 T2 273.15 K T2
3
131.7 cm × 273.15 K
Rearrangement gives T 2 =
3
= 239.8 K
150.0 cm
Subtracting 273.15 from 239.8 K, we find that the temperature of the boiling ammonia on the Celsius scale is –33.4 °C.
 Exercise 8.2.3
What is the volume of a sample of ethane at 467 K and 1.1 atm if it occupies 405 mL at 298 K and 1.1 atm?
Answer
635 mL

Volume and Pressure: Boyle’s Law
If we partially fill an airtight syringe with air, the syringe contains a specific amount of air at constant temperature, say 25 °C. If we slowly push in the plunger while keeping temperature constant,
the gas in the syringe is compressed into a smaller volume and its pressure increases; if we pull out the plunger, the volume increases and the pressure decreases. This example of the effect of
volume on the pressure of a given amount of a confined gas is true in general. Decreasing the volume of a contained gas will increase its pressure, and increasing its volume will decrease its
pressure. In fact, if the volume increases by a certain factor, the pressure decreases by the same factor, and vice versa. Volume-pressure data for an air sample at room temperature are graphed in
Figure 8.2.5.
Figure 8.2.5 : When a gas occupies a smaller volume, it exerts a higher pressure; when it occupies a larger volume, it exerts a lower pressure (assuming the amount of gas and the temperature do not
1
change). Since P and V are inversely proportional, a graph of vs. V is linear.
P
This figure contains a diagram and two graphs. The diagram shows a syringe labeled with a scale in m l or c c with multiples of 5 labeled beginning at 5 and ending at 30. The markings halfway
between these measurements are also provided. Attached at the top of the syringe is a pressure gauge with a scale marked by fives from 40 on the left to 5 on the right. The gauge needle rests
between 10 and 15, slightly closer to 15. The syringe plunger position indicates a volume measurement about halfway between 10 and 15 m l or c c. The first graph is labeled “V ( m L )” on the
horizontal axis and “P ( p s i )” on the vertical axis. Points are labeled at 5, 10, 15, 20, and 25 m L with corresponding values of 39.0, 19.5, 13.0, 9.8, and 6.5 p s i. The points are connected with a
smooth curve that is declining at a decreasing rate of change. The second graph is labeled “V ( m L )” on the horizontal axis and “1 divided by P ( p s i )” on the vertical axis. The horizontal axis is
labeled at multiples of 5, beginning at zero and extending up to 35 m L. The vertical axis is labeled by multiples of 0.02, beginning at 0 and extending up to 0.18. Six points indicated by black dots
on this graph are connected with a black line segment showing a positive linear trend.
Unlike the P-T and V-T relationships, pressure and volume are not directly proportional to each other. Instead, P and V exhibit inverse proportionality: Increasing the pressure results in a decrease
of the volume of the gas. Mathematically this can be written:
1
P ∝
V
or
1
P =k⋅
V
or
PV = k
or
P1 V1 = P2 V2
1
with k being a constant. Graphically, this relationship is shown by the straight line that results when plotting the inverse of the pressure ( ) versus the volume (V), or the inverse of volume
P
1
( ) versus the pressure (P ). Graphs with curved lines are difficult to read accurately at low or high values of the variables, and they are more difficult to use in fitting theoretical equations and
V
parameters to experimental data. For those reasons, scientists often try to find a way to “linearize” their data. If we plot P versus V, we obtain a hyperbola (Figure 8.2.6).
1
Figure 8.2.6 : The relationship between pressure and volume is inversely proportional. (a) The graph of P vs. V is a hyperbola, whereas (b) the graph of ( ) vs. V is linear.
P
This diagram shows two graphs. In a, a graph is shown with volume on the horizontal axis and pressure on the vertical axis. A curved line is shown on the graph showing a decreasing trend with a
decreasing rate of change. In b, a graph is shown with volume on the horizontal axis and one divided by pressure on the vertical axis. A line segment, beginning at the origin of the graph, shows a
positive, linear trend.
The relationship between the volume and pressure of a given amount of gas at constant temperature was first published by the English natural philosopher Robert Boyle over 300 years ago. It is
summarized in the statement now known as Boyle’s law: The volume of a given amount of gas held at constant temperature is inversely proportional to the pressure under which it is measured.
 Example 8.2.4: Volume of a Gas Sample

The sample of gas has a volume of 15.0 mL at a pressure of 13.0 psi. Determine the pressure of the gas at a volume of 7.5 mL, using:
a. the P-V graph in Figure 8.2.6a
1
b. the vs. V graph in Figure 8.2.6b
P
c. the Boyle’s law equation
Comment on the likely accuracy of each method.
Solution
a. Estimating from the P-V graph gives a value for P somewhere around 27 psi.
1
b. Estimating from the versus V graph give a value of about 26 psi.
P
c. From Boyle’s law, we know that the product of pressure and volume (PV) for a given sample of gas at a constant temperature is always equal to the same value. Therefore we have P1V1 = k
and P2V2 = k which means that P1V1 = P2V2.
Using P1 and V1 as the known values 13.0 psi and 15.0 mL, P2 as the pressure at which the volume is unknown, and V2 as the unknown volume, we have:
P1 V1 = P2 V2 or 13.0 psi × 15.0 mL = P2 × 7.5 mL
Solving:
13.0 psi × 15.0 mL

P2 = = 26 psi
7.5 mL
It was more difficult to estimate well from the P-V graph, so (a) is likely more inaccurate than (b) or (c). The calculation will be as accurate as the equation and measurements allow.
 Exercise 8.2.4
The sample of gas has a volume of 30.0 mL at a pressure of 6.5 psi. Determine the volume of the gas at a pressure of 11.0 psi, using:
a. the P-V graph in Figure 8.2.6a
1
b. the vs. V graph in Figure 8.2.6b
P
c. the Boyle’s law equation
Comment on the likely accuracy of each method.

Answer a
about 17–18 mL
Answer b
~18 mL
Answer c
17.7 mL; it was more difficult to estimate well from the P-V graph, so (a) is likely more inaccurate than (b); the calculation will be as accurate as the equation and measurements allow
 Breathing and Boyle’s Law

What do you do about 20 times per minute for your whole life, without break, and often without even being aware of it? The answer, of course, is respiration, or breathing. How does it work? It
turns out that the gas laws apply here. Your lungs take in gas that your body needs (oxygen) and get rid of waste gas (carbon dioxide). Lungs are made of spongy, stretchy tissue that expands
and contracts while you breathe. When you inhale, your diaphragm and intercostal muscles (the muscles between your ribs) contract, expanding your chest cavity and making your lung volume
larger. The increase in volume leads to a decrease in pressure (Boyle’s law). This causes air to flow into the lungs (from high pressure to low pressure). When you exhale, the process reverses:
Your diaphragm and rib muscles relax, your chest cavity contracts, and your lung volume decreases, causing the pressure to increase (Boyle’s law again), and air flows out of the lungs (from
high pressure to low pressure). You then breathe in and out again, and again, repeating this Boyle’s law cycle for the rest of your life (Figure 8.2.7).
Figure 8.2.7 : Breathing occurs because expanding and contracting lung volume creates small pressure differences between your lungs and your surroundings, causing air to be drawn into and
forced out of your lungs.
This figure contains two diagrams of a cross section of the human head and torso. The first diagram on the left is labeled “Inspiration.” It shows curved arrows in gray proceeding through the
nasal passages and mouth to the lungs. An arrow points downward from the diaphragm, which is relatively flat, just beneath the lungs. This arrow is labeled “Diaphragm contracts.” At the
entrance to the mouth and nasal passages, a label of P subscript lungs equals 1 dash 3 torr lower” is provided. The second, similar diagram, which is labeled “Expiration,” reverses the direction
of both arrows. Arrows extend from the lungs out through the nasal passages and mouth. Similarly, an arrow points up to the diaphragm, showing a curved diaphragm and lungs reduced in size
from the previous image. This arrow is labeled “Diaphragm relaxes.” At the entrance to the mouth and nasal passages, a label of P subscript lungs equals 1 dash 3 torr higher” is provided.
Moles of Gas and Volume: Avogadro’s Law

The Italian scientist Amedeo Avogadro advanced a hypothesis in 1811 to account for the behavior of gases, stating that equal volumes of all gases, measured under the same conditions of
temperature and pressure, contain the same number of molecules. Over time, this relationship was supported by many experimental observations as expressed by Avogadro’s law: For a confined
gas, the volume (V) and number of moles (n) are directly proportional if the pressure and temperature both remain constant.
In equation form, this is written as:
V1 V2
V ∝ n or V = k × n or =
n1 n2
Mathematical relationships can also be determined for the other variable pairs, such as P versus n, and n versus T.
Visit this interactive PhET simulation to investigate the relationships between pressure, volume, temperature, and amount of gas. Use the
simulation to examine the effect of changing one parameter on another while holding the other parameters constant (as described in the
preceding sections on the various gas laws).
The Ideal Gas Law

To this point, four separate laws have been discussed that relate pressure, volume, temperature, and the number of moles of the gas:
Boyle’s law: PV = constant at constant T and n
P
Amontons’s law: = constant at constant V and n
T
V
Charles’s law: = constant at constant P and n
T
V
Avogadro’s law: = constant at constant P and T
n
Combining these four laws yields the ideal gas law, a relation between the pressure, volume, temperature, and number of moles of a gas:
P V = nRT
where P is the pressure of a gas, V is its volume, n is the number of moles of the gas, T is its temperature on the kelvin scale, and R is a constant called the ideal gas constant or the universal gas
constant. The units used to express pressure, volume, and temperature will determine the proper form of the gas constant as required by dimensional analysis, the most commonly encountered
values being 0.08206 L atm mol–1 K–1 and 8.3145 kPa L mol–1 K–1.
The ideal gas law is easy to remember and apply in solving problems, as long as you use the proper values and units for the gas constant, R.

Gases whose properties of P, V, and T are accurately described by the ideal gas law (or the other gas laws) are said to exhibit ideal behavior or to approximate the traits of an ideal gas. An ideal gas
is a hypothetical construct that may be used along with kinetic molecular theory to effectively explain the gas laws as will be described in a later module of this chapter. Although all the calculations
presented in this module assume ideal behavior, this assumption is only reasonable for gases under conditions of relatively low pressure and high temperature. In the final module of this chapter, a
modified gas law will be introduced that accounts for the non-ideal behavior observed for many gases at relatively high pressures and low temperatures.
The ideal gas equation contains five terms, the gas constant R and the variable properties P, V, n, and T. Specifying any four of these terms will permit use of the ideal gas law to calculate the fifth
term as demonstrated in the following example exercises.
 Example 8.2.5: Using the Ideal Gas Law

Methane, CH4, is being considered for use as an alternative automotive fuel to replace gasoline. One gallon of gasoline could be replaced by 655 g of CH4. What is the volume of this much
methane at 25 °C and 745 torr?
Solution
 Exercise 8.2.5
Calculate the pressure in bar of 2520 moles of hydrogen gas stored at 27 °C in the 180-L storage tank of a modern hydrogen-powered car.
Answer
350 bar
P1 V1 P2 V2
If the number of moles of an ideal gas are kept constant under two different sets of conditions, a useful mathematical relationship called the combined gas law is obtained: = using
T1 T2
units of atm, L, and K. Both sets of conditions are equal to the product of n × R (where n = the number of moles of the gas and R is the ideal gas law constant).
 Example 8.2.6: Using the Combined Gas Law
When filled with air, a typical scuba tank with a volume of 13.2 L has a pressure of 153 atm (Figure 8.2.8). If the water temperature is 27 °C, how many liters of air will such a tank provide to a
diver’s lungs at a depth of approximately 70 feet in the ocean where the pressure is 3.13 atm?
Figure 8.2.8 : Scuba divers use compressed air to breathe while underwater. (credit: modification of work by Mark Goodchild)
This photograph shows a scuba diver underwater with a tank on his or her back and bubbles ascending from the breathing apparatus.
Letting 1 represent the air in the scuba tank and 2 represent the air in the lungs, and noting that body temperature (the temperature the air will be in the lungs) is 37 °C, we have:
P1 V1 P2 V2 (153 atm)(13.2 L) (3.13 atm)(V2 )

= ⟶ =
T1 T2 (300 K) (310 K)
Solving for V2:
(153 atm )(13.2 L)(310 K )

V2 = = 667 L
(300 K )(3.13 atm )
(Note: Be advised that this particular example is one in which the assumption of ideal gas behavior is not very reasonable, since it involves gases at relatively high pressures and low
temperatures. Despite this limitation, the calculated volume can be viewed as a good “ballpark” estimate.)
 Exercise 8.2.6
A sample of ammonia is found to occupy 0.250 L under laboratory conditions of 27 °C and 0.850 atm. Find the volume of this sample at 0 °C and 1.00 atm.
Answer
0.193 L
 The Interdependence between Ocean Depth and Pressure in Scuba Diving
Whether scuba diving at the Great Barrier Reef in Australia (shown in Figure 8.2.9) or in the Caribbean, divers must understand how pressure affects a number of issues related to their comfort
and safety.

Figure 8.2.9 : Scuba divers, whether at the Great Barrier Reef or in the Caribbean, must be aware of buoyancy, pressure equalization, and the amount of time they spend underwater, to avoid the
risks associated with pressurized gases in the body. (credit: Kyle Taylor).
This picture shows colorful underwater corals and anemones in hues of yellow, orange, green, and brown, surrounded by water that appears blue in color.
Pressure increases with ocean depth, and the pressure changes most rapidly as divers reach the surface. The pressure a diver experiences is the sum of all pressures above the diver (from the
water and the air). Most pressure measurements are given in units of atmospheres, expressed as “atmospheres absolute” or ATA in the diving community: Every 33 feet of salt water represents
1 ATA of pressure in addition to 1 ATA of pressure from the atmosphere at sea level. As a diver descends, the increase in pressure causes the body’s air pockets in the ears and lungs to
compress; on the ascent, the decrease in pressure causes these air pockets to expand, potentially rupturing eardrums or bursting the lungs. Divers must therefore undergo equalization by adding
air to body airspaces on the descent by breathing normally and adding air to the mask by breathing out of the nose or adding air to the ears and sinuses by equalization techniques; the corollary
is also true on ascent, divers must release air from the body to maintain equalization. Buoyancy, or the ability to control whether a diver sinks or floats, is controlled by the buoyancy
compensator (BCD). If a diver is ascending, the air in his BCD expands because of lower pressure according to Boyle’s law (decreasing the pressure of gases increases the volume). The
expanding air increases the buoyancy of the diver, and she or he begins to ascend. The diver must vent air from the BCD or risk an uncontrolled ascent that could rupture the lungs. In
descending, the increased pressure causes the air in the BCD to compress and the diver sinks much more quickly; the diver must add air to the BCD or risk an uncontrolled descent, facing much
higher pressures near the ocean floor. The pressure also impacts how long a diver can stay underwater before ascending. The deeper a diver dives, the more compressed the air that is breathed
because of increased pressure: If a diver dives 33 feet, the pressure is 2 ATA and the air would be compressed to one-half of its original volume. The diver uses up available air twice as fast as
at the surface.
Standard Conditions of Temperature and Pressure

We have seen that the volume of a given quantity of gas and the number of molecules (moles) in a given volume of gas vary with changes in pressure and temperature. Chemists sometimes make
comparisons against a standard temperature and pressure (STP) for reporting properties of gases: 273.15 K (0.00 °C) and 1 atm (101.325 kPa). At STP, an ideal gas has a volume of about 22.4 L—
this is referred to as the standard molar volume (Figure 8.2.10).
Figure 8.2.10 : Since the number of moles in a given volume of gas varies with pressure and temperature changes, chemists use standard temperature and pressure (273.15 K and 1 atm or 101.325
kPa) to report properties of gases.
This figure shows three balloons each filled with H e, N H subscript 2, and O subscript 2 respectively. Beneath the first balloon is the label “4 g of He” Beneath the second balloon is the label, “15 g
of N H subscript 2.” Beneath the third balloon is the label “32 g of O subscript 2.” Each balloon contains the same number of molecules of their respective gases.
Summary
The behavior of gases can be described by several laws based on experimental observations of their properties. The pressure of a given amount of gas is directly proportional to its absolute
temperature, provided that the volume does not change (Amontons’s law). The volume of a given gas sample is directly proportional to its absolute temperature at constant pressure (Charles’s law).
The volume of a given amount of gas is inversely proportional to its pressure when temperature is held constant (Boyle’s law). Under the same conditions of temperature and pressure, equal
volumes of all gases contain the same number of molecules (Avogadro’s law).
The equations describing these laws are special cases of the ideal gas law, PV = nRT, where P is the pressure of the gas, V is its volume, n is the number of moles of the gas, T is its kelvin
temperature, and R is the ideal (universal) gas constant.
Key Equations
PV = nRT
Summary
absolute zero
temperature at which the volume of a gas would be zero according to Charles’s law.
Amontons’s law
(also, Gay-Lussac’s law) pressure of a given number of moles of gas is directly proportional to its kelvin temperature when the volume is held constant
Avogadro’s law
volume of a gas at constant temperature and pressure is proportional to the number of gas molecules
Boyle’s law
volume of a given number of moles of gas held at constant temperature is inversely proportional to the pressure under which it is measured
Charles’s law

volume of a given number of moles of gas is directly proportional to its kelvin temperature when the pressure is held constant
ideal gas
hypothetical gas whose physical properties are perfectly described by the gas laws
ideal gas constant (R)

constant derived from the ideal gas equation R = 0.08226 L atm mol–1 K–1 or 8.314 L kPa mol–1 K–1
ideal gas law

relation between the pressure, volume, amount, and temperature of a gas under conditions derived by combination of the simple gas laws
standard conditions of temperature and pressure (STP)

273.15 K (0 °C) and 1 atm (101.325 kPa)
standard molar volume

volume of 1 mole of gas at STP, approximately 22.4 L for gases behaving ideally
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Use the ideal gas law to compute gas densities and molar masses
Perform stoichiometric calculations involving gaseous substances
State Dalton’s law of partial pressures and use it in calculations involving gaseous mixtures
The study of the chemical behavior of gases was part of the basis of perhaps the most fundamental chemical revolution in history.
French nobleman Antoine Lavoisier, widely regarded as the “father of modern chemistry,” changed chemistry from a qualitative to
a quantitative science through his work with gases. He discovered the law of conservation of matter, discovered the role of oxygen
in combustion reactions, determined the composition of air, explained respiration in terms of chemical reactions, and more. He was
a casualty of the French Revolution, guillotined in 1794. Of his death, mathematician and astronomer Joseph-Louis Lagrange said,
“It took the mob only a moment to remove his head; a century will not suffice to reproduce it."
As described in an earlier chapter of this text, we can turn to chemical stoichiometry for answers to many of the questions that ask
“How much?” We can answer the question with masses of substances or volumes of solutions. However, we can also answer this
question another way: with volumes of gases. We can use the ideal gas equation to relate the pressure, volume, temperature, and
number of moles of a gas. Here we will combine the ideal gas equation with other equations to find gas density and molar mass.
We will deal with mixtures of different gases, and calculate amounts of substances in reactions involving gases. This section will
not introduce any new material or ideas, but will provide examples of applications and ways to integrate concepts we have already
discussed.
Density of a Gas
m
Recall that the density of a gas is its mass to volume ratio, ρ = . Therefore, if we can determine the mass of some volume of a
V
gas, we will get its density. The density of an unknown gas can used to determine its molar mass and thereby assist in its
identification. The ideal gas law, PV = nRT, provides us with a means of deriving such a mathematical formula to relate the density
of a gas to its volume in the proof shown in Example 8.3.1.
 Example 8.3.1: Derivation of a Density Formula from the Ideal Gas Law
Use PV = nRT to derive a formula for the density of gas in g/L
Solution
P V = nRT
Rearrange to get (mol/L):

n P
=
v RT
Multiply each side of the equation by the molar mass, ℳ. When moles are multiplied by ℳ in g/mol, g are obtained:
n P
(M) ( ) =( ) (M)
V RT
PM
M/V = ρ =
RT
 Exercise 8.3.1
A gas was found to have a density of 0.0847 g/L at 17.0 °C and a pressure of 760 torr. What is its molar mass? What is the gas?
Answer

PM
ρ =
RT
1 atm M
0.0847 g/L = 760 torr × × × 290 K
760 torr 0.0821 L atm /mol K
ℳ = 2.02 g/mol; therefore, the gas must be hydrogen (H2, 2.02 g/mol)
We must specify both the temperature and the pressure of a gas when calculating its density because the number of moles of a gas
(and thus the mass of the gas) in a liter changes with temperature or pressure. Gas densities are often reported at STP.
 Example 8.3.2: Empirical/Molecular Formula Problems
Using the Ideal Gas Law and Density of a Gas Cyclopropane, a gas once used with oxygen as a general anesthetic, is
composed of 85.7% carbon and 14.3% hydrogen by mass. Find the empirical formula. If 1.56 g of cyclopropane occupies a
volume of 1.00 L at 0.984 atm and 50 °C, what is the molecular formula for cyclopropane?
Solution
Strategy:
First solve the empirical formula problem using methods discussed earlier. Assume 100 g and convert the percentage of each
element into grams. Determine the number of moles of carbon and hydrogen in the 100-g sample of cyclopropane. Divide by
the smallest number of moles to relate the number of moles of carbon to the number of moles of hydrogen. In the last step,
realize that the smallest whole number ratio is the empirical formula:
1 mol C 7.136
85.7 g C × = 7.136 mol C = 1.00 mol C
12.01 g C 7.136
1 mol H 14.158
14.3 g H × = 14.158 mol H = 1.98 mol H
1.01 g H 7.136
Empirical formula is CH2 [empirical mass (EM) of 14.03 g/empirical unit].

Next, use the density equation related to the ideal gas law to determine the molar mass:
PM 1.56 g M
d = = 0.984 atm × × 323 K
RT 1.00 L 0.0821 L atm/mol K
M 42.0
ℳ = 42.0 g/mol, = = 2.99 , so (3)(CH2) = C3H6 (molecular formula)
EM 14.03
 Exercise 8.3.2
Acetylene, a fuel used welding torches, is comprised of 92.3% C and 7.7% H by mass. Find the empirical formula. If 1.10 g of
acetylene occupies of volume of 1.00 L at 1.15 atm and 59.5 °C, what is the molecular formula for acetylene?
Answer
Empirical formula, CH; Molecular formula, C2H2
Molar Mass of a Gas

Another useful application of the ideal gas law involves the determination of molar mass. By definition, the molar mass of a
substance is the ratio of its mass in grams, m, to its amount in moles, n:
grams of substance m
M= =
moles of substance n
The ideal gas equation can be rearranged to isolate n:

PV
n =
RT
and then combined with the molar mass equation to yield:

mRT
M=
PV
This equation can be used to derive the molar mass of a gas from measurements of its pressure, volume, temperature, and mass.
 Example 8.3.3: Determining the Molar Mass of a Volatile Liquid
The approximate molar mass of a volatile liquid can be determined by:

1. Heating a sample of the liquid in a flask with a tiny hole at the top, which converts the liquid into gas that may escape
through the hole
2. Removing the flask from heat at the instant when the last bit of liquid becomes gas, at which time the flask will be filled
with only gaseous sample at ambient pressure
3. Sealing the flask and permitting the gaseous sample to condense to liquid, and then weighing the flask to determine the
sample’s mass (Figure 8.3.1)
Figure 8.3.1 : When the volatile liquid in the flask is heated past its boiling point, it becomes gas and drives air out of the flask.
At tl ⟶g , the flask is filled with volatile liquid gas at the same pressure as the atmosphere. If the flask is then cooled to room
temperature, the gas condenses and the mass of the gas that filled the flask, and is now liquid, can be measured. (credit:
modification of work by Mark Ott)
Using this procedure, a sample of chloroform gas weighing 0.494 g is collected in a flask with a volume of 129 cm3 at 99.6 °C
when the atmospheric pressure is 742.1 mm Hg. What is the approximate molar mass of chloroform?
Solution
Since
m
M=
n
and
PV
n =
RT
substituting and rearranging gives

mRT
M=
PV
then
mRT (0.494 g) × 0.08206 L ⋅ atm/mol K × 372.8 K
M= = = 120 g/mol
PV 0.976 atm × 0.129 L

 Exercise 8.3.3
A sample of phosphorus that weighs 3.243 × 10−2 g exerts a pressure of 31.89 kPa in a 56.0-mL bulb at 550 °C. What are the
molar mass and molecular formula of phosphorus vapor?
Answer
124 g/mol P4
The Pressure of a Mixture of Gases: Dalton’s Law

Unless they chemically react with each other, the individual gases in a mixture of gases do not affect each other’s pressure. Each
individual gas in a mixture exerts the same pressure that it would exert if it were present alone in the container ( Figure 8.3.2). The
pressure exerted by each individual gas in a mixture is called its partial pressure. This observation is summarized by Dalton’s law
of partial pressures: The total pressure of a mixture of ideal gases is equal to the sum of the partial pressures of the component
gases:
PT otal = PA + PB + PC +. . . = ∑ Pi
In the equation PTotal is the total pressure of a mixture of gases, PA is the partial pressure of gas A; PB is the partial pressure of gas
B; PC is the partial pressure of gas C; and so on.
Figure 8.3.2 : If equal-volume cylinders containing gas A at a pressure of 300 kPa, gas B at a pressure of 600 kPa, and gas C at a
pressure of 450 kPa are all combined in the same-size cylinder, the total pressure of the mixture is 1350 kPa.
This figure includes images of four gas-filled cylinders or tanks. Each has a valve at the top. The interior of the first cylinder is
shaded blue. This region contains 5 small blue circles that are evenly distributed. The label “300 k P a” is on the cylinder. The
second cylinder is shaded lavender. This region contains 8 small purple circles that are evenly distributed. The label “600 k P a” is
on the cylinder. To the right of these cylinders is a third cylinder. Its interior is shaded pale yellow. This region contains 12 small
yellow circles that are evenly distributed. The label “450 k P a” is on this region of the cylinder. An arrow labeled “Total pressure
combined” appears to the right of these three cylinders. This arrow points to a fourth cylinder. The interior of this cylinder is
shaded a pale green. It contains evenly distributed small circles in the following quantities and colors; 5 blue, 8 purple, and 12
yellow. This cylinder is labeled “1350 k P a.”
The partial pressure of gas A is related to the total pressure of the gas mixture via its mole fraction (X), a unit of concentration
defined as the number of moles of a component of a solution divided by the total number of moles of all components:
nA
PA = XA × PT otal where XA =
nT otal
where PA, XA, and nA are the partial pressure, mole fraction, and number of moles of gas A, respectively, and nTotal is the number of
moles of all components in the mixture.
 Example 8.3.2: The Pressure of a Mixture of Gases

A 10.0-L vessel contains 2.50 × 10−3 mol of H2, 1.00 × 10−3 mol of He, and 3.00 × 10−4 mol of Ne at 35 °C.
a. What are the partial pressures of each of the gases?
b. What is the total pressure in atmospheres?

Solution
The gases behave independently, so the partial pressure of each gas can be determined from the ideal gas equation, using
nRT
P = :
V
−3 −1 −1
(2.50 × 10 mol)(0.08206 L atm mol K )(308 K )
−3
PH2 = = 6.32 × 10 atm
10.0 L
−3 −1 −1
(1.00 × 10 mol )(0.08206 L atm mol K )(308 K )
−3
PHe = = 2.53 × 10 atm
10.0 L
−4 −1 −1
(3.00 × 10 mol )(0.08206 L atm mol K )(308 K )
−4
PNe = = 7.58 × 10 atm
10.0 L
The total pressure is given by the sum of the partial pressures:

−3
PT = PH2 + PHe + PNe = (0.00632 + 0.00253 + 0.00076) atm = 9.61 × 10 atm
 Exercise 8.3.2
A 5.73-L flask at 25 °C contains 0.0388 mol of N2, 0.147 mol of CO, and 0.0803 mol of H2. What is the total pressure in the
flask in atmospheres?
Answer
1.137 atm
Here is another example of this concept, but dealing with mole fraction calculations.
 Example 8.3.3: The Pressure of a Mixture of Gases
A gas mixture used for anesthesia contains 2.83 mol oxygen, O2, and 8.41 mol nitrous oxide, N2O. The total pressure of the
mixture is 192 kPa.
a. What are the mole fractions of O2 and N2O?
b. What are the partial pressures of O2 and N2O?
Solution
The mole fraction is given by
nA
XA =
nT otal
and the partial pressure is
PA = XA × PT otal
For O2,
nO2 2.83mol
XO2 = = = 0.252
nT otal (2.83 + 8.41) mol
and
PO = XO × PT otal = 0.252 × 192 kPa = 48.4 kPa

2 2
For N2O,

nN O 8.41 mol
2
XN2 O = = = 0.748
nT otal (2.83 + 8.41) mol
and
PN2 O = XN2 O × PT otal = (0.748) × 192 kPa = 143.6 kPa
 Exercise 8.3.3
What is the pressure of a mixture of 0.200 g of H2, 1.00 g of N2, and 0.820 g of Ar in a container with a volume of 2.00 L at 20
°C?
Answer
1.87 atm
Collection of Gases over Water
A simple way to collect gases that do not react with water is to capture them in a bottle that has been filled with water and inverted
into a dish filled with water. The pressure of the gas inside the bottle can be made equal to the air pressure outside by raising or
lowering the bottle. When the water level is the same both inside and outside the bottle (Figure 8.3.3), the pressure of the gas is
equal to the atmospheric pressure, which can be measured with a barometer.
Figure 8.3.3 : When a reaction produces a gas that is collected above water, the trapped gas is a mixture of the gas produced by the
reaction and water vapor. If the collection flask is appropriately positioned to equalize the water levels both within and outside the
flask, the pressure of the trapped gas mixture will equal the atmospheric pressure outside the flask (see the earlier discussion of
manometers).
This figure shows a diagram of equipment used for collecting a gas over water. To the left is an Erlenmeyer flask. It is
approximately two thirds full of a lavender colored liquid. Bubbles are evident in the liquid. The label “Reaction Producing Gas”
appears below the flask. A line segment connects this label to the liquid in the flask. The flask has a stopper in it through which a
single glass tube extends from the open region above the liquid in the flask up, through the stopper, to the right, then angles down
into a pan that is nearly full of light blue water. This tube again extends right once it is well beneath the water’s surface. It then
bends up into an inverted flask which is labeled “Collection Flask.” This collection flask is positioned with its mouth beneath the
surface of the light blue water and appears approximately half full. Bubbles are evident in the water in the inverted flask. The open
space above the water in the inverted flask is labeled “collected gas.”
However, there is another factor we must consider when we measure the pressure of the gas by this method. Water evaporates and
there is always gaseous water (water vapor) above a sample of liquid water. As a gas is collected over water, it becomes saturated
with water vapor and the total pressure of the mixture equals the partial pressure of the gas plus the partial pressure of the water
vapor. The pressure of the pure gas is therefore equal to the total pressure minus the pressure of the water vapor—this is referred to
as the “dry” gas pressure, that is, the pressure of the gas only, without water vapor.

Figure 8.3.4 : This graph shows the vapor pressure of water at sea level as a function of temperature.
A graph is shown. The horizontal axis is labeled “Temperature ( degrees C )” with markings and labels provided for multiples of 20
beginning at 0 and ending at 100. The vertical axis is labeled “Vapor pressure ( torr )” with marking and labels provided for
multiples of 200, beginning at 0 and ending at 800. A smooth solid black curve extends from the origin up and to the right across
the graph. The graph shows a positive trend with an increasing rate of change. On the vertical axis is ( 7 60) and an arrow pointing
to it. The arrow is labeled, “Vapor pressure at ( 100 degrees C ).”
The vapor pressure of water, which is the pressure exerted by water vapor in equilibrium with liquid water in a closed container,
depends on the temperature (Figure 8.3.4); more detailed information on the temperature dependence of water vapor can be found
in Table 8.3.1, and vapor pressure will be discussed in more detail in the next chapter on liquids.
Table 8.3.1 : Vapor Pressure of Ice and Water in Various Temperatures at Sea Level
Temperature Temperature Temperature
Pressure (torr) Pressure (torr) Pressure (torr)
(°C) (°C) (°C)
–10 1.95 18 15.5 30 31.8
–5 3.0 19 16.5 35 42.2
–2 3.9 20 17.5 40 55.3
0 4.6 21 18.7 50 92.5
2 5.3 22 19.8 60 149.4
4 6.1 23 21.1 70 233.7
6 7.0 24 22.4 80 355.1
8 8.0 25 23.8 90 525.8
10 9.2 26 25.2 95 633.9
12 10.5 27 26.7 99 733.2
14 12.0 28 28.3 100.0 760.0
16 13.6 29 30.0 101.0 787.6
 Example 8.3.4: Pressure of a Gas Collected Over Water
If 0.200 L of argon is collected over water at a temperature of 26 °C and a pressure of 750 torr in a system like that shown in
Figure 8.3.3, what is the partial pressure of argon?
Solution
According to Dalton’s law, the total pressure in the bottle (750 torr) is the sum of the partial pressure of argon and the partial
pressure of gaseous water:
PT = PAr + PH2 O

Rearranging this equation to solve for the pressure of argon gives:
PAr = PT − PH2 O
The pressure of water vapor above a sample of liquid water at 26 °C is 25.2 torr (Appendix E), so:
PAr = 750 torr − 25.2 torr = 725 torr
 Exercise 8.3.4
A sample of oxygen collected over water at a temperature of 29.0 °C and a pressure of 764 torr has a volume of 0.560 L. What
volume would the dry oxygen have under the same conditions of temperature and pressure?
Answer
0.583 L
Chemical Stoichiometry and Gases
Chemical stoichiometry describes the quantitative relationships between reactants and products in chemical reactions. We have
previously measured quantities of reactants and products using masses for solids and volumes in conjunction with the molarity for
solutions; now we can also use gas volumes to indicate quantities. If we know the volume, pressure, and temperature of a gas, we
can use the ideal gas equation to calculate how many moles of the gas are present. If we know how many moles of a gas are
involved, we can calculate the volume of a gas at any temperature and pressure.
Avogadro’s Law Revisited
Sometimes we can take advantage of a simplifying feature of the stoichiometry of gases that solids and solutions do not exhibit: All
gases that show ideal behavior contain the same number of molecules in the same volume (at the same temperature and pressure).
Thus, the ratios of volumes of gases involved in a chemical reaction are given by the coefficients in the equation for the reaction,
provided that the gas volumes are measured at the same temperature and pressure.
We can extend Avogadro’s law (that the volume of a gas is directly proportional to the number of moles of the gas) to chemical
reactions with gases: Gases combine, or react, in definite and simple proportions by volume, provided that all gas volumes are
measured at the same temperature and pressure. For example, since nitrogen and hydrogen gases react to produce ammonia gas
according to
N (g) + 3 H (g) ⟶ 2 NH (g)

2 2 3
a given volume of nitrogen gas reacts with three times that volume of hydrogen gas to produce two times that volume of ammonia
gas, if pressure and temperature remain constant.
The explanation for this is illustrated in Figure 8.3.4. According to Avogadro’s law, equal volumes of gaseous N2, H2, and NH3, at
the same temperature and pressure, contain the same number of molecules. Because one molecule of N2 reacts with three
molecules of H2 to produce two molecules of NH3, the volume of H2 required is three times the volume of N2, and the volume of
NH3 produced is two times the volume of N2.

Figure 8.3.5 : One volume of N2 combines with three volumes of H2 to form two volumes of NH3.
This diagram provided models the chemical reaction written with formulas across the bottom of the figure. The reaction is written;
N subscript 2 plus 3 H subscript 2 followed by an arrow pointing right to N H subscript 3. Just above the formulas, space-filling
models are provided. Above N H subscript 2, two blue spheres are bonded. Above 3 H subscript 2, three pairs of two slightly
smaller white spheres are bonded. Above N H subscript 3, two molecules are shown composed each of a central blue sphere to
which three slightly smaller white spheres are bonded. Across the top of the diagram, the reaction is illustrated with balloons. To
the left is a light blue balloon which is labeled “N subscript 2”. This balloon contains a single space-filling model composed of two
bonded blue spheres. This balloon is followed by a plus sign, then three grey balloons which are each labeled “H subscript 2.” Each
of these balloons similarly contain a single space-filling model composed of two bonded white spheres. These white spheres are
slightly smaller than the blue spheres. An arrow follows which points right to two light green balloons which are each labeled “N H
subscript 3.” Each light green balloon contains a space-filling model composed of a single central blue sphere to which three
slightly smaller white spheres are bonded.
 Example 8.3.5: Reaction of Gases
Propane, C3H8(g), is used in gas grills to provide the heat for cooking. What volume of O2(g) measured at 25 °C and 760 torr is
required to react with 2.7 L of propane measured under the same conditions of temperature and pressure? Assume that the
propane undergoes complete combustion.
Solution
The ratio of the volumes of C3H8 and O2 will be equal to the ratio of their coefficients in the balanced equation for the reaction:
C H (g) + 5 O (g) ⟶ 3 CO (g) + 4 H O(l) (8.3.1)
3 8 2 2 2
1 volume + 5 volumes 3 volumes + 4 volumes (8.3.2)
From the equation, we see that one volume of C3H8 will react with five volumes of O2:
5 LO
2
2.7 L C3 H8 × = 13.5 L O
2
1 L C3 H8
A volume of 13.5 L of O2 will be required to react with 2.7 L of C3H8.
 Exercise 8.3.5
An acetylene tank for an oxyacetylene welding torch provides 9340 L of acetylene gas, C2H2, at 0 °C and 1 atm. How many
tanks of oxygen, each providing 7.00 × 103 L of O2 at 0 °C and 1 atm, will be required to burn the acetylene?
2C H +5 O ⟶ 4 CO +2 H O
2 2 2 2 2
Answer
3.34 tanks (2.34 × 104 L)

 Example 8.3.6: Volumes of Reacting Gases
Ammonia is an important fertilizer and industrial chemical. Suppose that a volume of 683 billion cubic feet of gaseous
ammonia, measured at 25 °C and 1 atm, was manufactured. What volume of H2(g), measured under the same conditions, was
required to prepare this amount of ammonia by reaction with N2?
N (g) + 3 H (g) ⟶ 2 NH (g)

2 2 3
Solution
Because equal volumes of H2 and NH3 contain equal numbers of molecules and each three molecules of H2 that react produce
two molecules of NH3, the ratio of the volumes of H2 and NH3 will be equal to 3:2. Two volumes of NH3, in this case in units
of billion ft3, will be formed from three volumes of H2:
3
3 billion f t H2
3 3 3
683 billion f t NH3 × = 1.02 × 10 billion f t H2
3
2 billion f t NH3
The manufacture of 683 billion ft3 of NH3 required 1020 billion ft3 of H2. (At 25 °C and 1 atm, this is the volume of a cube
with an edge length of approximately 1.9 miles.)
 Exercise 8.3.6
What volume of O2(g) measured at 25 °C and 760 torr is required to react with 17.0 L of ethylene, C2H4(g), measured under
the same conditions of temperature and pressure? The products are CO2 and water vapor.
Answer
51.0 L
 Example 8.3.7: Volume of Gaseous Product
What volume of hydrogen at 27 °C and 723 torr may be prepared by the reaction of 8.88 g of gallium with an excess of
hydrochloric acid?
2 Ga(s) + 6 HCl(aq) ⟶ 2 GaCl (aq) + 3 H (g)

3 2
Solution
To convert from the mass of gallium to the volume of H2(g), we need to do something like this:
The first two conversions are:
1 mol Ga 3 mol H2
8.88 g Ga × × = 0.191 mol H2
69.723 g Ga 2 mol Ga
Finally, we can use the ideal gas law:

−1 −1
nRT 0.191 mol × 0.08206 L atm mol K × 300 K
VH2 = ( ) = = 4.94 L
P 0.951 atm
H2

 Exercise 8.3.7
Sulfur dioxide is an intermediate in the preparation of sulfuric acid. What volume of SO2 at 343 °C and 1.21 atm is produced
by burning l.00 kg of sulfur in oxygen?
Answer
1.30 × 103 L
 Greenhouse Gases and Climate Change
The thin skin of our atmosphere keeps the earth from being an ice planet and makes it habitable. In fact, this is due to less than
1
0.5% of the air molecules. Of the energy from the sun that reaches the earth, almost is reflected back into space, with the
3
rest absorbed by the atmosphere and the surface of the earth. Some of the energy that the earth absorbs is re-emitted as infrared
(IR) radiation, a portion of which passes back out through the atmosphere into space. However, most of this IR radiation is
absorbed by certain substances in the atmosphere, known as greenhouse gases, which re-emit this energy in all directions,
trapping some of the heat. This maintains favorable living conditions—without atmosphere, the average global average
temperature of 14 °C (57 °F) would be about –19 °C (–2 °F). The major greenhouse gases (GHGs) are water vapor, carbon
dioxide, methane, and ozone. Since the Industrial Revolution, human activity has been increasing the concentrations of GHGs,
which have changed the energy balance and are significantly altering the earth’s climate (Figure 8.3.6).
Figure 8.3.6 : Greenhouse gases trap enough of the sun’s energy to make the planet habitable—this is known as the greenhouse
effect. Human activities are increasing greenhouse gas levels, warming the planet and causing more extreme weather events.
There is strong evidence from multiple sources that higher atmospheric levels of CO2 are caused by human activity, with fossil
3
fuel burning accounting for about of the recent increase in CO2. Reliable data from ice cores reveals that CO2 concentration
4
in the atmosphere is at the highest level in the past 800,000 years; other evidence indicates that it may be at its highest level in
20 million years. In recent years, the CO2 concentration has increased from historical levels of below 300 ppm to almost 400
ppm today (Figure 8.3.7).

Figure 8.3.7 : Figure CO2 levels over the past 700,000 years were typically from 200–300 ppm, with a steep, unprecedented
increase over the past 50 years.
Summary
The ideal gas law can be used to derive a number of convenient equations relating directly measured quantities to properties of
interest for gaseous substances and mixtures. Appropriate rearrangement of the ideal gas equation may be made to permit the
calculation of gas densities and molar masses. Dalton’s law of partial pressures may be used to relate measured gas pressures for
gaseous mixtures to their compositions. Avogadro’s law may be used in stoichiometric computations for chemical reactions
involving gaseous reactants or products.
Key Equations
PTotal = PA + PB + PC + … = ƩiPi
PA = XA PTotal
nA
XA =
nT otal
Footnotes
1. “Quotations by Joseph-Louis Lagrange,” last modified February 2006, accessed February 10, 2015, www-history.mcs.st-
andrews.ac.../Lagrange.html
Summary
Dalton’s law of partial pressures
total pressure of a mixture of ideal gases is equal to the sum of the partial pressures of the component gases.
mole fraction (X)

concentration unit defined as the ratio of the molar amount of a mixture component to the total number of moles of all mixture
components
partial pressure
pressure exerted by an individual gas in a mixture
vapor pressure of water

pressure exerted by water vapor in equilibrium with liquid water in a closed container at a specific temperature
This page titled 8.3: Stoichiometry of Gaseous Substances, Mixtures, and Reactions is shared under a CC BY license and was authored, remixed,
and/or curated by OpenStax.

9.3: Stoichiometry of Gaseous Substances, Mixtures, and Reactions is licensed CC BY 4.0. Original source:

Define and explain effusion and diffusion
State Graham’s law and use it to compute relevant gas properties
If you have ever been in a room when a piping hot pizza was delivered, you have been made aware of the fact that gaseous
molecules can quickly spread throughout a room, as evidenced by the pleasant aroma that soon reaches your nose. Although
gaseous molecules travel at tremendous speeds (hundreds of meters per second), they collide with other gaseous molecules and
travel in many different directions before reaching the desired target. At room temperature, a gaseous molecule will experience
billions of collisions per second. The mean free path is the average distance a molecule travels between collisions. The mean free
path increases with decreasing pressure; in general, the mean free path for a gaseous molecule will be hundreds of times the
diameter of the molecule
In general, we know that when a sample of gas is introduced to one part of a closed container, its molecules very quickly disperse
throughout the container; this process by which molecules disperse in space in response to differences in concentration is called
diffusion (shown in Figure 8.4.1). The gaseous atoms or molecules are, of course, unaware of any concentration gradient, they
simply move randomly—regions of higher concentration have more particles than regions of lower concentrations, and so a net
movement of species from high to low concentration areas takes place. In a closed environment, diffusion will ultimately result in
equal concentrations of gas throughout, as depicted in Figure 8.4.1. The gaseous atoms and molecules continue to move, but since
their concentrations are the same in both bulbs, the rates of transfer between the bulbs are equal (no net transfer of molecules
occurs).
Figure 8.4.1 : (a) Two gases, H2 and O2, are initially separated. (b) When the stopcock is opened, they mix together. The lighter gas,
H2, passes through the opening faster than O2, so just after the stopcock is opened, more H2 molecules move to the O2 side than O2
molecules move to the H2 side. (c) After a short time, both the slower-moving O2 molecules and the faster-moving H2 molecules
have distributed themselves evenly on both sides of the vessel.
In this figure, three pairs of gas filled spheres or vessels are shown connected with a stopcock between them. In a, the figure is
labeled, “Stopcock closed.” Above, the left sphere is labeled, “H subscript 2.” It contains approximately 30 small, white, evenly
distributed circles. The sphere to its right is labeled, “O subscript 2.” It contains approximately 30 small red evenly distributed
circles. In b, the figure is labeled, “Stopcock open.” The stopcock valve handle is now parallel to the tube connecting the two
spheres. On the left, approximately 9 small, white circles and 4 small, red circles are present, with the red spheres appearing
slightly closer to the stopcock. On the right side, approximately 25 small, red spheres and 21 small, white spheres are present, with
the concentration of white spheres slightly greater near the stopcock. In c, the figure is labeled “Some time after Stopcock open.” In
this situation, the red and white spheres appear evenly mixed and uniformly distributed throughout both spheres.
We are often interested in the rate of diffusion, the amount of gas passing through some area per unit time:
amount of gas passing through an area
rate of diffusion =
unit of time
The diffusion rate depends on several factors: the concentration gradient (the increase or decrease in concentration from one point
to another); the amount of surface area available for diffusion; and the distance the gas particles must travel. Note also that the time
required for diffusion to occur is inversely proportional to the rate of diffusion, as shown in the rate of diffusion equation.
A process involving movement of gaseous species similar to diffusion is effusion, the escape of gas molecules through a tiny hole
such as a pinhole in a balloon into a vacuum (Figure 8.4.1). Although diffusion and effusion rates both depend on the molar mass
of the gas involved, their rates are not equal; however, the ratios of their rates are the same.

Figure 8.4.2 : Diffusion occurs when gas molecules disperse throughout a container. Effusion occurs when a gas passes through an
opening that is smaller than the mean free path of the particles, that is, the average distance traveled between collisions. Effectively,
this means that only one particle passes through at a time.
This figure contains two cylindrical containers which are oriented horizontally. The first is labeled “Diffusion.” In this container,
approximately 25 purple and 25 green circles are shown, evenly distributed throughout the container. “Trails” behind some of the
circles indicate motion. In the second container, which is labeled “Effusion,” a boundary layer is evident across the center of the
cylindrical container, dividing the cylinder into two halves. A black arrow is drawn pointing through this boundary from left to
right. To the left of the boundary, approximately 16 green circles and 20 purple circles are shown again with motion indicated by
“trails” behind some of the circles. To the right of the boundary, only 4 purple and 16 green circles are shown.
If a mixture of gases is placed in a container with porous walls, the gases effuse through the small openings in the walls. The lighter
gases pass through the small openings more rapidly (at a higher rate) than the heavier ones (Figure 8.4.2). In 1832, Thomas
Graham studied the rates of effusion of different gases and formulated Graham’s law of effusion: The rate of effusion of a gas is
inversely proportional to the square root of the mass of its particles:
1
rate of effusion ∝ −−
√M
This means that if two gases A and B are at the same temperature and pressure, the ratio of their effusion rates is inversely
proportional to the ratio of the square roots of the masses of their particles:
−−−
rate of effusion of B √MA
= −−−
rate of effusion of A √MB
Figure 8.4.3 : A balloon filled with air (the blue one) remains full overnight. A balloon filled with helium (the green one) partially
deflates because the smaller, light helium atoms effuse through small holes in the rubber much more readily than the heavier
molecules of nitrogen and oxygen found in air. (credit: modification of work by Mark Ott)
This figure shows two photos. The first photo shows a blue balloon which floats above a green balloon. The green balloon is
resting on a surface. Both balloons are about the same size. The second photo shows the same two balloons, but the blue one is now
smaller than the green one. Both are resting on a surface.
 Example 8.4.1: Applying Graham’s Law to Rates of Effusion

Calculate the ratio of the rate of effusion of hydrogen to the rate of effusion of oxygen.
Solution
From Graham’s law, we have:

−−−−−−−−−
√1.43 g L−1
rate of effusion of hydrogen 1.20 4
= = =
−−−−−−−−−−−
rate of effusion of oxygen 0.300 1
√0.0899 g L−1
Using molar masses:

−1 −−
32 g mol √16
rate of effusion of hydrogen 4
= = – =
rate of effusion of oxygen −1 √1 1
2 g mol
Hydrogen effuses four times as rapidly as oxygen.
 Exercise 8.4.1
At a particular pressure and temperature, nitrogen gas effuses at the rate of 79 mL/s. Using the same apparatus at the same
temperature and pressure, at what rate will sulfur dioxide effuse?
Answer
52 mL/s
Here’s another example, making the point about how determining times differs from determining rates.
 Example 8.4.2: Effusion Time Calculations
It takes 243 s for 4.46 × 10−5 mol Xe to effuse through a tiny hole. Under the same conditions, how long will it take 4.46 ×
10−5 mol Ne to effuse?
Solution
It is important to resist the temptation to use the times directly, and to remember how rate relates to time as well as how it
relates to mass. Recall the definition of rate of effusion:
amount of gas transferred
rate of effusion =
time
and combine it with Graham’s law:

−−−−
rate of effusion of gas Xe √MNe
= −−−−
rate of effusion of gas Ne √MXe
To get:
amount of Xe transferred
−−−−
√MNe
time for Xe
= −−−−
amount of Ne transferred √MXe
time for Ne
Noting that amount of A = amount of B, and solving for time for Ne:
amount of Xe
−−−− −−−−
time for Ne √MNe √MNe
time for Xe
= = =
−−−− −−−−
time for Xe √MXe √MXe
amount of Ne
time for Ne
and substitute values:

−−−−−−−−− −

time f or Ne  20.2 g mol
= = 0.392
243 s ⎷
131.3 g mol
Finally, solve for the desired quantity:
time f or Ne = 0.392 × 243 s = 95.3 s
Note that this answer is reasonable: Since Ne is lighter than Xe, the effusion rate for Ne will be larger than that for Xe, which
means the time of effusion for Ne will be smaller than that for Xe.
 Exercise 8.4.2
2
A party balloon filled with helium deflates to of its original volume in 8.0 hours. How long will it take an identical balloon
3
1
filled with the same number of moles of air (ℳ = 28.2 g/mol) to deflate to of its original volume?
2
Answer
32 h
Finally, here is one more example showing how to calculate molar mass from effusion rate data.
 Example 8.4.3: Determining Molar Mass Using Graham’s Law
An unknown gas effuses 1.66 times more rapidly than CO2. What is the molar mass of the unknown gas? Can you make a
reasonable guess as to its identity?
Solution
From Graham’s law, we have:
−−−−−
rate of ef f usion of Unknown √MCO2
= −−−−−−−−
rate of ef f usion of CO2 √MUnknown
Plug in known data:

−−−−− −−−−
1.66 √44.0 g/mol
=
−−−−−−−−
1 √MUnknown
Solve:
44.0 g/mol
MUnknown = = 16.0 g/mol
2
(1.66)
The gas could well be CH4, the only gas with this molar mass.
 Exercise
Hydrogen gas effuses through a porous container 8.97-times faster than an unknown gas. Estimate the molar mass of the
unknown gas.
Answer
163 g/mol

 Application: Use of Diffusion for Uranium Enrichment
Gaseous diffusion has been used to produce enriched uranium for use in nuclear power plants and weapons. Naturally
occurring uranium contains only 0.72% of 235U, the kind of uranium that is “fissile,” that is, capable of sustaining a nuclear
fission chain reaction. Nuclear reactors require fuel that is 2–5% 235U, and nuclear bombs need even higher concentrations.
One way to enrich uranium to the desired levels is to take advantage of Graham’s law. In a gaseous diffusion enrichment plant,
uranium hexafluoride (UF6, the only uranium compound that is volatile enough to work) is slowly pumped through large
cylindrical vessels called diffusers, which contain porous barriers with microscopic openings. The process is one of diffusion
because the other side of the barrier is not evacuated. The 235UF6 molecules have a higher average speed and diffuse through
the barrier a little faster than the heavier 238UF6 molecules. The gas that has passed through the barrier is slightly enriched in
235UF and the residual gas is slightly depleted. The small difference in molecular weights between 235UF and 238UF only
6 6 6
about 0.4% enrichment, is achieved in one diffuser (Figure 8.4.4). But by connecting many diffusers in a sequence of stages
(called a cascade), the desired level of enrichment can be attained.
Figure 8.4.4 : In a diffuser, gaseous UF6 is pumped through a porous barrier, which partially separates 235UF6 from 238UF6 The
UF6 must pass through many large diffuser units to achieve sufficient enrichment in 235U.
This figure shows a large cylindrical container oriented horizontally. A narrow tube or pipe which is labeled “porous barrier”
runs horizontally through the center of the tube and extends a short distance out from the left and right ends of the cylinder. At
the far left, an arrow points right into the tube. This arrow is labele, “Uranium hexafluoride ( U F subscript 6 ).” A line segment
connects the label, “High pressure feed tube,” to the tube where it enters the cylinder. In the short region of tube outside the
cylinder, 5 small, purple circles and 4 small, green circles are present. Inside the cylinder, an arrow points right through the
tube which contains many evenly distributed, purple circles and a handful of green circles which decrease in quantity moving
left to right through the cylinder. Curved arrows extend from the inner area of the tube into the outer region of the cylinder.
Three of these arrows point into the area above the tube and three point into the area below. Two line segments extend from the
label, “Higher speed superscript 235 U F subscript 6 diffuses through barrier faster than superscript 238 U F subscript 6,” to
two green circles in the space above the tube. In the short section of tubing just outside the cylinder, 8 small, purple circles are
present. An arrow labeled, “Depleted superscript 238 U F subscript 6,” points right extending from the end of this tube. The
larger space outside the tube contains approximately 100 evenly distributed small green circles and only 5 purple circles. Eight
of the purple circles appear at the left end of the cylinder. A tube exits the lower right end of the cylinder. It has 5 green circles
followed by a right pointing arrow and the label, “Enriched superscript 235 U F subscript 6.”
The large scale separation of gaseous 235UF6 from 238UF6 was first done during the World War II, at the atomic energy
installation in Oak Ridge, Tennessee, as part of the Manhattan Project (the development of the first atomic bomb). Although
the theory is simple, this required surmounting many daunting technical challenges to make it work in practice. The barrier
must have tiny, uniform holes (about 10–6 cm in diameter) and be porous enough to produce high flow rates. All materials (the
barrier, tubing, surface coatings, lubricants, and gaskets) need to be able to contain, but not react with, the highly reactive and
corrosive UF6.
Because gaseous diffusion plants require very large amounts of energy (to compress the gas to the high pressures required and
drive it through the diffuser cascade, to remove the heat produced during compression, and so on), it is now being replaced by
gas centrifuge technology, which requires far less energy. A current hot political issue is how to deny this technology to Iran, to
prevent it from producing enough enriched uranium for them to use to make nuclear weapons.

Summary
Gaseous atoms and molecules move freely and randomly through space. Diffusion is the process whereby gaseous atoms and
molecules are transferred from regions of relatively high concentration to regions of relatively low concentration. Effusion is a
similar process in which gaseous species pass from a container to a vacuum through very small orifices. The rates of effusion of
gases are inversely proportional to the square roots of their densities or to the square roots of their atoms/molecules’ masses
(Graham’s law).
Key Equations
amount of gas passing through an area
rate of diffusion =
unit of time
−−
− −− −
rate of effusion of gas A √mB √MB
= =
−−
− −− −
rate of effusion of gas B √mA √MA
Summary
diffusion
movement of an atom or molecule from a region of relatively high concentration to one of relatively low concentration
(discussed in this chapter with regard to gaseous species, but applicable to species in any phase)
effusion
transfer of gaseous atoms or molecules from a container to a vacuum through very small openings
Graham’s law of effusion

rates of diffusion and effusion of gases are inversely proportional to the square roots of their molecular masses
mean free path

average distance a molecule travels between collisions
rate of diffusion
amount of gas diffusing through a given area over a given time
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State the postulates of the kinetic-molecular theory
Use this theory’s postulates to explain the gas laws
The gas laws that we have seen to this point, as well as the ideal gas equation, are empirical, that is, they have been derived from
experimental observations. The mathematical forms of these laws closely describe the macroscopic behavior of most gases at
pressures less than about 1 or 2 atm. Although the gas laws describe relationships that have been verified by many experiments,
they do not tell us why gases follow these relationships.
The kinetic molecular theory (KMT) is a simple microscopic model that effectively explains the gas laws described in previous
modules of this chapter. This theory is based on the following five postulates described here. (Note: The term “molecule” will be
used to refer to the individual chemical species that compose the gas, although some gases are composed of atomic species, for
example, the noble gases.)
1. Gases are composed of molecules that are in continuous motion, travelling in straight lines and changing direction only when
they collide with other molecules or with the walls of a container.
2. The molecules composing the gas are negligibly small compared to the distances between them.
3. The pressure exerted by a gas in a container results from collisions between the gas molecules and the container walls.
4. Gas molecules exert no attractive or repulsive forces on each other or the container walls; therefore, their collisions are elastic
(do not involve a loss of energy).
5. The average kinetic energy of the gas molecules is proportional to the kelvin temperature of the gas.
The test of the KMT and its postulates is its ability to explain and describe the behavior of a gas. The various gas laws can be
derived from the assumptions of the KMT, which have led chemists to believe that the assumptions of the theory accurately
represent the properties of gas molecules. We will first look at the individual gas laws (Boyle’s, Charles’s, Amontons’s,
Avogadro’s, and Dalton’s laws) conceptually to see how the KMT explains them. Then, we will more carefully consider the
relationships between molecular masses, speeds, and kinetic energies with temperature, and explain Graham’s law.
The Kinetic-Molecular Theory Explains the Behavior of Gases, Part I

Recalling that gas pressure is exerted by rapidly moving gas molecules and depends directly on the number of molecules hitting a
unit area of the wall per unit of time, we see that the KMT conceptually explains the behavior of a gas as follows:
Amontons’s law. If the temperature is increased, the average speed and kinetic energy of the gas molecules increase. If the
volume is held constant, the increased speed of the gas molecules results in more frequent and more forceful collisions with the
walls of the container, therefore increasing the pressure (Figure 8.5.1a).
Charles’s law. If the temperature of a gas is increased, a constant pressure may be maintained only if the volume occupied by
the gas increases. This will result in greater average distances traveled by the molecules to reach the container walls, as well as
increased wall surface area. These conditions will decrease both the frequency of molecule-wall collisions and the number of
collisions per unit area, the combined effects of which balance the effect of increased collision forces due to the greater kinetic
energy at the higher temperature.
Boyle’s law. If the gas volume is decreased, the container wall area decreases and the molecule-wall collision frequency
increases, both of which increase the pressure exerted by the gas (Figure 8.5.1b).
Avogadro’s law. At constant pressure and temperature, the frequency and force of molecule-wall collisions are constant. Under
such conditions, increasing the number of gaseous molecules will require a proportional increase in the container volume in
order to yield a decrease in the number of collisions per unit area to compensate for the increased frequency of collisions
(Figure 8.5.1c).
Dalton’s Law. Because of the large distances between them, the molecules of one gas in a mixture bombard the container walls
with the same frequency whether other gases are present or not, and the total pressure of a gas mixture equals the sum of the
(partial) pressures of the individual gases.

Figure 8.5.1 : (a) When gas temperature increases, gas pressure increases due to increased force and frequency of molecular
collisions. (b) When volume decreases, gas pressure increases due to increased frequency of molecular collisions. (c) When the
amount of gas increases at a constant pressure, volume increases to yield a constant number of collisions per unit wall area per unit
time.
This figure shows 3 pairs of pistons and cylinders. In a, which is labeled, “Charles’s Law,” the piston is positioned for the first
cylinder so that just over half of the available volume contains 6 purple spheres with trails behind them. The trails indicate
movement. Orange dashes extend from the interior surface of the cylinder where the spheres have collided. This cylinder is labeled,
“Baseline.” In the second cylinder, the piston is in the same position, and the label, “Heat” is indicated in red capitalized text. Four
red arrows with wavy stems are pointing upward to the base of the cylinder. The six purple spheres have longer trails behind them
and the number of orange dashes indicating points of collision with the container walls has increased. A rectangle beneath the
diagram states, “Temperature increased, Volume constant equals Increased pressure.” In b, which is labeled, “Boyle’s Law,” the
first, baseline cylinder shown is identical to the first cylinder in a. In the second cylinder, the piston has been moved, decreasing the
volume available to the 6 purple spheres to half of the initial volume. The six purple spheres have longer trails behind them and the
number of orange dashes indicating points of collision with the container walls has increased. This second cylinder is labeled,
“Volume decreased.” A rectangle beneath the diagram states, “Volume decreased, Wall area decreased equals Increased pressure.”
In c, which is labeled “Avogadro’s Law,” the first, baseline cylinder shown is identical to the first cylinder in a. In the second
cylinder, the number of purple spheres has changed from 6 to 12 and volume has doubled. This second cylinder is labeled
“Increased gas.” A rectangle beneath the diagram states, “At constant pressure, More gas molecules added equals Increased
volume.”
Molecular Velocities and Kinetic Energy

The previous discussion showed that the KMT qualitatively explains the behaviors described by the various gas laws. The
postulates of this theory may be applied in a more quantitative fashion to derive these individual laws. To do this, we must first
look at velocities and kinetic energies of gas molecules, and the temperature of a gas sample.
In a gas sample, individual molecules have widely varying speeds; however, because of the vast number of molecules and
collisions involved, the molecular speed distribution and average speed are constant. This molecular speed distribution is known as
a Maxwell-Boltzmann distribution, and it depicts the relative numbers of molecules in a bulk sample of gas that possesses a given
speed (Figure 8.5.2).

Figure 8.5.2 : The molecular speed distribution for oxygen gas at 300 K is shown here. Very few molecules move at either very low
or very high speeds. The number of molecules with intermediate speeds increases rapidly up to a maximum, which is the most
probable speed, then drops off rapidly. Note that the most probable speed, νp, is a little less than 400 m/s, while the root mean
square speed, urms, is closer to 500 m/s.
The kinetic energy (KE) of a particle of mass (m) and speed (u) is given by:
1
2
KE = mu
2
Expressing mass in kilograms and speed in meters per second will yield energy values in units of joules (J = kg m2 s–2). To deal
with a large number of gas molecules, we use averages for both speed and kinetic energy. In the KMT, the root mean square
velocity of a particle, urms, is defined as the square root of the average of the squares of the velocities with n = the number of
particles:
−−−−−−−−−−−−−−−−−−−
−− 2 2 2 2
¯
¯¯¯
¯ u +u +u +u +…
√ 2 1 2 3 4
urms = u =√
n
The average kinetic energy, KEavg, is then equal to:

1
2
KEavg = m urms
2
The KEavg of a collection of gas molecules is also directly proportional to the temperature of the gas and may be described by the
equation:
3
KEavg = RT
2
where R is the gas constant and T is the kelvin temperature. When used in this equation, the appropriate form of the gas constant is
8.314 J mol-1K-1 (8.314 kg m2s–2mol-1K–1). These two separate equations for KEavg may be combined and rearranged to yield a
relation between molecular speed and temperature:
1 3
2
m urms = RT
2 2
−−−−−
3RT
urms = √ (8.5.1)
m
 Example 8.5.1: Calculation of urms
Calculate the root-mean-square velocity for a nitrogen molecule at 30 °C.
Solution
Convert the temperature into Kelvin:
30°C + 273 = 303 K
Determine the mass of a nitrogen molecule in kilograms:

28.0 g
1 kg
× = 0.028 kg/mol
1 mol 1000 g
Replace the variables and constants in the root-mean-square velocity formula (Equation 8.5.1 ), replacing Joules with the
equivalent kg m2s–2:
−−−−−
3RT
urms = √
m
−−−−−−−−−−−−−−−−−−−−−
3(8.314 J/mol K)(303 K)
urms = √
(0.028 kg/mol)
− −−−− −−−− −−− −−

5 2 −2
= √ 2.70 × 10 m s
= 519 m/s
 Exercise 8.5.1
Calculate the root-mean-square velocity for an oxygen molecule at –23 °C.
Answer
441 m/s
If the temperature of a gas increases, its KEavg increases, more molecules have higher speeds and fewer molecules have lower
speeds, and the distribution shifts toward higher speeds overall, that is, to the right. If temperature decreases, KEavg decreases, more
molecules have lower speeds and fewer molecules have higher speeds, and the distribution shifts toward lower speeds overall, that
is, to the left. This behavior is illustrated for nitrogen gas in Figure 8.5.3.
Figure 8.5.3 : The molecular speed distribution for nitrogen gas (N2) shifts to the right and flattens as the temperature increases; it
shifts to the left and heightens as the temperature decreases.
A graph with four positively or right-skewed curves of varying heights is shown. The horizontal axis is labeled, “Velocity v ( m
divided by s ).” This axis is marked by increments of 500 beginning at 0 and extending up to 1500. The vertical axis is labeled,
“Fraction of molecules.” The label, “N subscript 2,” appears in the open space in the upper right area of the graph. The tallest and
narrowest of these curves is labeled, “100 K.” Its right end appears to touch the horizontal axis around 700 m per s. It is followed
by a slightly wider curve which is labeled, “200 K,” that is about three quarters of the height of the initial curve. Its right end
appears to touch the horizontal axis around 850 m per s. The third curve is significantly wider and only about half the height of the
initial curve. It is labeled, “500 K.” Its right end appears to touch the horizontal axis around 1450 m per s. The final curve is only
about one third the height of the initial curve. It is much wider than the others, so much so that its right end has not yet reached the
horizontal axis. This curve is labeled, “1000 K.”
At a given temperature, all gases have the same KEavg for their molecules. Gases composed of lighter molecules have more high-
speed particles and a higher urms, with a speed distribution that peaks at relatively higher velocities. Gases consisting of heavier
molecules have more low-speed particles, a lower urms, and a speed distribution that peaks at relatively lower velocities. This trend
is demonstrated by the data for a series of noble gases shown in Figure 8.5.4.

Figure 8.5.4 : Molecular velocity is directly related to molecular mass. At a given temperature, lighter molecules move faster on
average than heavier molecules.
A graph is shown with four positively or right-skewed curves of varying heights. The horizontal axis is labeled, “Velocity v ( m
divided by s ).” This axis is marked by increments of 500 beginning at 0 and extending up to 3000. The vertical axis is labeled,
“Fraction of molecules.” The tallest and narrowest of these curves is labeled, “X e.” Its right end appears to touch the horizontal
axis around 600 m per s. It is followed by a slightly wider curve which is labeled, “A r,” that is about half the height of the initial
curve. Its right end appears to touch the horizontal axis around 900 m per s. The third curve is significantly wider and just over a
third of the height of the initial curve. It is labeled, “N e.” Its right end appears to touch the horizontal axis around 1200 m per s.
The final curve is only about one fourth the height of the initial curve. It is much wider than the others, so much so that its right
reaches the horizontal axis around 2500 m per s. This curve is labeled, “H e.”
The gas simulator may be used to examine the effect of temperature on molecular
velocities. Examine the simulator’s “energy histograms” (molecular speed distributions)
and “species information” (which gives average speed values) for molecules of different
masses at various temperatures.
The Kinetic-Molecular Theory Explains the Behavior of Gases, Part II

According to Graham’s law, the molecules of a gas are in rapid motion and the molecules themselves are small. The average
distance between the molecules of a gas is large compared to the size of the molecules. As a consequence, gas molecules can move
past each other easily and diffuse at relatively fast rates.
The rate of effusion of a gas depends directly on the (average) speed of its molecules:
effusion rate ∝ urms
Using this relation, and the equation relating molecular speed to mass, Graham’s law may be easily derived as shown here:
−−−−−
3RT
urms = √
m
3RT 3RT
m = =
2 2
urms ¯¯
ū
−−−−−
3RT
√
−−−
−
ef f usion rate A urms A
mA mB
= = =√
−−−−−
ef f usion rate B urms B 3RT mA
√
mB
The ratio of the rates of effusion is thus derived to be inversely proportional to the ratio of the square roots of their masses. This is
the same relation observed experimentally and expressed as Graham’s law.
Summary
The kinetic molecular theory is a simple but very effective model that effectively explains ideal gas behavior. The theory assumes
that gases consist of widely separated molecules of negligible volume that are in constant motion, colliding elastically with one
another and the walls of their container with average velocities determined by their absolute temperatures. The individual

molecules of a gas exhibit a range of velocities, the distribution of these velocities being dependent on the temperature of the gas
and the mass of its molecules.
Key Equations
−−−−−−−−−−−−−−−−−−−
−− 2 2 2 2
¯
¯¯¯
¯
u +u +u +u +…
1 2 3 4
√ 2
urms = u =√
n
3
KEavg = RT
2
−−−−−
3RT
urms =√
m
Summary
kinetic molecular theory
theory based on simple principles and assumptions that effectively explains ideal gas behavior
root mean square velocity (urms)

measure of average velocity for a group of particles calculated as the square root of the average squared velocity
This page titled 8.5: The Kinetic-Molecular Theory is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
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Describe the physical factors that lead to deviations from ideal gas behavior
Explain how these factors are represented in the van der Waals equation
Define compressibility (Z) and describe how its variation with pressure reflects non-ideal behavior
Quantify non-ideal behavior by comparing computations of gas properties using the ideal gas law and the van der Waals
equation
Thus far, the ideal gas law, PV = nRT, has been applied to a variety of different types of problems, ranging from reaction
stoichiometry and empirical and molecular formula problems to determining the density and molar mass of a gas. As mentioned in
the previous modules of this chapter, however, the behavior of a gas is often non-ideal, meaning that the observed relationships
between its pressure, volume, and temperature are not accurately described by the gas laws. In this section, the reasons for these
deviations from ideal gas behavior are considered.
One way in which the accuracy of PV = nRT can be judged is by comparing the actual volume of 1 mole of gas (its molar volume,
Vm) to the molar volume of an ideal gas at the same temperature and pressure. This ratio is called the compressibility factor (Z)
with:
molar volume of gas at same T and P P Vm
Z = =( )
molar volume of ideal gas at same T and P RT
measured
Ideal gas behavior is therefore indicated when this ratio is equal to 1, and any deviation from 1 is an indication of non-ideal
behavior. Figure 8.6.1 shows plots of Z over a large pressure range for several common gases.
Figure 8.6.1 : A graph of the compressibility factor (Z) vs. pressure shows that gases can exhibit significant deviations from the
behavior predicted by the ideal gas law.
A graph is shown. The horizontal axis is labeled, “P ( a t m ).” Its scale begins at zero with markings provided by multiples of 200
up to 1000. The vertical axis is labeled, “Z le( k P a ).” This scale begins at zero and includes multiples of 0.5 up to 2.0. Six curves
are drawn of varying colors. One of these curves is a horizontal, light purple line extending right from 1.0 k P a on the vertical axis,
which is labeled “Ideal gas.” The region of the graph beneath this line is shaded tan. The remaining curves also start at the same
point on the vertical axis. An orange line extends to the upper right corner of the graph, reaching a value of approximately 1.7 k P a
at 1000 a t m. This orange curve is labeled, “H subscript 2.” A blue curve dips below the horizontal ideal gas line initially, then
increases to cross the line just past 200 a t m. This curve reaches a value of nearly 2.0 k P a at about 800 a t m. This curve is
labeled, “N subscript 2.” A red curve dips below the horizontal ideal gas line initially, then increases to cross the line just past 400 a
t m. This curve reaches a value of nearly 1.5 k P a at about 750 a t m. This curve is labeled, “O subscript 2.” A purple curve dips
below the horizontal ideal gas line, dipping even lower than the O subscript 2 curve initially, then increases to cross the ideal gas
line at about 400 a t m. This curve reaches a value of nearly 2.0 k P a at about 850 a t m. This curve is labeled, “C H subscript 4.” A
yellow curve dips below the horizontal ideal gas line, dipping lower than the other curves to a minimum of about 0.4 k P a at about
0.75 a t m, then increases to cross the ideal gas line at about 500 a t m. This curve reaches a value of about 1.6 k P a at about 900 a t
m. This curve is labeled, “C O subscript 2.”
As is apparent from Figure 8.6.1, the ideal gas law does not describe gas behavior well at relatively high pressures. To determine
why this is, consider the differences between real gas properties and what is expected of a hypothetical ideal gas.

Particles of a hypothetical ideal gas have no significant volume and do not attract or repel each other. In general, real gases
approximate this behavior at relatively low pressures and high temperatures. However, at high pressures, the molecules of a gas are
crowded closer together, and the amount of empty space between the molecules is reduced. At these higher pressures, the volume
of the gas molecules themselves becomes appreciable relative to the total volume occupied by the gas (Figure 8.6.2). The gas
therefore becomes less compressible at these high pressures, and although its volume continues to decrease with increasing
pressure, this decrease is not proportional as predicted by Boyle’s law.
Figure 8.6.2 : Raising the pressure of a gas increases the fraction of its volume that is occupied by the gas molecules and makes the
gas less compressible.
This figure includes three diagrams. In a, a cylinder with 9 purple spheres with trails indicating motion are shown. Above the
cylinder, the label, “Particles ideal gas,” is connected to two of the spheres with line segments extending into the square. The label
“Assumes” is beneath the square. In b, a cylinder and piston is shown. A relatively small open space is shaded lavender with 9
purple spheres packed close together. No motion trails are present on the spheres. Above the piston, a downward arrow labeled
“Pressure” is directed toward the enclosed area. In c, the cylinder is exactly the same as the first, but the number of molecules has
doubled.
At relatively low pressures, gas molecules have practically no attraction for one another because they are (on average) so far apart,
and they behave almost like particles of an ideal gas. At higher pressures, however, the force of attraction is also no longer
insignificant. This force pulls the molecules a little closer together, slightly decreasing the pressure (if the volume is constant) or
decreasing the volume (at constant pressure) (Figure 8.6.3). This change is more pronounced at low temperatures because the
molecules have lower KE relative to the attractive forces, and so they are less effective in overcoming these attractions after
colliding with one another.
Figure 8.6.3 : (a) Attractions between gas molecules serve to decrease the gas volume at constant pressure compared to an ideal gas
whose molecules experience no attractive forces. (b) These attractive forces will decrease the force of collisions between the
molecules and container walls, therefore reducing the pressure exerted compared to an ideal gas.
This figure includes two diagrams. Each involves two lavender shaded boxes that contain 14 relatively evenly distributed, purple
spheres. In the first box in a, a nearly centrally located purple sphere has 6 double-headed arrows extending outward from it to
nearby spheres. A single purple arrow is pointing right into open space. This box is labeled, “real.” There is a second box that looks
slightly larger than the first box in a. It has the same number of particles but no arrows. This box is labeled, “ideal.” In b, the first
box has a purple sphere at the right side which has 4 double-headed arrows radiating out to the top, bottom, and left to other
spheres. A single purple arrow points right through open space to the edge of the box. This box has no spheres positioned near its
right edge This box is labeled, “real.” The second box is the same size as the first box and contains the same number of particles.
There are no arrows in it, except for the purple arrow which appears to be bigger and bolder. This box is labeled, “ideal.”

There are several different equations that better approximate gas behavior than does the ideal gas law. The first, and simplest, of
these was developed by the Dutch scientist Johannes van der Waals in 1879. The van der Waals equation improves upon the ideal
gas law by adding two terms: one to account for the volume of the gas molecules and another for the attractive forces between
them.
This figure shows the equation P V equals n R T, with the P in blue text and the V in red text. This equation is followed by a right
pointing arrow. Following this arrow, to the right in blue text appears the equation ( P minus a n superscript 2 divided by V squared
),” which is followed by the red text ( V minus n b ). This is followed in black text with equals n R T. Beneath the second equation
appears the label, “Correction for molecular attraction” which is connected with a line segment to V squared. A second label,
“Correction for volume of molecules,” is similarly connected to n b which appears in red.
The constant a corresponds to the strength of the attraction between molecules of a particular gas, and the constant b corresponds to
2
n a
the size of the molecules of a particular gas. The “correction” to the pressure term in the ideal gas law is 2
, and the “correction”
V
to the volume is nb. Note that when V is relatively large and n is relatively small, both of these correction terms become negligible,
and the van der Waals equation reduces to the ideal gas law, PV = nRT. Such a condition corresponds to a gas in which a relatively
low number of molecules is occupying a relatively large volume, that is, a gas at a relatively low pressure. Experimental values for
the van der Waals constants of some common gases are given in Table 8.6.1.
Table 8.6.1 : Values of van der Waals Constants for Some Common Gases
Gas a (L2 atm/mol2) b (L/mol)
N2 1.39 0.0391
O2 1.36 0.0318
CO2 3.59 0.0427
H2O 5.46 0.0305
He 0.0342 0.0237
CCl4 20.4 0.1383
At low pressures, the correction for intermolecular attraction, a, is more important than the one for molecular volume, b. At high
pressures and small volumes, the correction for the volume of the molecules becomes important because the molecules themselves
are incompressible and constitute an appreciable fraction of the total volume. At some intermediate pressure, the two corrections
have opposing influences and the gas appears to follow the relationship given by PV = nRT over a small range of pressures. This
behavior is reflected by the “dips” in several of the compressibility curves shown in Figure 8.6.1. The attractive force between
molecules initially makes the gas more compressible than an ideal gas, as pressure is raised (Z decreases with increasing P). At
very high pressures, the gas becomes less compressible (Z increases with P), as the gas molecules begin to occupy an increasingly
significant fraction of the total gas volume.
Strictly speaking, the ideal gas equation functions well when intermolecular attractions between gas molecules are negligible and
the gas molecules themselves do not occupy an appreciable part of the whole volume. These criteria are satisfied under conditions
of low pressure and high temperature. Under such conditions, the gas is said to behave ideally, and deviations from the gas laws are
small enough that they may be disregarded—this is, however, very often not the case.
 Example 8.6.1: Comparison of Ideal Gas Law and van der Waals Equation
A 4.25-L flask contains 3.46 mol CO2 at 229 °C. Calculate the pressure of this sample of CO2:
a. from the ideal gas law
b. from the van der Waals equation

c. Explain the reason(s) for the difference.
Solution
(a) From the ideal gas law:
−1 −1
nRT 3.46 mol × 0.08206 L atm mol K × 502 K
P = = = 33.5 atm
V 4.25 L
(b) From the van der Waals equation:

2 2
n a nRT n a
(P + ) × (V − nb) = nRT ⟶ P = −
2 2
V (V − nb) V
−1 −1 2 2 2
3.46 mol × 0.08206 L atm mo l K × 502 K (3.46 mol ) × 3.59 L atm mo l
P = −
−1 2
(4.25 L − 3.46 mol × 0.0427 L mo l ) (4.25 L)
This finally yields P = 32.4 atm.

(c) This is not very different from the value from the ideal gas law because the pressure is not very high and the temperature is not
very low. The value is somewhat different because CO2 molecules do have some volume and attractions between molecules, and
the ideal gas law assumes they do not have volume or attractions.
 Exercise 8.6.1
A 560-mL flask contains 21.3 g N2 at 145 °C. Calculate the pressure of N2:
a. from the ideal gas law
b. from the van der Waals equation
c. Explain the reason(s) for the difference.
Answer a
46.562 atm
Answer b
46.594 atm
Answer c
The van der Waals equation takes into account the volume of the gas molecules themselves as well as intermolecular
attractions.
Summary
Gas molecules possess a finite volume and experience forces of attraction for one another. Consequently, gas behavior is not
necessarily described well by the ideal gas law. Under conditions of low pressure and high temperature, these factors are negligible,
the ideal gas equation is an accurate description of gas behavior, and the gas is said to exhibit ideal behavior. However, at lower
temperatures and higher pressures, corrections for molecular volume and molecular attractions are required to account for finite
molecular size and attractive forces. The van der Waals equation is a modified version of the ideal gas law that can be used to
account for the non-ideal behavior of gases under these conditions.
Key Equations
molar volume of gas at same T and P P × Vm
Z = =( )
molar volume of ideal gas at same T and P R×T
measured
2
n a
(P + ) × (V − nb) = nRT
2
V

Glossary
compressibility factor (Z)
ratio of the experimentally measured molar volume for a gas to its molar volume as computed from the ideal gas equation
van der Waals equation

modified version of the ideal gas equation containing additional terms to account for non-ideal gas behavior
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9.1: Gas Pressure
Q9.1.1
Why are sharp knives more effective than dull knives (Hint: think about the definition of pressure)?
S9.1.1
The cutting edge of a knife that has been sharpened has a smaller surface area than a dull knife. Since pressure is force per unit
area, a sharp knife will exert a higher pressure with the same amount of force and cut through material more effectively.
Q9.1.2
Why do some small bridges have weight limits that depend on how many wheels or axles the crossing vehicle has?
Q9.1.3
Why should you roll or belly-crawl rather than walk across a thinly-frozen pond?
S9.1.3
Lying down distributes your weight over a larger surface area, exerting less pressure on the ice compared to standing up. If you
exert less pressure, you are less likely to break through thin ice.
Q9.1.4
A typical barometric pressure in Redding, California, is about 750 mm Hg. Calculate this pressure in atm and kPa.
Q9.1.5
A typical barometric pressure in Denver, Colorado, is 615 mm Hg. What is this pressure in atmospheres and kilopascals?
S9.1.5
0.809 atm; 82.0 kPa
Q9.1.6
A typical barometric pressure in Kansas City is 740 torr. What is this pressure in atmospheres, in millimeters of mercury, and in
kilopascals?
Q9.1.7
Canadian tire pressure gauges are marked in units of kilopascals. What reading on such a gauge corresponds to 32 psi?
S9.1.7
2.2 × 102 kPa
Q9.1.8
During the Viking landings on Mars, the atmospheric pressure was determined to be on the average about 6.50 millibars (1 bar =
0.987 atm). What is that pressure in torr and kPa?
Q9.1.9
The pressure of the atmosphere on the surface of the planet Venus is about 88.8 atm. Compare that pressure in psi to the normal
pressure on earth at sea level in psi.
S9.1.9
Earth: 14.7 lb in–2; Venus: 13.1× 103 lb in−2
Q9.1.10
A medical laboratory catalog describes the pressure in a cylinder of a gas as 14.82 MPa. What is the pressure of this gas in
atmospheres and torr?

Q9.1.11
Consider this scenario and answer the following questions: On a mid-August day in the northeastern United States, the following
information appeared in the local newspaper: atmospheric pressure at sea level 29.97 in., 1013.9 mbar.
a. What was the pressure in kPa?
b. The pressure near the seacoast in the northeastern United States is usually reported near 30.0 in. Hg. During a hurricane, the
pressure may fall to near 28.0 in. Hg. Calculate the drop in pressure in torr.
S9.1.11
(a) 101.5 kPa; (b) 51 torr drop
Q9.1.12
Why is it necessary to use a nonvolatile liquid in a barometer or manometer?
Q9.1.13
The pressure of a sample of gas is measured at sea level with a closed-end manometer. The liquid in the manometer is mercury.
Determine the pressure of the gas in:
a. torr
b. Pa
c. bar
S9.1.13
(a) 264 torr; (b) 35,200 Pa; (c) 0.352 bar
Q9.1.14
The pressure of a sample of gas is measured with an open-end manometer, partially shown to the right. The liquid in the
manometer is mercury. Assuming atmospheric pressure is 29.92 in. Hg, determine the pressure of the gas in:
a. torr
b. Pa
c. bar

Q9.1.15
The pressure of a sample of gas is measured at sea level with an open-end mercury manometer. Assuming atmospheric pressure is
760.0 mm Hg, determine the pressure of the gas in:
a. mm Hg
b. atm
c. kPa
S9.1.15
(a) 623 mm Hg; (b) 0.820 atm; (c) 83.1 kPa
Q9.1.16
The pressure of a sample of gas is measured at sea level with an open-end mercury manometer. Assuming atmospheric pressure is
760 mm Hg, determine the pressure of the gas in:
a. mm Hg
b. atm
c. kPa
Q9.1.17
How would the use of a volatile liquid affect the measurement of a gas using open-ended manometers vs. closed-end manometers?
S9.1.17
With a closed-end manometer, no change would be observed, since the vaporized liquid would contribute equal, opposing pressures
in both arms of the manometer tube. However, with an open-ended manometer, a higher pressure reading of the gas would be
obtained than expected, since Pgas = Patm + Pvol liquid.

9.2: Relating Pressure, Volume, Amount, and Temperature: The Ideal Gas Law
Q9.2.1
Sometimes leaving a bicycle in the sun on a hot day will cause a blowout. Why?
Q9.2.2
Explain how the volume of the bubbles exhausted by a scuba diver (Figure) change as they rise to the surface, assuming that they
remain intact.
S9.2.2
As the bubbles rise, the pressure decreases, so their volume increases as suggested by Boyle’s law.
Q9.2.3
One way to state Boyle’s law is “All other things being equal, the pressure of a gas is inversely proportional to its volume.” (a)
What is the meaning of the term “inversely proportional?” (b) What are the “other things” that must be equal?
Q9.2.4
An alternate way to state Avogadro’s law is “All other things being equal, the number of molecules in a gas is directly proportional
to the volume of the gas.”
a. What is the meaning of the term “directly proportional?”
b. What are the “other things” that must be equal?
S9.2.4
(a) The number of particles in the gas increases as the volume increases. (b) temperature, pressure
Q9.2.5
How would the graph in Figure change if the number of moles of gas in the sample used to determine the curve were doubled?
The volume and temperature are linearly related for 1 mole of methane gas at a constant pressure of 1 atm. If the temperature is in
kelvin, volume and temperature are directly proportional. The line stops at 111 K because methane liquefies at this temperature;
when extrapolated, it intersects the graph’s origin, representing a temperature of absolute zero.
Q9.2.6
How would the graph in Figure change if the number of moles of gas in the sample used to determine the curve were doubled?

When a gas occupies a smaller volume, it exerts a higher pressure; when it occupies a larger volume, it exerts a lower pressure
(assuming the amount of gas and the temperature do not change). Since P and V are inversely proportional, a graph of 1/P vs. \
(V\) is linear.
S9.2.6
The curve would be farther to the right and higher up, but the same basic shape.
Q9.2.7
In addition to the data found in Figure, what other information do we need to find the mass of the sample of air used to determine
the graph?
Q9.2.8
Determine the volume of 1 mol of CH4 gas at 150 K and 1 atm, using Figure.
S9.2.8
16.3 to 16.5 L
Q9.2.9
Determine the pressure of the gas in the syringe shown in Figure when its volume is 12.5 mL, using:
a. the appropriate graph
b. Boyle’s law
Q9.2.10
A spray can is used until it is empty except for the propellant gas, which has a pressure of 1344 torr at 23 °C. If the can is thrown
into a fire (T = 475 °C), what will be the pressure in the hot can?
S9.2.10
3.40 × 103 torr

Q9.2.11
What is the temperature of an 11.2-L sample of carbon monoxide, CO, at 744 torr if it occupies 13.3 L at 55 °C and 744 torr?
S9.2.11
P1 V1 P2 V2
we must use = and solve for T1
T1 T2
P1 V1 T2
T1 =
P2 V2
Where:
P1 = 744 torr
V1 = 11.2 L
P2 = 744 torr
V2 = 13.3 L
T2 = 328.15° K
(744 torr)(11.2 L)(328.15° K)

= 276° K
(744 torr)(13.3 L)
276°K ; 3°C
Q9.2.12
A 2.50-L volume of hydrogen measured at –196 °C is warmed to 100 °C. Calculate the volume of the gas at the higher
temperature, assuming no change in pressure.
S9.2.13
12.1 L
Q9.2.14
A balloon inflated with three breaths of air has a volume of 1.7 L. At the same temperature and pressure, what is the volume of the
balloon if five more same-sized breaths are added to the balloon?
Q9.2.15
A weather balloon contains 8.80 moles of helium at a pressure of 0.992 atm and a temperature of 25 °C at ground level. What is the
volume of the balloon under these conditions?
S9.2.15
217 L
Q9.2.16
The volume of an automobile air bag was 66.8 L when inflated at 25 °C with 77.8 g of nitrogen gas. What was the pressure in the
bag in kPa?

Q9.2.17
How many moles of gaseous boron trifluoride, BF3, are contained in a 4.3410-L bulb at 788.0 K if the pressure is 1.220 atm? How
many grams of BF3?
S9.2.17
8.190 × 10–2 mol; 5.553 g
Q9.2.18
Iodine, I2, is a solid at room temperature but sublimes (converts from a solid into a gas) when warmed. What is the temperature in a
73.3-mL bulb that contains 0.292 g of I2 vapor at a pressure of 0.462 atm?
S9.2.18
1.) Use the equation P V = nRT and solve for T
PV
T =
nR
2.) convert grams of I2 to moles of I2 and convert mL to L

1 mole I
2 −3
0.292g I × = 1.15 × 10 moles I
2 2
253.8g I
2
73.3 mL = 0.0733 L
atm L
3.) Use these values along with R = 0.08206 to solve for T
mole °K
(0.462 atm )(0.0733 L )

T = = 359 °K
atm L
−3
(1.15 × 10 moles )(0.08206 )
mole °K
359°K ; 86°C
Q9.2.19
How many grams of gas are present in each of the following cases?
a. 0.100 L of CO2 at 307 torr and 26 °C
b. 8.75 L of C2H4, at 378.3 kPa and 483 K
c. 221 mL of Ar at 0.23 torr and –54 °C
S9.2.19
(a) 7.24 × 10–2 g; (b) 23.1 g; (c) 1.5 × 10–4 g
Q9.2.20
A high altitude balloon is filled with 1.41 × 104 L of hydrogen at a temperature of 21 °C and a pressure of 745 torr. What is the
volume of the balloon at a height of 20 km, where the temperature is –48 °C and the pressure is 63.1 torr?
Q9.2.21
A cylinder of medical oxygen has a volume of 35.4 L, and contains O2 at a pressure of 151 atm and a temperature of 25 °C. What
volume of O2 does this correspond to at normal body conditions, that is, 1 atm and 37 °C?
S9.2.21
5561 L
Q9.2.22
A large scuba tank (Figure) with a volume of 18 L is rated for a pressure of 220 bar. The tank is filled at 20 °C and contains enough
air to supply 1860 L of air to a diver at a pressure of 2.37 atm (a depth of 45 feet). Was the tank filled to capacity at 20 °C?

Q9.2.23
A 20.0-L cylinder containing 11.34 kg of butane, C4H10, was opened to the atmosphere. Calculate the mass of the gas remaining in
the cylinder if it were opened and the gas escaped until the pressure in the cylinder was equal to the atmospheric pressure, 0.983
atm, and a temperature of 27 °C.
S9.2.23
46.4 g
Q9.2.24
While resting, the average 70-kg human male consumes 14 L of pure O2 per hour at 25 °C and 100 kPa. How many moles of O2
are consumed by a 70 kg man while resting for 1.0 h?
Q9.2.25
For a given amount of gas showing ideal behavior, draw labeled graphs of:
a. the variation of P with V
b. the variation of V with T
c. the variation of P with T
1
d. the variation of with V
P
Q9.2.26
For a gas exhibiting ideal behavior:
Q9.2.27
A liter of methane gas, CH4, at STP contains more atoms of hydrogen than does a liter of pure hydrogen gas, H2, at STP. Using
Avogadro’s law as a starting point, explain why.

Q9.2.28
The effect of chlorofluorocarbons (such as CCl2F2) on the depletion of the ozone layer is well known. The use of substitutes, such
as CH3CH2F(g), for the chlorofluorocarbons, has largely corrected the problem. Calculate the volume occupied by 10.0 g of each
of these compounds at STP:
a. CCl2F2(g)
b. CH3CH2F(g)
S9.2.28
(a) 1.85 L CCl2F2; (b) 4.66 L CH3CH2F
Q9.2.29
As 1 g of the radioactive element radium decays over 1 year, it produces 1.16 × 1018 alpha particles (helium nuclei). Each alpha
particle becomes an atom of helium gas. What is the pressure in pascal of the helium gas produced if it occupies a volume of 125
mL at a temperature of 25 °C?
Q9.2.30
A balloon that is 100.21 L at 21 °C and 0.981 atm is released and just barely clears the top of Mount Crumpet in British Columbia.
If the final volume of the balloon is 144.53 L at a temperature of 5.24 °C, what is the pressure experienced by the balloon as it
clears Mount Crumpet?
S9.2.30
0.644 atm
Q9.2.31
If the temperature of a fixed amount of a gas is doubled at constant volume, what happens to the pressure?
Q9.2.32
If the volume of a fixed amount of a gas is tripled at constant temperature, what happens to the pressure?
S9.2.32
The pressure decreases by a factor of 3.

Q9.3.1
What is the density of laughing gas, dinitrogen monoxide, N2O, at a temperature of 325 K and a pressure of 113.0 kPa?
S9.3.1
1.) First convert kPa to atm
1 atm
113.0 kP a × = 1.115 atm
101.325 kP a
PM
2.) The use the equation d = where d = density in g L-1 and M = molar mass in g mol-1
RT
g
(1.115 atm)(44.02 )
mol g
d = = 1.84
atm L L
(0.08206 )(325 °K )
mole °K
Q9.3.2
Calculate the density of Freon 12, CF2Cl2, at 30.0 °C and 0.954 atm.

S9.3.2
4.64 g L−1
Q9.3.3
Which is denser at the same temperature and pressure, dry air or air saturated with water vapor? Explain.
Q9.3.4
A cylinder of O2(g) used in breathing by emphysema patients has a volume of 3.00 L at a pressure of 10.0 atm. If the temperature
of the cylinder is 28.0 °C, what mass of oxygen is in the cylinder?
S9.3.4
38.8 g
Q9.3.5
What is the molar mass of a gas if 0.0494 g of the gas occupies a volume of 0.100 L at a temperature 26 °C and a pressure of 307
torr?
S9.3.5
1.) convert torr to atm and °C to °K
307 torr = 0.404atm
26°C = 300.°K
2.) Use the equation P V = nRT and solve for n

PV
n =
RT
(0.404 atm )(0.100 L )

n = = 0.00165 moles
atm L
(0.08206 )(300. °K )
mol °K
3.) Then divide grams by the number of moles to obtain the molar mass:
0.0494g g
= 30.0
0.00165 moles mole
Q9.3.6
What is the molar mass of a gas if 0.281 g of the gas occupies a volume of 125 mL at a temperature 126 °C and a pressure of 777
torr?
S9.3.6
72.0 g mol−1
Q9.3.7
How could you show experimentally that the molecular formula of propene is C3H6, not CH2?
Q9.3.8
The density of a certain gaseous fluoride of phosphorus is 3.93 g/L at STP. Calculate the molar mass of this fluoride and determine
its molecular formula.
S9.3.8
88.1 g mol−1; PF3
Q9.3.9
Consider this question: What is the molecular formula of a compound that contains 39% C, 45% N, and 16% H if 0.157 g of the
compound occupies 125 mL with a pressure of 99.5 kPa at 22 °C?

a. Outline the steps necessary to answer the question.
Q9.3.10
A 36.0–L cylinder of a gas used for calibration of blood gas analyzers in medical laboratories contains 350 g CO2, 805 g O2, and
4,880 g N2. At 25 degrees C, what is the pressure in the cylinder in atmospheres?
S9.3.10
141 atm
Q9.3.11
A cylinder of a gas mixture used for calibration of blood gas analyzers in medical laboratories contains 5.0% CO2, 12.0% O2, and
the remainder N2 at a total pressure of 146 atm. What is the partial pressure of each component of this gas? (The percentages given
indicate the percent of the total pressure that is due to each component.)
Q9.3.12
A sample of gas isolated from unrefined petroleum contains 90.0% CH4, 8.9% C2H6, and 1.1% C3H8 at a total pressure of 307.2
kPa. What is the partial pressure of each component of this gas? (The percentages given indicate the percent of the total pressure
that is due to each component.)
S9.3.12
CH4: 276 kPa; C2H6: 27 kPa; C3H8: 3.4 kPa
Q9.3.13
A mixture of 0.200 g of H2, 1.00 g of N2, and 0.820 g of Ar is stored in a closed container at STP. Find the volume of the container,
assuming that the gases exhibit ideal behavior.
Q9.3.14
Most mixtures of hydrogen gas with oxygen gas are explosive. However, a mixture that contains less than 3.0 % O2 is not. If
enough O2 is added to a cylinder of H2 at 33.2 atm to bring the total pressure to 34.5 atm, is the mixture explosive?
S9.3.14
Yes
Q9.3.15
A commercial mercury vapor analyzer can detect, in air, concentrations of gaseous Hg atoms (which are poisonous) as low as 2 ×
10−6 mg/L of air. At this concentration, what is the partial pressure of gaseous mercury if the atmospheric pressure is 733 torr at 26
°C?
Q9.3.16
A sample of carbon monoxide was collected over water at a total pressure of 756 torr and a temperature of 18 °C. What is the
pressure of the carbon monoxide? (See Table for the vapor pressure of water.)
S9.3.16
740 torr
Q9.3.17
In an experiment in a general chemistry laboratory, a student collected a sample of a gas over water. The volume of the gas was 265
mL at a pressure of 753 torr and a temperature of 27 °C. The mass of the gas was 0.472 g. What was the molar mass of the gas?
Q9.3.18
Joseph Priestley first prepared pure oxygen by heating mercuric oxide, HgO:
2 HgO(s) ⟶ 2 Hg(l) + O (g)
2

a. Outline the steps necessary to answer the following question: What volume of O2 at 23 °C and 0.975 atm is produced by the
decomposition of 5.36 g of HgO?
S9.3.18
(a) Determine the moles of HgO that decompose; using the chemical equation, determine the moles of O2 produced by
decomposition of this amount of HgO; and determine the volume of O2 from the moles of O2, temperature, and pressure. (b) 0.308
L
Q9.3.19
Cavendish prepared hydrogen in 1766 by the novel method of passing steam through a red-hot gun barrel:
4 H O(g) + 3 Fe(s) ⟶ Fe O (s) + 4 H (g) (8.E.1)
2 3 4 2
a. Outline the steps necessary to answer the following question: What volume of H2 at a pressure of 745 torr and a temperature of
20 °C can be prepared from the reaction of 15.O g of H2O?
Q9.3.20
The chlorofluorocarbon CCl2F2 can be recycled into a different compound by reaction with hydrogen to produce CH2F2(g), a
compound useful in chemical manufacturing:
CCl F (g) + 4 H (g) ⟶ CH F (g) + 2 HCl(g) (8.E.2)
2 2 2 2 2
a. Outline the steps necessary to answer the following question: What volume of hydrogen at 225 atm and 35.5 °C would be
required to react with 1 ton (1.000 × 103 kg) of CCl2F2?
S9.3.20
a. Determine the molar mass of CCl2F2. From the balanced equation, calculate the moles of H2 needed for the complete reaction.
From the ideal gas law, convert moles of H2 into volume.
b. 3.72 × 103 L
Q9.3.21
Automobile air bags are inflated with nitrogen gas, which is formed by the decomposition of solid sodium azide (NaN3). The other
product is sodium metal. Calculate the volume of nitrogen gas at 27 °C and 756 torr formed by the decomposition of 125 g of
sodium azide.
Q9.3.22
Lime, CaO, is produced by heating calcium carbonate, CaCO3; carbon dioxide is the other product.
a. Outline the steps necessary to answer the following question: What volume of carbon dioxide at 875° and 0.966 atm is
produced by the decomposition of 1 ton (1.000 × 103 kg) of calcium carbonate?
S9.3.22
(a) Balance the equation. Determine the grams of CO2 produced and the number of moles. From the ideal gas law, determine the
volume of gas. (b) 7.43 × 105 L
Q9.3.23
Before small batteries were available, carbide lamps were used for bicycle lights. Acetylene gas, C2H2, and solid calcium
hydroxide were formed by the reaction of calcium carbide, CaC2, with water. The ignition of the acetylene gas provided the light.
Currently, the same lamps are used by some cavers, and calcium carbide is used to produce acetylene for carbide cannons.
a. Outline the steps necessary to answer the following question: What volume of C2H2 at 1.005 atm and 12.2 °C is formed by the
reaction of 15.48 g of CaC2 with water?

Q9.3.24
Calculate the volume of oxygen required to burn 12.00 L of ethane gas, C2H6, to produce carbon dioxide and water, if the volumes
of C2H6 and O2 are measured under the same conditions of temperature and pressure.
S9.3.24
42.00 L
Q9.3.25
What volume of O2 at STP is required to oxidize 8.0 L of NO at STP to NO2? What volume of NO2 is produced at STP?
Q9.3.26
Consider the following questions:
a. What is the total volume of the CO2(g) and H2O(g) at 600 °C and 0.888 atm produced by the combustion of 1.00 L of C2H6(g)
measured at STP?
b. What is the partial pressure of H2O in the product gases?
S9.3.26
(a) 18.0 L; (b) 0.533 atm
Q9.3.27
Methanol, CH3OH, is produced industrially by the following reaction:
copper catalyst 300 °C, 300 atm
CO(g) + 2 H (g) −−−−−−−−−−−−−−−−−−→ CH OH(g) (8.E.3)

2 3
Q9.3.28
Assuming that the gases behave as ideal gases, find the ratio of the total volume of the reactants to the final volume.
Q9.3.29
What volume of oxygen at 423.0 K and a pressure of 127.4 kPa is produced by the decomposition of 129.7 g of BaO2 to BaO and
O2?
S9.3.29
10.57 L O2
Q9.3.30
A 2.50-L sample of a colorless gas at STP decomposed to give 2.50 L of N2 and 1.25 L of O2 at STP. What is the colorless gas?
Q9.3.31
Ethanol, C2H5OH, is produced industrially from ethylene, C2H4, by the following sequence of reactions:
3C H + 2 H SO ⟶ C H HSO + (C H ) SO (8.E.4)
2 4 2 4 2 5 4 2 5 2 4
C H HSO + (C H ) SO + 3 H O ⟶ 3 C H OH + 2 H SO (8.E.5)
2 5 4 2 5 2 4 2 2 5 2 4
What volume of ethylene at STP is required to produce 1.000 metric ton (1000 kg) of ethanol if the overall yield of ethanol is
90.1%?
S9.3.31
5.40 × 105 L
Q9.3.32
One molecule of hemoglobin will combine with four molecules of oxygen. If 1.0 g of hemoglobin combines with 1.53 mL of
oxygen at body temperature (37 °C) and a pressure of 743 torr, what is the molar mass of hemoglobin?

Q9.3.33
A sample of a compound of xenon and fluorine was confined in a bulb with a pressure of 18 torr. Hydrogen was added to the bulb
until the pressure was 72 torr. Passage of an electric spark through the mixture produced Xe and HF. After the HF was removed by
reaction with solid KOH, the final pressure of xenon and unreacted hydrogen in the bulb was 36 torr. What is the empirical formula
of the xenon fluoride in the original sample? (Note: Xenon fluorides contain only one xenon atom per molecule.)
S9.3.33
XeF2
Q9.3.34
One method of analyzing amino acids is the van Slyke method. The characteristic amino groups (−NH2) in protein material are
allowed to react with nitrous acid, HNO2, to form N2 gas. From the volume of the gas, the amount of amino acid can be
determined. A 0.0604-g sample of a biological sample containing glycine, CH2(NH2)COOH, was analyzed by the van Slyke
method and yielded 3.70 mL of N2 collected over water at a pressure of 735 torr and 29 °C. What was the percentage of glycine in
the sample?
CH (NH )CO H + HNO ⟶ CH (OH)CO H + H O + N
2 2 2 2 2 2 2 2

Q9.4.1
A balloon filled with helium gas is found to take 6 hours to deflate to 50% of its original volume. How long will it take for an
identical balloon filled with the same volume of hydrogen gas (instead of helium) to decrease its volume by 50%?
S9.4.1
4.2 hours
Q9.4.2
Explain why the numbers of molecules are not identical in the left- and right-hand bulbs shown in the center illustration of Figure.
Q9.4.3
Starting with the definition of rate of effusion and Graham’s finding relating rate and molar mass, show how to derive the Graham’s
law equation, relating the relative rates of effusion for two gases to their molecular masses.
S9.4.3
Effusion can be defined as the process by which a gas escapes through a pinhole into a vacuum. Graham’s law states that with a
1/2
rate A molar mass of B
mixture of two gases A and B: ( ) =( ) . Both A and B are in the same container at the same
rate B molar mass of A
temperature, and therefore will have the same kinetic energy:

1/2
2 2 1/2 1/2
1 1 1 v mB v mB vA mB
KEA = KEB KE = mv
2
Therefore, 2
mA v
A
= mB v
2
B
A
= (
A
) =( ) =( )
2 2
2 2 2 v mA v mA vB mA
B B
Q9.4.4
Heavy water, D2O (molar mass = 20.03 g mol–1), can be separated from ordinary water, H2O (molar mass = 18.01), as a result of
the difference in the relative rates of diffusion of the molecules in the gas phase. Calculate the relative rates of diffusion of H2O and
D2O.
Q9.4.5
Which of the following gases diffuse more slowly than oxygen? F2, Ne, N2O, C2H2, NO, Cl2, H2S
S9.4.5
F2, N2O, Cl2, H2S

Q9.4.6
During the discussion of gaseous diffusion for enriching uranium, it was claimed that 235UF6 diffuses 0.4% faster than 238UF6.
Show the calculation that supports this value. The molar mass of 235UF6 = 235.043930 + 6 × 18.998403 = 349.034348 g/mol, and
the molar mass of 238UF6 = 238.050788 + 6 × 18.998403 = 352.041206 g/mol.
Q9.4.7
Calculate the relative rate of diffusion of 1H2 (molar mass 2.0 g/mol) compared to that of 2H2 (molar mass 4.0 g/mol) and the
relative rate of diffusion of O2 (molar mass 32 g/mol) compared to that of O3 (molar mass 48 g/mol).
S9.4.7
1.4; 1.2
Q9.4.8
A gas of unknown identity diffuses at a rate of 83.3 mL/s in a diffusion apparatus in which carbon dioxide diffuses at the rate of
102 mL/s. Calculate the molecular mass of the unknown gas.
Q9.4.9
When two cotton plugs, one moistened with ammonia and the other with hydrochloric acid, are simultaneously inserted into
opposite ends of a glass tube that is 87.0 cm long, a white ring of NH4Cl forms where gaseous NH3 and gaseous HCl first come
into contact. (Hint: Calculate the rates of diffusion for both NH3 and HCl, and find out how much faster NH3 diffuses than HCl.)
NH (g) + HCl(g) ⟶ NH Cl(s) (8.E.6)
3 4
Q9.4.10
At approximately what distance from the ammonia moistened plug does this occur?
S9.4.10
51.7 cm
Q9.5.1
Using the postulates of the kinetic molecular theory, explain why a gas uniformly fills a container of any shape.
Q9.5.2
Can the speed of a given molecule in a gas double at constant temperature? Explain your answer.
S9.5.2
Yes. At any given instant, there are a range of values of molecular speeds in a sample of gas. Any single molecule can speed up or
slow down as it collides with other molecules. The average velocity of all the molecules is constant at constant temperature.
Q9.5.3
Describe what happens to the average kinetic energy of ideal gas molecules when the conditions are changed as follows:
a. The pressure of the gas is increased by reducing the volume at constant temperature.
b. The pressure of the gas is increased by increasing the temperature at constant volume.
c. The average velocity of the molecules is increased by a factor of 2.
Q9.5.4
The distribution of molecular velocities in a sample of helium is shown in Figure. If the sample is cooled, will the distribution of
velocities look more like that of H2 or of H2O? Explain your answer.

S9.5.4
H2O. Cooling slows the velocities of the He atoms, causing them to behave as though they were heavier.
Q9.5.5
What is the ratio of the average kinetic energy of a SO2 molecule to that of an O2 molecule in a mixture of two gases? What is the
ratio of the root mean square speeds, urms, of the two gases?
Q9.5.6
A 1-L sample of CO initially at STP is heated to 546 °C, and its volume is increased to 2 L.
a. What effect do these changes have on the number of collisions of the molecules of the gas per unit area of the container wall?
b. What is the effect on the average kinetic energy of the molecules?
c. What is the effect on the root mean square speed of the molecules?
S9.5.6
(a) The number of collisions per unit area of the container wall is constant. (b) The average kinetic energy doubles. (c) The root
–
mean square speed increases to √2 times its initial value; urms is proportional to KE . avg
Q9.5.7
The root mean square speed of H2 molecules at 25 °C is about 1.6 km/s. What is the root mean square speed of a N2 molecule at 25
°C?
Q9.5.8
a. Is the pressure of the gas in the hot air balloon shown at the opening of this chapter greater than, less than, or equal to that of the
atmosphere outside the balloon?
b. Is the density of the gas in the hot air balloon shown at the opening of this chapter greater than, less than, or equal to that of the
atmosphere outside the balloon?
c. At a pressure of 1 atm and a temperature of 20 °C, dry air has a density of 1.2256 g/L. What is the (average) molar mass of dry
air?
d. The average temperature of the gas in a hot air balloon is 1.30 × 102 °F. Calculate its density, assuming the molar mass equals
that of dry air.
e. The lifting capacity of a hot air balloon is equal to the difference in the mass of the cool air displaced by the balloon and the
mass of the gas in the balloon. What is the difference in the mass of 1.00 L of the cool air in part (c) and the hot air in part (d)?
f. An average balloon has a diameter of 60 feet and a volume of 1.1 × 105 ft3. What is the lifting power of such a balloon? If the
weight of the balloon and its rigging is 500 pounds, what is its capacity for carrying passengers and cargo?
g. A balloon carries 40.0 gallons of liquid propane (density 0.5005 g/L). What volume of CO2 and H2O gas is produced by the
combustion of this propane?
h. A balloon flight can last about 90 minutes. If all of the fuel is burned during this time, what is the approximate rate of heat loss
(in kJ/min) from the hot air in the bag during the flight?
S9.5.1
(a) equal; (b) less than; (c) 29.48 g mol−1; (d) 1.0966 g L−1; (e) 0.129 g/L; (f) 4.01 × 105 g; net lifting capacity = 384 lb; (g) 270 L;
(h) 39.1 kJ min−1
Q9.5.1
R1
Show that the ratio of the rate of diffusion of Gas 1 to the rate of diffusion of Gas 2, , is the same at 0 °C and 100 °C.
R2

Q9.6.1
Graphs showing the behavior of several different gases follow. Which of these gases exhibit behavior significantly different from
that expected for ideal gases?
S9.6.1
Gases C, E, and F
Q9.6.3
Explain why the plot of PV for CO2 differs from that of an ideal gas.

Q9.6.3
Under which of the following sets of conditions does a real gas behave most like an ideal gas, and for which conditions is a real gas
expected to deviate from ideal behavior? Explain.
a. high pressure, small volume
b. high temperature, low pressure
c. low temperature, high pressure
S9.6.3
The gas behavior most like an ideal gas will occur under the conditions in (b). Molecules have high speeds and move through
greater distances between collision; they also have shorter contact times and interactions are less likely. Deviations occur with the
conditions described in (a) and (c). Under conditions of (a), some gases may liquefy. Under conditions of (c), most gases will
liquefy.
Q9.6.4
Describe the factors responsible for the deviation of the behavior of real gases from that of an ideal gas.
Q9.6.5
For which of the following gases should the correction for the molecular volume be largest: CO, CO2, H2, He, NH3, SF6?
S9.6.6
SF6
Q9.6.7
A 0.245-L flask contains 0.467 mol CO2 at 159 °C. Calculate the pressure:
a. using the ideal gas law
b. using the van der Waals equation
c. Explain the reason for the difference.
d. Identify which correction (that for P or V) is dominant and why.

Q9.6.8
a. If XX behaved as an ideal gas, what would its graph of Z vs. P look like?
b. For most of this chapter, we performed calculations treating gases as ideal. Was this justified?
c. What is the effect of the volume of gas molecules on Z? Under what conditions is this effect small? When is it large? Explain
using an appropriate diagram.
d. What is the effect of intermolecular attractions on the value of Z? Under what conditions is this effect small? When is it large?
Explain using an appropriate diagram.
e. In general, under what temperature conditions would you expect Z to have the largest deviations from the Z for an ideal gas?
S9.6.8
(a) A straight horizontal line at 1.0; (b) When real gases are at low pressures and high temperatures they behave close enough to
ideal gases that they are approximated as such, however, in some cases, we see that at a high pressure and temperature, the ideal
gas approximation breaks down and is significantly different from the pressure calculated by the van der Waals equation (c) The
greater the compressibility, the more the volume matters. At low pressures, the correction factor for intermolecular attractions is
more significant, and the effect of the volume of the gas molecules on Z would be a small lowering compressibility. At higher
pressures, the effect of the volume of the gas molecules themselves on Z would increase compressibility (see Figure) (d) Once
again, at low pressures, the effect of intermolecular attractions on Z would be more important than the correction factor for the
volume of the gas molecules themselves, though perhaps still small. At higher pressures and low temperatures, the effect of
intermolecular attractions would be larger. See Figure. (e) low temperatures
Exercises
Graphs showing the behavior of several different gases follow. Which of these gases exhibit behavior significantly different from
that expected for ideal gases?
Gases C, E, and F
Explain why the plot of PV for CO2 differs from that of an ideal gas.

A graph is shown. The horizontal axis is labeled, “P ( a t m ).” Its scale is marked at 0, 1, and 2. The vertical axis is labeled, “P V ( a t m L ).” This scale includes markings at 0, 22.4, 22.5, and 22.6. Two curves and
two lines are drawn of varying colors. One line is a horizontal, blue line extending right from about 22.42 a t m L on the vertical axis, and is labeled, “Ideal gas.” The remaining two curves and one line start at the same
point on the vertical axis. A green line extends up and to the right slightly on the graph, reaching a value of approximately 22.46 a t m L at 2 a t m. This green line is labeled, “H e.” An orange curve dips below the
horizontal ideal gas line initially, then increases to cross the line just past 1 a t m. This curve reaches a value of about 22.52 a t m L at 2 a t m. This curve is labeled, “C H subscript 4.” A purple curve dips below the
horizontal ideal gas line initially, then increases to cross the line at about 0.8 a t m. This curve reaches a value of nearly 22.62 a t m L at nearly 1.2 a t m. This curve is labeled, “C O subscript 2.”
Under which of the following sets of conditions does a real gas behave most like an ideal gas, and for which conditions is a real gas
expected to deviate from ideal behavior? Explain.
(a) high pressure, small volume
(b) high temperature, low pressure
(c) low temperature, high pressure
The gas behavior most like an ideal gas will occur under the conditions in (b). Molecules have high speeds and move through
greater distances between collision; they also have shorter contact times and interactions are less likely. Deviations occur with the
conditions described in (a) and (c). Under conditions of (a), some gases may liquefy. Under conditions of (c), most gases will
liquefy.
Describe the factors responsible for the deviation of the behavior of real gases from that of an
ideal gas.
For which of the following gases should the correction for the molecular volume be largest:
CO, CO2, H2, He, NH3, SF6?
SF6
A 0.245-L flask contains 0.467 mol CO2 at 159 °C. Calculate the pressure:
(a) using the ideal gas law
(b) using the van der Waals equation
(c) Explain the reason for the difference.
(d) Identify which correction (that for P or V) is dominant and why.
(a) If XX behaved as an ideal gas, what would its graph of Z vs. P look like?
(b) For most of this chapter, we performed calculations treating gases as ideal. Was this justified?
(c) What is the effect of the volume of gas molecules on Z? Under what conditions is this effect small? When is it large? Explain
using an appropriate diagram.
(d) What is the effect of intermolecular attractions on the value of Z? Under what conditions is this effect small? When is it large?
Explain using an appropriate diagram.
(e) In general, under what temperature conditions would you expect Z to have the largest deviations from the Z for an ideal gas?
(a) A straight horizontal line at 1.0; (b) When real gases are at low pressures and high temperatures they behave close enough to
ideal gases that they are approximated as such, however, in some cases, we see that at a high pressure and temperature, the ideal
gas approximation breaks down and is significantly different from the pressure calculated by the van der Waals equation (c) The
greater the compressibility, the more the volume matters. At low pressures, the correction factor for intermolecular attractions is
more significant, and the effect of the volume of the gas molecules on Z would be a small lowering compressibility. At higher
pressures, the effect of the volume of the gas molecules themselves on Z would increase compressibility (see Figure) (d) Once
again, at low pressures, the effect of intermolecular attractions on Z would be more important than the correction factor for the
volume of the gas molecules themselves, though perhaps still small. At higher pressures and low temperatures, the effect of
intermolecular attractions would be larger. See Figure. (e) low temperatures
This page titled 8.E: Gases (Exercises) is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.

CHAPTER OVERVIEW
9: Thermochemistry

General Chemistry
Useful forms of energy are also available from a variety of chemical reactions other than combustion. For example, the energy
produced by the batteries in a cell phone, car, or flashlight results from chemical reactions. This chapter introduces many of the
basic ideas necessary to explore the relationships between chemical changes and energy, with a focus on thermal energy.
9.2: Energy Basics
9.3: Calorimetry
9.4: Enthalpy
Contributors
[email protected]).
This page titled 9: Thermochemistry is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
1
Chemical reactions, such as those that occur when you light a match, involve changes in energy as well as matter. Societies at all
levels of development could not function without the energy released by chemical reactions. In 2012, about 85% of US energy
consumption came from the combustion of petroleum products, coal, wood, and garbage. We use this energy to produce electricity
(38%); to transport food, raw materials, manufactured goods, and people (27%); for industrial production (21%); and to heat and
power our homes and businesses (10%).1 While these combustion reactions help us meet our essential energy needs, they are also
recognized by the majority of the scientific community as a major contributor to global climate change.
Figure 9.1.1 : Sliding a match head along a rough surface initiates a combustion reaction that produces energy in the form of heat
and light. (credit: modification of work by Laszlo Ilyes).
Useful forms of energy are also available from a variety of chemical reactions other than combustion. For example, the energy
produced by the batteries in a cell phone, car, or flashlight results from chemical reactions. This chapter introduces many of the
basic ideas necessary to explore the relationships between chemical changes and energy, with a focus on thermal energy.
Footnotes
1. US Energy Information Administration, Primary Energy Consumption by Source and Sector, 2012, Total Energy
[www.eia.gov]. Data derived from US Energy Information Administration, Monthly Energy Review (January 2014).
This page titled 9.1: Prelude to Thermochemistry is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
5.0: Prelude to Thermochemistry is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

9.2: Energy Basics
Define energy, distinguish types of energy, and describe the nature of energy changes that accompany chemical and
physical changes
Distinguish the related properties of heat, thermal energy, and temperature
Define and distinguish specific heat and heat capacity, and describe the physical implications of both
Perform calculations involving heat, specific heat, and temperature change
Chemical changes and their accompanying changes in energy are important parts of our everyday world (Figure 9.2.1). The
macronutrients in food (proteins, fats, and carbohydrates) undergo metabolic reactions that provide the energy to keep our bodies
functioning. We burn a variety of fuels (gasoline, natural gas, coal) to produce energy for transportation, heating, and the
generation of electricity. Industrial chemical reactions use enormous amounts of energy to produce raw materials (such as iron and
aluminum). Energy is then used to manufacture those raw materials into useful products, such as cars, skyscrapers, and bridges.
Figure 9.2.1 : The energy involved in chemical changes is important to our daily lives: (a) A cheeseburger for lunch provides the
energy you need to get through the rest of the day; (b) the combustion of gasoline provides the energy that moves your car (and
you) between home, work, and school; and (c) coke, a processed form of coal, provides the energy needed to convert iron ore into
iron, which is essential for making many of the products we use daily. (credit a: modification of work by “Pink Sherbet
Photography”/Flickr; credit b: modification of work by Jeffery Turner).
Three pictures are shown and labeled a, b, and c. Picture a is a cheeseburger. Picture b depicts a highway that is full of traffic.
Picture c is a view into an industrial metal furnace. The view into the furnace shows a hot fire burning inside.
Over 90% of the energy we use comes originally from the sun. Every day, the sun provides the earth with almost 10,000 times the
amount of energy necessary to meet all of the world’s energy needs for that day. Our challenge is to find ways to convert and store
incoming solar energy so that it can be used in reactions or chemical processes that are both convenient and nonpolluting. Plants
and many bacteria capture solar energy through photosynthesis. We release the energy stored in plants when we burn wood or plant
products such as ethanol. We also use this energy to fuel our bodies by eating food that comes directly from plants or from animals
that got their energy by eating plants. Burning coal and petroleum also releases stored solar energy: These fuels are fossilized plant
and animal matter.
This chapter will introduce the basic ideas of an important area of science concerned with the amount of heat absorbed or released
during chemical and physical changes—an area called thermochemistry. The concepts introduced in this chapter are widely used in
almost all scientific and technical fields. Food scientists use them to determine the energy content of foods. Biologists study the
energetics of living organisms, such as the metabolic combustion of sugar into carbon dioxide and water. The oil, gas, and
transportation industries, renewable energy providers, and many others endeavor to find better methods to produce energy for our
commercial and personal needs. Engineers strive to improve energy efficiency, find better ways to heat and cool our homes,
refrigerate our food and drinks, and meet the energy and cooling needs of computers and electronics, among other applications.
Understanding thermochemical principles is essential for chemists, physicists, biologists, geologists, every type of engineer, and
just about anyone who studies or does any kind of science.
Energy
Energy can be defined as the capacity to supply heat or do work. One type of work (w) is the process of causing matter to move
against an opposing force. For example, we do work when we inflate a bicycle tire—we move matter (the air in the pump) against
the opposing force of the air surrounding the tire.

Like matter, energy comes in different types. One scheme classifies energy into two types: potential energy, the energy an object
has because of its relative position, composition, or condition, and kinetic energy, the energy that an object possesses because of its
motion. Water at the top of a waterfall or dam has potential energy because of its position; when it flows downward through
generators, it has kinetic energy that can be used to do work and produce electricity in a hydroelectric plant (Figure 9.2.2). A
battery has potential energy because the chemicals within it can produce electricity that can do work.
Figure 9.2.2 : (a) Water that is higher in elevation, for example, at the top of Victoria Falls, has a higher potential energy than water
at a lower elevation. As the water falls, some of its potential energy is converted into kinetic energy. (b) If the water flows through
generators at the bottom of a dam, such as the Hoover Dam shown here, its kinetic energy is converted into electrical energy.
(credit a: modification of work by Steve Jurvetson; credit b: modification of work by “curimedia”/Wikimedia commons).
Two pictures are shown and labeled a and b. Picture a shows a large waterfall with water falling from a high elevation at the top of
the falls to a lower elevation. The second picture is a view looking down into the Hoover Dam. Water is shown behind the high
wall of the dam on one side and at the base of the dam on the other.
Energy can be converted from one form into another, but all of the energy present before a change occurs always exists in some
form after the change is completed. This observation is expressed in the law of conservation of energy: during a chemical or
physical change, energy can be neither created nor destroyed, although it can be changed in form. (This is also one version of the
first law of thermodynamics, as you will learn later.)
When one substance is converted into another, there is always an associated conversion of one form of energy into another. Heat is
usually released or absorbed, but sometimes the conversion involves light, electrical energy, or some other form of energy. For
example, chemical energy (a type of potential energy) is stored in the molecules that compose gasoline. When gasoline is
combusted within the cylinders of a car’s engine, the rapidly expanding gaseous products of this chemical reaction generate
mechanical energy (a type of kinetic energy) when they move the cylinders’ pistons.
According to the law of conservation of matter (seen in an earlier chapter), there is no detectable change in the total amount of
matter during a chemical change. When chemical reactions occur, the energy changes are relatively modest and the mass changes
are too small to measure, so the laws of conservation of matter and energy hold well. However, in nuclear reactions, the energy
changes are much larger (by factors of a million or so), the mass changes are measurable, and matter-energy conversions are
significant. This will be examined in more detail in a later chapter on nuclear chemistry. To encompass both chemical and nuclear
changes, we combine these laws into one statement: The total quantity of matter and energy in the universe is fixed.
Thermal Energy, Temperature, and Heat

Thermal energy is kinetic energy associated with the random motion of atoms and molecules. Temperature is a quantitative
measure of “hot” or “cold.” When the atoms and molecules in an object are moving or vibrating quickly, they have a higher
average kinetic energy (KE), and we say that the object is “hot.” When the atoms and molecules are moving slowly, they have
lower KE, and we say that the object is “cold” (Figure 9.2.3). Assuming that no chemical reaction or phase change (such as
melting or vaporizing) occurs, increasing the amount of thermal energy in a sample of matter will cause its temperature to increase.
And, assuming that no chemical reaction or phase change (such as condensation or freezing) occurs, decreasing the amount of
thermal energy in a sample of matter will cause its temperature to decrease.

Figure 9.2.3 : (a) The molecules in a sample of hot water move more rapidly than (b) those in a sample of cold water.
Two molecular drawings are shown and labeled a and b. Drawing a is a box containing fourteen red spheres that are surrounded by
lines indicating that the particles are moving rapidly. This drawing has a label that reads “Hot water.” Drawing b depicts another
box of equal size that also contains fourteen spheres, but these are blue. They are all surrounded by smaller lines that depict some
particle motion, but not as much as in drawing a. This drawing has a label that reads “Cold water.”
Most substances expand as their temperature increases and contract as their temperature decreases. This property can be used to
measure temperature changes, as shown in Figure 9.2.4. The operation of many thermometers depends on the expansion and
contraction of substances in response to temperature changes.
A picture labeled a is shown as well as a pair of drawings labeled b. Picture a shows the lower portion of an alcohol thermometer.
The thermometer has a printed scale to the left of the tube in the center that reads from negative forty degrees at the bottom to forty
degrees at the top. It also has a scale printed to the right of the tube that reads from negative thirty degrees at the bottom to thirty
five degrees at the top. On both scales, the volume of the alcohol in the tube reads between nine and ten degrees. The two images
labeled b both depict a metal strip coiled into a spiral and composed of brass and steel. The left coil, which is loosely coiled, is
labeled along its upper edge with the 30 degrees C and 10 degrees C. The end of the coil is near the 30 degrees C label. The right
hand coil is much more tightly wound and the end is near the 10 degree C label.
Figure 9.2.4 : (a) In an alcohol or mercury thermometer, the liquid (dyed red for visibility) expands when heated and contracts
when cooled, much more so than the glass tube that contains the liquid. (b) In a bimetallic thermometer, two different metals (such
as brass and steel) form a two-layered strip. When heated or cooled, one of the metals (brass) expands or contracts more than the
other metal (steel), causing the strip to coil or uncoil. Both types of thermometers have a calibrated scale that indicates the
temperature. (credit a: modification of work by “dwstucke”/Flickr). (c) The demonstration allows one to view the effects of heating
and cooling a coiled bimetallic strip.A bimetallic coil from a thermometer reacts to the heat from a lighter, by uncoiling and then
coiling back up when the lighter is removed. Animation used with permission from Hustvedt (via Wikipedia).
Heat (q) is the transfer of thermal energy between two bodies at different temperatures. Heat flow (a redundant term, but one
commonly used) increases the thermal energy of one body and decreases the thermal energy of the other. Suppose we initially have
a high temperature (and high thermal energy) substance (H) and a low temperature (and low thermal energy) substance (L). The
atoms and molecules in H have a higher average KE than those in L. If we place substance H in contact with substance L, the
thermal energy will flow spontaneously from substance H to substance L. The temperature of substance H will decrease, as will the
average KE of its molecules; the temperature of substance L will increase, along with the average KE of its molecules. Heat flow
will continue until the two substances are at the same temperature (Figure 9.2.5).

Figure 9.2.5 : (a) Substances H and L are initially at different temperatures, and their atoms have different average kinetic energies.
(b) When they are put into contact with each other, collisions between the molecules result in the transfer of kinetic (thermal)
energy from the hotter to the cooler matter. (c) The two objects reach “thermal equilibrium” when both substances are at the same
temperature, and their molecules have the same average kinetic energy.
Three drawings are shown and labeled a, b, and c, respectively. The first drawing labeled a depicts two boxes, with a space in
between and the pair is captioned “Different temperatures.” The left hand box is labeled H and holds fourteen well-spaced red
spheres with lines drawn around them to indicate rapid motion. The right hand box is labeled L and depicts fourteen blue spheres
that are closer together than the red spheres and have smaller lines around them showing less particle motion. The second drawing
labeled b depicts two boxes that are touching one another. The left box is labeled H and contains fourteen maroon spheres that are
spaced evenly apart. There are tiny lines around each sphere depicting particle movement. The right box is labeled L and holds
fourteen purple spheres that are slightly closer together than the maroon spheres. There are also tiny lines around each sphere
depicting particle movement. A black arrow points from the left box to the right box and the pair of diagrams is captioned
“Contact.” The third drawing labeled c, is labeled “Thermal equilibrium.” There are two boxes shown in contact with one another.
Both boxes contain fourteen purple spheres with small lines around them depicting moderate movement. The left box is labeled H
and the right box is labeled L.
Matter undergoing chemical reactions and physical changes can release or absorb heat. A change that releases heat is called an
exothermic process. For example, the combustion reaction that occurs when using an oxyacetylene torch is an exothermic process
—this process also releases energy in the form of light as evidenced by the torch’s flame (Figure 9.2.6a). A reaction or change that
absorbs heat is an endothermic process. A cold pack used to treat muscle strains provides an example of an endothermic process.
When the substances in the cold pack (water and a salt like ammonium nitrate) are brought together, the resulting process absorbs
heat, leading to the sensation of cold.
Figure 9.2.6 : (a) An oxyacetylene torch produces heat by the combustion of acetylene in oxygen. The energy released by this
exothermic reaction heats and then melts the metal being cut. The sparks are tiny bits of the molten metal flying away. (b) A cold
pack uses an endothermic process to create the sensation of cold. (credit a: modification of work by “Skatebiker”/Wikimedia
commons).
Two pictures are shown and labeled a and b. Picture a shows a metal railroad tie being cut with the flame of an acetylene torch.
Picture b shows a chemical cold pack containing ammonium nitrate.
Measuring Energy and Heat Capacity

Historically, energy was measured in units of calories (cal). A calorie is the amount of energy required to raise one gram of water
by 1 degree C (1 kelvin). However, this quantity depends on the atmospheric pressure and the starting temperature of the water.
The ease of measurement of energy changes in calories has meant that the calorie is still frequently used. The Calorie (with a
capital C), or large calorie, commonly used in quantifying food energy content, is a kilocalorie. The SI unit of heat, work, and
energy is the joule. A joule (J) is defined as the amount of energy used when a force of 1 newton moves an object 1 meter. It is
named in honor of the English physicist James Prescott Joule. One joule is equivalent to 1 kg m2/s2, which is also called 1 newton–
meter. A kilojoule (kJ) is 1000 joules. To standardize its definition, 1 calorie has been set to equal 4.184 joules.
We now introduce two concepts useful in describing heat flow and temperature change. The heat capacity (C) of a body of matter is
the quantity of heat (q) it absorbs or releases when it experiences a temperature change (ΔT) of 1 degree Celsius (or equivalently, 1

kelvin)
q
C = (9.2.1)
ΔT
Heat capacity is determined by both the type and amount of substance that absorbs or releases heat. It is therefore an extensive
property—its value is proportional to the amount of the substance.
For example, consider the heat capacities of two cast iron frying pans. The heat capacity of the large pan is five times greater than
that of the small pan because, although both are made of the same material, the mass of the large pan is five times greater than the
mass of the small pan. More mass means more atoms are present in the larger pan, so it takes more energy to make all of those
atoms vibrate faster. The heat capacity of the small cast iron frying pan is found by observing that it takes 18,150 J of energy to
raise the temperature of the pan by 50.0 °C
18, 140 J
Csmall pan = = 363 J/°C (9.2.2)
50.0 °C
The larger cast iron frying pan, while made of the same substance, requires 90,700 J of energy to raise its temperature by 50.0 °C.
The larger pan has a (proportionally) larger heat capacity because the larger amount of material requires a (proportionally) larger
amount of energy to yield the same temperature change:
90, 700 J
Clarge pan = = 1814 J/°C (9.2.3)
50.0 °C
The specific heat capacity (c) of a substance, commonly called its “specific heat,” is the quantity of heat required to raise the
temperature of 1 gram of a substance by 1 degree Celsius (or 1 kelvin):
q
c = (9.2.4)
mΔT
Specific heat capacity depends only on the kind of substance absorbing or releasing heat. It is an intensive property—the type, but
not the amount, of the substance is all that matters. For example, the small cast iron frying pan has a mass of 808 g. The specific
heat of iron (the material used to make the pan) is therefore:
18, 140 J
ciron = = 0.449 J/g °C (9.2.5)
(808 g)(50.0 °C)
The large frying pan has a mass of 4040 g. Using the data for this pan, we can also calculate the specific heat of iron:
90, 700 J
ciron = = 0.449 J/g °C (9.2.6)
(4, 040 g)(50.0 °C)
Although the large pan is more massive than the small pan, since both are made of the same material, they both yield the same
value for specific heat (for the material of construction, iron). Note that specific heat is measured in units of energy per temperature
per mass and is an intensive property, being derived from a ratio of two extensive properties (heat and mass). The molar heat
capacity, also an intensive property, is the heat capacity per mole of a particular substance and has units of J/mol °C (Figure 9.2.7).
Figure 9.2.7 : Due to its larger mass, a large frying pan has a larger heat capacity than a small frying pan. Because they are made of
the same material, both frying pans have the same specific heat. (credit: Mark Blaser).
The picture shows two black metal frying pans sitting on a flat surface. The left pan is about half the size of the right pan.

Liquid water has a relatively high specific heat (about 4.2 J/g °C); most metals have much lower specific heats (usually less than 1
J/g °C). The specific heat of a substance varies somewhat with temperature. However, this variation is usually small enough that we
will treat specific heat as constant over the range of temperatures that will be considered in this chapter. Specific heats of some
common substances are listed in Table 9.2.1.
Table 9.2.1 : Specific Heats of Common Substances at 25 °C and 1 bar
Substance Symbol (state) Specific Heat (J/g °C)
helium He(g) 5.193
water H2O(l) 4.184
ethanol C2H6O(l) 2.376
ice H2O(s) 2.093 (at −10 °C)
water vapor H2O(g) 1.864
nitrogen N2(g) 1.040
air 1.007
oxygen O2(g) 0.918
aluminum Al(s) 0.897
carbon dioxide CO2(g) 0.853
argon Ar(g) 0.522
iron Fe(s) 0.449
copper Cu(s) 0.385
lead Pb(s) 0.130
gold Au(s) 0.129
silicon Si(s) 0.712
If we know the mass of a substance and its specific heat, we can determine the amount of heat, q, entering or leaving the substance
by measuring the temperature change before and after the heat is gained or lost:
q = (specific heat) × (mass of substance) × (temperature change)
q = c × m × ΔT
= c × m × (Tfinal − Tinitial)
In this equation, c is the specific heat of the substance, m is its mass, and ΔT (which is read “delta T”) is the temperature change,
Tfinal − Tinitial. If a substance gains thermal energy, its temperature increases, its final temperature is higher than its initial
temperature, Tfinal − Tinitial has a positive value, and the value of q is positive. If a substance loses thermal energy, its temperature
decreases, the final temperature is lower than the initial temperature, Tfinal − Tinitial has a negative value, and the value of q is
negative.
 Example 9.2.1: Measuring Heat
A flask containing 8.0 × 10 2

g of water is heated, and the temperature of the water increases from 21 °C to 85 °C. How much
heat did the water absorb?
Solution
To answer this question, consider these factors:
the specific heat of the substance being heated (in this case, water)

the amount of substance being heated (in this case, 800 g)
the magnitude of the temperature change (in this case, from 21 °C to 85 °C).
The specific heat of water is 4.184 J/g °C, so to heat 1 g of water by 1 °C requires 4.184 J. We note that since 4.184 J is
required to heat 1 g of water by 1 °C, we will need 800 times as much to heat 800 g of water by 1 °C. Finally, we observe that
since 4.184 J are required to heat 1 g of water by 1 °C, we will need 64 times as much to heat it by 64 °C (that is, from 21 °C to
85 °C).
This can be summarized using the equation:
q = c × m × ΔT
= (4.184 J/ g °C) × (800 g ) × (85 − 21)°C
= (4.184 J/ g ° C ) × (800 g ) × (64)° C
= 210, 000 J(= 210 kJ)
Because the temperature increased, the water absorbed heat and q is positive.
 Exercise 9.2.1
How much heat, in joules, must be added to a 5.00 × 10 2

g iron skillet to increase its temperature from 25 °C to 250 °C? The
specific heat of iron is 0.451 J/g °C.
Answer
4
5.05 × 10 J
Note that the relationship between heat, specific heat, mass, and temperature change can be used to determine any of these
quantities (not just heat) if the other three are known or can be deduced.
 Example 9.2.2: Determining Other Quantities
A piece of unknown metal weighs 348 g. When the metal piece absorbs 6.64 kJ of heat, its temperature increases from 22.4 °C
to 43.6 °C. Determine the specific heat of this metal (which might provide a clue to its identity).
Solution
Since mass, heat, and temperature change are known for this metal, we can determine its specific heat using the relationship:
q = c × m × ΔT
Substituting the known values:
6, 640 J = c × (348 g) × (43.6 − 22.4) °C
Solving:
6, 640 J
c = = 0.900 J/g °C
(348 g) × (21.2°C)
Comparing this value with the values in Table 9.2.1, this value matches the specific heat of aluminum, which suggests that the
unknown metal may be aluminum.

 Exercise 9.2.2
A piece of unknown metal weighs 217 g. When the metal piece absorbs 1.43 kJ of heat, its temperature increases from 24.5 °C
to 39.1 °C. Determine the specific heat of this metal, and predict its identity.
Answer
c = 0.45 J/g °C ; the metal is likely to be iron from checking Table 9.2.1.
Solar Thermal Energy Power Plants

The sunlight that reaches the earth contains thousands of times more energy than we presently capture. Solar thermal systems
provide one possible solution to the problem of converting energy from the sun into energy we can use. Large-scale solar thermal
plants have different design specifics, but all concentrate sunlight to heat some substance; the heat “stored” in that substance is then
converted into electricity.
The Solana Generating Station in Arizona’s Sonora Desert produces 280 megawatts of electrical power. It uses parabolic mirrors
that focus sunlight on pipes filled with a heat transfer fluid (HTF) (Figure 9.2.8). The HTF then does two things: It turns water into
steam, which spins turbines, which in turn produces electricity, and it melts and heats a mixture of salts, which functions as a
thermal energy storage system. After the sun goes down, the molten salt mixture can then release enough of its stored heat to
produce steam to run the turbines for 6 hours. Molten salts are used because they possess a number of beneficial properties,
including high heat capacities and thermal conductivities.
Figure 9.2.8 : This solar thermal plant uses parabolic trough mirrors to concentrate sunlight. (credit a: modification of work by
Bureau of Land Management)
This figure has two parts labeled a and b. Part a shows rows and rows of trough mirrors. Part b shows how a solar thermal plant
works. Heat transfer fluid enters a tank via pipes. The tank contains water which is heated. As the heat is exchanged from the pipes
to the water, the water becomes steam. The steam travels to a steam turbine. The steam turbine begins to turn which powers a
generator. Exhaust steam exits the steam turbine and enters a cooling tower.
The 377-megawatt Ivanpah Solar Generating System, located in the Mojave Desert in California, is the largest solar thermal power
plant in the world (Figure 9.2.9). Its 170,000 mirrors focus huge amounts of sunlight on three water-filled towers, producing steam
at over 538 °C that drives electricity-producing turbines. It produces enough energy to power 140,000 homes. Water is used as the
working fluid because of its large heat capacity and heat of vaporization.

Figure 9.2.9 : (a) The Ivanpah solar thermal plant uses 170,000 mirrors to concentrate sunlight on water-filled towers. (b) It covers
4000 acres of public land near the Mojave Desert and the California-Nevada border. (credit a: modification of work by Craig
Dietrich; credit b: modification of work by “USFWS Pacific Southwest Region”/Flickr)
Two pictures are shown and labeled a and b. Picture a shows a thermal plant with three tall metal towers. Picture b is an arial
picture of the mirrors used at the plant. They are arranged in rows.
Summary
Energy is the capacity to do work (applying a force to move matter). Kinetic energy (KE) is the energy of motion; potential energy
is energy due to relative position, composition, or condition. When energy is converted from one form into another, energy is
neither created nor destroyed (law of conservation of energy or first law of thermodynamics). Matter has thermal energy due to the
KE of its molecules and temperature that corresponds to the average KE of its molecules. Heat is energy that is transferred between
objects at different temperatures; it flows from a high to a low temperature. Chemical and physical processes can absorb heat
(endothermic) or release heat (exothermic). The SI unit of energy, heat, and work is the joule (J). Specific heat and heat capacity
are measures of the energy needed to change the temperature of a substance or object. The amount of heat absorbed or released by
a substance depends directly on the type of substance, its mass, and the temperature change it undergoes.
Key Equations
q = c × m × ΔT = c × m × (Tfinal − Tinitial)
Glossary
calorie (cal)
unit of heat or other energy; the amount of energy required to raise 1 gram of water by 1 degree Celsius; 1 cal is defined as
4.184 J
endothermic process
chemical reaction or physical change that absorbs heat
energy
capacity to supply heat or do work
exothermic process
chemical reaction or physical change that releases heat
heat (q)
transfer of thermal energy between two bodies
heat capacity (C)

extensive property of a body of matter that represents the quantity of heat required to increase its temperature by 1 degree
Celsius (or 1 kelvin)
joule (J)
SI unit of energy; 1 joule is the kinetic energy of an object with a mass of 2 kilograms moving with a velocity of 1 meter per
second, 1 J = 1 kg m2/s and 4.184 J = 1 cal

kinetic energy
1
energy of a moving body, in joules, equal to mv
2
(where m = mass and v = velocity)
2
potential energy
energy of a particle or system of particles derived from relative position, composition, or condition
specific heat capacity (c)

intensive property of a substance that represents the quantity of heat required to raise the temperature of 1 gram of the substance
by 1 degree Celsius (or 1 kelvin)
temperature
intensive property of matter that is a quantitative measure of “hotness” and “coldness”
thermal energy
kinetic energy associated with the random motion of atoms and molecules
thermochemistry
study of measuring the amount of heat absorbed or released during a chemical reaction or a physical change
work (w)
energy transfer due to changes in external, macroscopic variables such as pressure and volume; or causing matter to move
against an opposing force
This page titled 9.2: Energy Basics is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
5.1: Energy Basics is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

9.3: Calorimetry
Explain the technique of calorimetry
Calculate and interpret heat and related properties using typical calorimetry data
One technique we can use to measure the amount of heat involved in a chemical or physical process is known as calorimetry. Calorimetry is used
to measure amounts of heat transferred to or from a substance. To do so, the heat is exchanged with a calibrated object (calorimeter). The change
in temperature of the measuring part of the calorimeter is converted into the amount of heat (since the previous calibration was used to establish
its heat capacity). The measurement of heat transfer using this approach requires the definition of a system (the substance or substances
undergoing the chemical or physical change) and its surroundings (the other components of the measurement apparatus that serve to either
provide heat to the system or absorb heat from the system). Knowledge of the heat capacity of the surroundings, and careful measurements of the
masses of the system and surroundings and their temperatures before and after the process allows one to calculate the heat transferred as
described in this section.
A calorimeter is a device used to measure the amount of heat involved in a chemical or physical process. For example, when an exothermic
reaction occurs in solution in a calorimeter, the heat produced by the reaction is absorbed by the solution, which increases its temperature. When
an endothermic reaction occurs, the heat required is absorbed from the thermal energy of the solution, which decreases its temperature (Figure
9.3.1). The temperature change, along with the specific heat and mass of the solution, can then be used to calculate the amount of heat involved
in either case.
Figure 9.3.1 : In a calorimetric determination, either (a) an exothermic process occurs and heat, q, is negative, indicating that thermal energy is
transferred from the system to its surroundings, or (b) an endothermic process occurs and heat, q, is positive, indicating that thermal energy is
transferred from the surroundings to the system.
Two diagrams labeled a and b are shown. Each is made up of two rectangular containers with a thermometer inserted into the top right and
extending inside. There is a right facing arrow connecting each box in each diagram. The left container in diagram a depicts a pink and green
swirling solution with the terms “Exothermic process” and “System” written in the center with arrows facing away from the terms pointing to
“q.” The labels “Solution” and “Surroundings” are written at the bottom of the container. The right container in diagram a has the term “Solution”
written at the bottom of the container and a red arrow facing up near the thermometer with the phrase “Temperature increased” next to it. The
pink and green swirls are more blended in this container. The left container in diagram b depicts a purple and blue swirling solution with the
terms “Endothermic process” and “System” written in the center with arrows facing away from the terms and “Solution” and “Surroundings”
written at the bottom. The arrows point away from the letter “q.” The right container in diagram b has the term “Solution” written at the bottom
and a red arrow facing down near the thermometer with the phrase “Temperature decreased” next to it. The blue and purple swirls are more
blended in this container.
By convention, q is given a negative (-) sign when the system releases heat to the surroundings (exothermic); q is given a positive (+) sign
when the system absorbs heat from the surroundings (endothermic).
Scientists use well-insulated calorimeters that all but prevent the transfer of heat between the calorimeter and its environment. This enables the
accurate determination of the heat involved in chemical processes, the energy content of foods, and so on. General chemistry students often use
simple calorimeters constructed from polystyrene cups (Figure 9.3.2). These easy-to-use “coffee cup” calorimeters allow more heat exchange
with their surroundings, and therefore produce less accurate energy values.

Figure 9.3.2 : A simple calorimeter can be constructed from two polystyrene cups. A thermometer and stirrer extend through the cover into the
reaction mixture.
Two Styrofoam cups are shown nested in one another with a cover over the top. A thermometer and stirring rod are inserted through the cover
and into the solution inside the cup, which is shown as a cut-away. The stirring rod has a double headed arrow next to it facing up and down. The
liquid mixture inside the cup is labeled “Reaction mixture.”
Commercial solution calorimeters are also available. Relatively inexpensive calorimeters often consist of two thin-walled cups that are nested in a
way that minimizes thermal contact during use, along with an insulated cover, handheld stirrer, and simple thermometer. More expensive
calorimeters used for industry and research typically have a well-insulated, fully enclosed reaction vessel, motorized stirring mechanism, and a
more accurate temperature sensor (Figure 9.3.3).
Figure 9.3.3 : Commercial solution calorimeters range from (a) simple, inexpensive models for student use to (b) expensive, more accurate
models for industry and research.
Two diagrams are shown and labeled a and b. Diagram a depicts a thermometer which passes through a disk-like insulating cover and into a metal
cylinder which is labeled “metal inner vessel,” which is in turn nested in a metal cylinder labeled “metal outer vessel.” The inner cylinder rests on
an insulating support ring. A stirrer passes through the insulating cover and into the inner cylinder as well. Diagram b shows an inner metal vessel
half full of liquid resting on an insulating support ring and nested in a metal outer vessel. A precision temperature probe and motorized stirring
rod are placed into the solution in the inner vessel and connected by wires to equipment exterior to the set-up.
Before we practice calorimetry problems involving chemical reactions, consider a simple example that illustrates the core idea behind
calorimetry. Suppose we initially have a high-temperature substance, such as a hot piece of metal (M), and a low-temperature substance, such as
cool water (W). If we place the metal in the water, heat will flow from M to W. The temperature of M will decrease, and the temperature of W
will increase, until the two substances have the same temperature—that is, when they reach thermal equilibrium (Figure 9.3.4). If this occurs in a
calorimeter, ideally all of this heat transfer occurs between the two substances, with no heat gained or lost by either the calorimeter or the
calorimeter’s surroundings. Under these ideal circumstances, the net heat change is zero:
q substance M +q substance W =0 (9.3.1)
This relationship can be rearranged to show that the heat gained by substance M is equal to the heat lost by substance W:
q substance M = −q substance W (9.3.2)

The magnitude of the heat (change) is therefore the same for both substances, and the negative sign merely shows that q and substance M
q are opposite in direction of heat flow (gain or loss) but does not indicate the arithmetic sign of either q value (that is determined by
substance W
whether the matter in question gains or loses heat, per definition). In the specific situation described, q is a negative value and
substance M
q is positive, since heat is transferred from M to W.

substance W
Figure 9.3.4 : In a simple calorimetry process, (a) heat, q, is transferred from the hot metal, M, to the cool water, W, until (b) both are at the same
temperature.
Two diagrams are shown and labeled a and b. Each diagram is composed of a rectangular container with a thermometer inserted inside from the
top right corner. Both containers are connected by a right-facing arrow. Both containers are full of water, which is depicted by the letter “W,” and
each container has a square in the middle which represents a metal which is labeled with a letter “M.” In diagram a, the metal is drawn in brown
and has three arrows facing away from it. Each arrow has the letter “q” at its end. The metal is labeled “system” and the water is labeled
“surroundings.” The thermometer in this diagram has a relatively low reading. In diagram b, the metal is depicted in purple and the thermometer
has a relatively high reading.
 Example 9.3.1: Heat Transfer between Substances at Different Temperatures
A hot 360-g piece of rebar (a steel rod used for reinforcing concrete) is dropped into 425 mL of water at 24.0 °C. The final temperature of the
water is measured as 42.7 °C. Calculate the initial temperature of the piece of rebar. Assume the specific heat of steel is approximately the
same as that for iron (Table T4), and that all heat transfer occurs between the rebar and the water (there is no heat exchange with the
surroundings).
Solution
The temperature of the water increases from 24.0 °C to 42.7 °C, so the water absorbs heat. That heat came from the piece of rebar, which
initially was at a higher temperature. Assuming that all heat transfer was between the rebar and the water, with no heat “lost” to the
surroundings, then heat given off by rebar = − heat taken in by water, or:
qrebar = −qwater
Since we know how heat is related to other measurable quantities, we have:
(c × m × ΔT )rebar = −(c × m × ΔT )water
Letting f = final and i = initial, in expanded form, this becomes:
crebar × mrebar × (Tf ,rebar − Ti,rebar) = −cwater × mwater × (Tf ,water − Ti,water)
The density of water is 1.0 g/mL, so 425 mL of water = 425 g. Noting that the final temperature of both the rebar and water is 42.7 °C,
substituting known values yields:
(0.449 J/g °C)(360g)(42.7°C − Ti,rebar) = −(4.184 J/g °C)(425 g)(42.7°C − 24.0°C)
(4.184 J/g °C)(425 g)(42.7°C − 24.0°C)

Ti,rebar = + 42.7°C
(0.449 J/g °C)(360 g)
Solving this gives Ti,rebar= 248 °C, so the initial temperature of the rebar was 248 °C.

 Exercise 9.3.1A
A 248-g piece of copper is dropped into 390 mL of water at 22.6 °C. The final temperature of the water was measured as 39.9 °C. Calculate
the initial temperature of the piece of copper. Assume that all heat transfer occurs between the copper and the water.
Answer
The initial temperature of the copper was 335.6 °C.
 Exercise 9.3.1B
A 248-g piece of copper initially at 314 °C is dropped into 390 mL of water initially at 22.6 °C. Assuming that all heat transfer occurs
between the copper and the water, calculate the final temperature.
Answer
The final temperature (reached by both copper and water) is 38.7 °C.
This method can also be used to determine other quantities, such as the specific heat of an unknown metal.
 Example 9.3.2: Identifying a Metal by Measuring Specific Heat
A 59.7 g piece of metal that had been submerged in boiling water was quickly transferred into 60.0 mL of water initially at 22.0 °C. The final
temperature is 28.5 °C. Use these data to determine the specific heat of the metal. Use this result to identify the metal.
Solution
Assuming perfect heat transfer, heat given off by metal = −heat taken in by water, or:
qmetal = −qwater
In expanded form, this is:
cmetal × mmetal × (Tf ,metal − Ti,metal) = −cwater × mwater × (Tf ,water − Ti,water)
Noting that since the metal was submerged in boiling water, its initial temperature was 100.0 °C; and that for water, 60.0 mL = 60.0 g; we
have:
(cmetal )(59.7 g)(28.5°C − 100.0°C) = −(4.18 J/g °C)(60.0 g)(28.5°C − 22.0°C)
Solving this:
−(4.184 J/g °C)(60.0 g)(6.5°C)
cmetal = = 0.38 J/g °C
(59.7 g)(−71.5°C)
Comparing this with values in Table T4, our experimental specific heat is closest to the value for copper (0.39 J/g °C), so we identify the
metal as copper.
 Exercise 9.3.2
A 92.9-g piece of a silver/gray metal is heated to 178.0 °C, and then quickly transferred into 75.0 mL of water initially at 24.0 °C. After 5
minutes, both the metal and the water have reached the same temperature: 29.7 °C. Determine the specific heat and the identity of the metal.
(Note: You should find that the specific heat is close to that of two different metals. Explain how you can confidently determine the identity
of the metal).
Answer
cmetal = 0.13 J/g °C
This specific heat is close to that of either gold or lead. It would be difficult to determine which metal this was based solely on the
numerical values. However, the observation that the metal is silver/gray in addition to the value for the specific heat indicates that the
metal is lead.

When we use calorimetry to determine the heat involved in a chemical reaction, the same principles we have been discussing apply. The amount
of heat absorbed by the calorimeter is often small enough that we can neglect it (though not for highly accurate measurements, as discussed later),
and the calorimeter minimizes energy exchange with the surroundings. Because energy is neither created nor destroyed during a chemical
reaction, there is no overall energy change during the reaction. The heat produced or consumed in the reaction (the “system”), qreaction, plus the
heat absorbed or lost by the solution (the “surroundings”), q , must add up to zero:
solution
qreaction + qsolution = 0 (9.3.3)
This means that the amount of heat produced or consumed in the reaction equals the amount of heat absorbed or lost by the solution:
qreaction = −qsolution (9.3.4)
This concept lies at the heart of all calorimetry problems and calculations.
 Example 9.3.3: Heat Produced by an Exothermic Reaction
When 50.0 mL of 0.10 M HCl(aq) and 50.0 mL of 1.00 M NaOH(aq), both at 22.0 °C, are added to a coffee cup calorimeter, the temperature
of the mixture reaches a maximum of 28.9 °C. What is the approximate amount of heat produced by this reaction?
HCl(aq) + NaOH(aq) ⟶ NaCl(aq) + H O(l)

2
Solution
To visualize what is going on, imagine that you could combine the two solutions so quickly that no reaction took place while they mixed;
then after mixing, the reaction took place. At the instant of mixing, you have 100.0 mL of a mixture of HCl and NaOH at 22.0 °C. The HCl
and NaOH then react until the solution temperature reaches 28.9 °C.
The heat given off by the reaction is equal to that taken in by the solution. Therefore:
qreaction = −qsolution
(It is important to remember that this relationship only holds if the calorimeter does not absorb any heat from the reaction, and there is no
heat exchange between the calorimeter and its surroundings.)
Next, we know that the heat absorbed by the solution depends on its specific heat, mass, and temperature change:
qsolution = (c × m × ΔT )solution
To proceed with this calculation, we need to make a few more reasonable assumptions or approximations. Since the solution is aqueous, we
can proceed as if it were water in terms of its specific heat and mass values. The density of water is approximately 1.0 g/mL, so 100.0 mL has
a mass of about 1.0 × 102 g (two significant figures). The specific heat of water is approximately 4.18 J/g °C, so we use that for the specific
heat of the solution. Substituting these values gives:
2 3
qsolution = (4.184 J/g °C)(1.0 × 10 g)(28.9°C − 22.0°C) = 2.89 × 10 J
Finally, since we are trying to find the heat of the reaction, we have:
3
qreaction = −qsolution = −2.89 × 10 J
The negative sign indicates that the reaction is exothermic. It produces 2.89 kJ of heat.
 Exercise 9.3.3
When 100 mL of 0.200 M NaCl(aq) and 100 mL of 0.200 M AgNO3(aq), both at 21.9 °C, are mixed in a coffee cup calorimeter, the
temperature increases to 23.5 °C as solid AgCl forms. How much heat is produced by this precipitation reaction? What assumptions did you
make to determine your value?
Answer
J; assume no heat is absorbed by the calorimeter, no heat is exchanged between the calorimeter and its surroundings, and that
3
1.34 × 10
the specific heat and mass of the solution are the same as those for water
 Thermochemistry of Hand Warmers
When working or playing outdoors on a cold day, you might use a hand warmer to warm your hands (Figure 9.3.5). A common reusable
hand warmer contains a supersaturated solution of NaC2H3O2 (sodium acetate) and a metal disc. Bending the disk creates nucleation sites

around which the metastable NaC2H3O2 quickly crystallizes (a later chapter on solutions will investigate saturation and supersaturation in
more detail).
The process NaC H O (aq) ⟶ NaC H O (s) is exothermic, and the heat produced by this process is absorbed by your hands, thereby
2 3 2 2 3 2
warming them (at least for a while). If the hand warmer is reheated, the NaC2H3O2 redissolves and can be reused.
Figure 9.3.5 : Chemical hand warmers produce heat that warms your hand on a cold day. In this one, you can see the metal disc that initiates
the exothermic precipitation reaction. (credit: modification of work by Science Buddies TV/YouTube)
A series of three photos is shown. There are two right-facing arrows connecting one photo to the next. The first photo shows a chemical hand
warmer. It is a bag that contains a clear, colorless liquid. There is a white disk located to the right inside the bag. The second photo shows the
same thing, except the white disc has become a white, cloudy substance. The third photo shows the entire bag filled with this white
substance.
Another common hand warmer produces heat when it is ripped open, exposing iron and water in the hand warmer to oxygen in the air. One
simplified version of this exothermic reaction is
3
2 Fe(s) + O (g) ⟶ Fe O (s). n
2 2 2 3
Salt in the hand warmer catalyzes the reaction, so it produces heat more rapidly; cellulose, vermiculite, and activated carbon help distribute
the heat evenly. Other types of hand warmers use lighter fluid (a platinum catalyst helps lighter fluid oxidize exothermically), charcoal
(charcoal oxidizes in a special case), or electrical units that produce heat by passing an electrical current from a battery through resistive
wires.
 Example 9.3.4: Heat Flow in an Instant Ice Pack
When solid ammonium nitrate dissolves in water, the solution becomes cold. This is the basis for an “instant ice pack” (Figure 9.3.5). When
3.21 g of solid NH4NO3 dissolves in 50.0 g of water at 24.9 °C in a calorimeter, the temperature decreases to 20.3 °C.
Calculate the value of q for this reaction and explain the meaning of its arithmetic sign. State any assumptions that you made.
Figure 9.3.5 : An instant cold pack consists of a bag containing solid ammonium nitrate and a second bag of water. When the bag of water is
broken, the pack becomes cold because the dissolution of ammonium nitrate is an endothermic process that removes thermal energy from the
water. The cold pack then removes thermal energy from your body.
Solution
We assume that the calorimeter prevents heat transfer between the solution and its external environment (including the calorimeter itself), in
which case:
qrxn = −qsoln
with “rxn” and “soln” used as shorthand for “reaction” and “solution,” respectively.
Assuming also that the specific heat of the solution is the same as that for water, we have:

qrxn = −qsoln = −(c × m × ΔT )soln
= −[(4.184J/g °C) × (53.2 g) × (20.3°C − 24.9°C)]
= −[(4.184J/g °C) × (53.2 g) × (−4.6°C)]
3
+ 1.0 × 10 J = +1.0 kJ
The positive sign for q indicates that the dissolution is an endothermic process.
 Exercise 9.3.4
When a 3.00-g sample of KCl was added to 3.00 × 102 g of water in a coffee cup calorimeter, the temperature decreased by 1.05 °C. How
much heat is involved in the dissolution of the KCl? What assumptions did you make?
Answer
1.33 kJ; assume that the calorimeter prevents heat transfer between the solution and its external environment (including the calorimeter
itself) and that the specific heat of the solution is the same as that for water.
If the amount of heat absorbed by a calorimeter is too large to neglect or if we require more accurate results, then we must take into account the
heat absorbed both by the solution and by the calorimeter.
Figure 9.3.6 : (a) A bomb calorimeter is used to measure heat produced by reactions involving gaseous reactants or products, such as combustion.
(b) The reactants are contained in the gas-tight “bomb,” which is submerged in water and surrounded by insulating materials. (credit a:
modification of work by “Harbor1”/Wikimedia commons)
A picture and a diagram are shown, labeled a and b, respectively. Picture a depicts a bomb calorimeter. It is a cube-shaped machine with a cavity
in the top, a metal cylinder that is above the cavity, and a read-out panel attached to the top-right side. Diagram b depicts a cut away figure of a
cube with a cylindrical container full of water in the middle of it. Another container, labeled “bomb,” sits inside of a smaller cylinder which holds
a sample cup and is nested in the cylindrical container surrounded by the water. A black line extends into the water and is labeled “Precision
thermometer.” Two wires labeled “Electrodes” extend away from a cover that sits on top of the interior container. A read-out panel is located at
the top right of the cube.
The calorimeters described are designed to operate at constant (atmospheric) pressure and are convenient to measure heat flow accompanying
processes that occur in solution. A different type of calorimeter that operates at constant volume, colloquially known as a bomb calorimeter, is
used to measure the energy produced by reactions that yield large amounts of heat and gaseous products, such as combustion reactions. (The term
“bomb” comes from the observation that these reactions can be vigorous enough to resemble explosions that would damage other calorimeters.)
This type of calorimeter consists of a robust steel container (the “bomb”) that contains the reactants and is itself submerged in water (Figure
9.3.6). The sample is placed in the bomb, which is then filled with oxygen at high pressure. A small electrical spark is used to ignite the sample.
The energy produced by the reaction is trapped in the steel bomb and the surrounding water. The temperature increase is measured and, along
with the known heat capacity of the calorimeter, is used to calculate the energy produced by the reaction. Bomb calorimeters require calibration
to determine the heat capacity of the calorimeter and ensure accurate results. The calibration is accomplished using a reaction with a known q,
such as a measured quantity of benzoic acid ignited by a spark from a nickel fuse wire that is weighed before and after the reaction. The
temperature change produced by the known reaction is used to determine the heat capacity of the calorimeter. The calibration is generally
performed each time before the calorimeter is used to gather research data.

Physical Chemistry iBook - Bomb Calorimetry
Video 9.3.1 : Video of view how a bomb calorimeter is prepared for action.
 Example 9.3.5: Bomb Calorimetry
When 3.12 g of glucose, C6H12O6, is burned in a bomb calorimeter, the temperature of the calorimeter increases from 23.8 °C to 35.6 °C.
The calorimeter contains 775 g of water, and the bomb itself has a heat capacity of 893 J/°C. How much heat was produced by the
combustion of the glucose sample?
Solution
The combustion produces heat that is primarily absorbed by the water and the bomb. (The amounts of heat absorbed by the reaction products
and the unreacted excess oxygen are relatively small and dealing with them is beyond the scope of this text. We will neglect them in our
calculations.)
The heat produced by the reaction is absorbed by the water and the bomb:
qrxn = −(qwater + qbomb )
= −[(4.184 J/g °C) × (775 g) × (35.6°C − 23.8°C) + 893 J/°C × (35.6°C − 23.8°C)]
= −(38, 300 J + 10, 500 J)
= −48, 800 J = −48.8 kJ
This reaction released 48.7 kJ of heat when 3.12 g of glucose was burned.
 Exercise 9.3.5
When 0.963 g of benzene, C6H6, is burned in a bomb calorimeter, the temperature of the calorimeter increases by 8.39 °C. The bomb has a
heat capacity of 784 J/°C and is submerged in 925 mL of water. How much heat was produced by the combustion of the glucose sample?
Answer
39.0 kJ
Since the first one was constructed in 1899, 35 calorimeters have been built to measure the heat produced by a living person.1 These whole-body
calorimeters of various designs are large enough to hold an individual human being. More recently, whole-room calorimeters allow for relatively
normal activities to be performed, and these calorimeters generate data that more closely reflect the real world. These calorimeters are used to
measure the metabolism of individuals under different environmental conditions, different dietary regimes, and with different health conditions,
such as diabetes. In humans, metabolism is typically measured in Calories per day. A nutritional calorie (Calorie) is the energy unit used to
quantify the amount of energy derived from the metabolism of foods; one Calorie is equal to 1000 calories (1 kcal), the amount of energy needed
to heat 1 kg of water by 1 °C.

 Measuring Nutritional Calories
In your day-to-day life, you may be more familiar with energy being given in Calories, or nutritional calories, which are used to quantify the
amount of energy in foods. One calorie (cal) = exactly 4.184 joules, and one Calorie (note the capitalization) = 1000 cal, or 1 kcal. (This is
approximately the amount of energy needed to heat 1 kg of water by 1 °C.)
The macronutrients in food are proteins, carbohydrates, and fats or oils. Proteins provide about 4 Calories per gram, carbohydrates also
provide about 4 Calories per gram, and fats and oils provide about 9 Calories/g. Nutritional labels on food packages show the caloric content
of one serving of the food, as well as the breakdown into Calories from each of the three macronutrients (Figure 9.3.7).
Figure 9.3.7 : (a) Macaroni and cheese contain energy in the form of the macronutrients in the food. (b) The food’s nutritional information is
shown on the package label. In the US, the energy content is given in Calories (per serving); the rest of the world usually uses kilojoules.
(credit a: modification of work by “Rex Roof”/Flickr)
For the example shown in (b), the total energy per 228-g portion is calculated by:
(5 g protein × 4 Calories/g) + (31 g carb × 4 Calories/g) + (12 g f at × 9 Calories/g) = 252 Calories (9.3.5)
So, you can use food labels to count your Calories. But where do the values come from? And how accurate are they? The caloric content of
foods can be determined by using bomb calorimetry; that is, by burning the food and measuring the energy it contains. A sample of food is
weighed, mixed in a blender, freeze-dried, ground into powder, and formed into a pellet. The pellet is burned inside a bomb calorimeter, and
the measured temperature change is converted into energy per gram of food.
Today, the caloric content on food labels is derived using a method called the Atwater system that uses the average caloric content of the
different chemical constituents of food, protein, carbohydrate, and fats. The average amounts are those given in the equation and are derived
from the various results given by bomb calorimetry of whole foods. The carbohydrate amount is discounted a certain amount for the fiber
content, which is indigestible carbohydrate. To determine the energy content of a food, the quantities of carbohydrate, protein, and fat are
each multiplied by the average Calories per gram for each and the products summed to obtain the total energy.
Summary
Calorimetry is used to measure the amount of thermal energy transferred in a chemical or physical process. This requires careful measurement of
the temperature change that occurs during the process and the masses of the system and surroundings. These measured quantities are then used to
compute the amount of heat produced or consumed in the process using known mathematical relations. Calorimeters are designed to minimize
energy exchange between the system being studied and its surroundings. They range from simple coffee cup calorimeters used by introductory
chemistry students to sophisticated bomb calorimeters used to determine the energy content of food.
Footnotes
1. 1 Francis D. Reardon et al. “The Snellen human calorimeter revisited, re-engineered and upgraded: Design and performance characteristics.”
Medical and Biological Engineering and Computing 8 (2006)721–28, The Snellen human calorimeter revisited, re-engineered and upgraded:
design and performance characteristics [link.springer.com].
Glossary
bomb calorimeter
device designed to measure the energy change for processes occurring under conditions of constant volume; commonly used for reactions
involving solid and gaseous reactants or products

calorimeter
device used to measure the amount of heat absorbed or released in a chemical or physical process
calorimetry
process of measuring the amount of heat involved in a chemical or physical process
nutritional calorie (Calorie)

unit used for quantifying energy provided by digestion of foods, defined as 1000 cal or 1 kcal
surroundings
all matter other than the system being studied
system
portion of matter undergoing a chemical or physical change being studied
This page titled 9.3: Calorimetry is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
5.2: Calorimetry is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

9.4: Enthalpy
State the first law of thermodynamics
Define enthalpy and explain its classification as a state function
Write and balance thermochemical equations
Calculate enthalpy changes for various chemical reactions
Explain Hess’s law and use it to compute reaction enthalpies
Thermochemistry is a branch of chemical thermodynamics, the science that deals with the relationships between heat, work, and
other forms of energy in the context of chemical and physical processes. As we concentrate on thermochemistry in this chapter, we
need to consider some widely used concepts of thermodynamics.
Substances act as reservoirs of energy, meaning that energy can be added to them or removed from them. Energy is stored in a
substance when the kinetic energy of its atoms or molecules is raised. The greater kinetic energy may be in the form of increased
translations (travel or straight-line motions), vibrations, or rotations of the atoms or molecules. When thermal energy is lost, the
intensities of these motions decrease and the kinetic energy falls. The total of all possible kinds of energy present in a substance is
called the internal energy (U), sometimes symbolized as E.
As a system undergoes a change, its internal energy can change, and energy can be transferred from the system to the surroundings,
or from the surroundings to the system. Energy is transferred into a system when it absorbs heat (q) from the surroundings or when
the surroundings do work (w) on the system. For example, energy is transferred into room-temperature metal wire if it is immersed
in hot water (the wire absorbs heat from the water), or if you rapidly bend the wire back and forth (the wire becomes warmer
because of the work done on it). Both processes increase the internal energy of the wire, which is reflected in an increase in the
wire’s temperature. Conversely, energy is transferred out of a system when heat is lost from the system, or when the system does
work on the surroundings.
The relationship between internal energy, heat, and work can be represented by the equation:
ΔU = q + w (9.4.1)
as shown in Figure 9.4.1. This is one version of the first law of thermodynamics, and it shows that the internal energy of a system
changes through heat flow into or out of the system (positive q is heat flow in; negative q is heat flow out) or work done on or by
the system. The work, w, is positive if it is done on the system and negative if it is done by the system.
Figure 9.4.1 : The internal energy, U, of a system can be changed by heat flow and work. If heat flows into the system, qin, or work
is done on the system, won, its internal energy increases, ΔU > 0. If heat flows out of the system, qout, or work is done by the
system, wby, its internal energy decreases, ΔU < 0.
A type of work called expansion work (or pressure-volume work) occurs when a system pushes back the surroundings against a
restraining pressure, or when the surroundings compress the system. An example of this occurs during the operation of an internal
combustion engine. The reaction of gasoline and oxygen is exothermic. Some of this energy is given off as heat, and some does
work pushing the piston in the cylinder. The substances involved in the reaction are the system, and the engine and the rest of the

universe are the surroundings. The system loses energy by both heating and doing work on the surroundings, and its internal energy
decreases. (The engine is able to keep the car moving because this process is repeated many times per second while the engine is
running.) We will consider how to determine the amount of work involved in a chemical or physical change in the chapter on
thermodynamics.
As discussed, the relationship between internal energy, heat, and work can be represented as ΔU = q + w. Internal energy is a type
of quantity known as a state function (or state variable), whereas heat and work are not state functions. The value of a state function
depends only on the state that a system is in, and not on how that state is reached. If a quantity is not a state function, then its value
does depend on how the state is reached. An example of a state function is altitude or elevation. If you stand on the summit of Mt.
Kilimanjaro, you are at an altitude of 5895 m, and it does not matter whether you hiked there or parachuted there. The distance you
traveled to the top of Kilimanjaro, however, is not a state function. You could climb to the summit by a direct route or by a more
roundabout, circuitous path (Figure 9.4.2). The distances traveled would differ (distance is not a state function) but the elevation
reached would be the same (altitude is a state function).
Figure 9.4.2 : Paths X and Y represent two different routes to the summit of Mt. Kilimanjaro. Both have the same change in
elevation (altitude or elevation on a mountain is a state function; it does not depend on path), but they have very different distances
traveled (distance walked is not a state function; it depends on the path). (credit: modification of work by Paul Shaffner)
An aerial photo depicts a view of Mount Kilimanjaro. A straight, green arrow labeled X is drawn from the term “base,” written at
the bottom of the mountain, to the term “Summit,” written at the top of the mountain. Another arrow labeled Y is draw from the
base to the summit alongside the green arrow, but this arrow is pink and has three large S-shaped curves along its length.
Chemists ordinarily use a property known as enthalpy (H ) to describe the thermodynamics of chemical and physical processes.
Enthalpy is defined as the sum of a system’s internal energy (U ) and the mathematical product of its pressure (P ) and volume (V ):
H = U +PV (9.4.2)
Since it is derived from three state functions (U , P , and V ), enthalpy is also a state function. Enthalpy values for specific
substances cannot be measured directly; only enthalpy changes for chemical or physical processes can be determined. For
processes that take place at constant pressure (a common condition for many chemical and physical changes), the enthalpy change (
ΔH ) is:
ΔH = ΔU + P ΔV (9.4.3)
The mathematical product P ΔV represents work (w), namely, expansion or pressure-volume work as noted. By their definitions,
the arithmetic signs of ΔV and w will always be opposite:
P ΔV = −w (9.4.4)
Substituting Equation 9.4.4 and the definition of internal energy (Equation 9.4.1) into Equation 9.4.3 yields:
ΔH = ΔU + P ΔV (9.4.5)
= qp + w − w (9.4.6)
= qp (9.4.7)
where q is the heat of reaction under conditions of constant pressure.

p
And so, if a chemical or physical process is carried out at constant pressure with the only work done caused by expansion or
contraction, then the heat flow (q ) and enthalpy change (ΔH ) for the process are equal.
p

The heat given off when you operate a Bunsen burner is equal to the enthalpy change of the methane combustion reaction that takes
place, since it occurs at the essentially constant pressure of the atmosphere. On the other hand, the heat produced by a reaction
measured in a bomb calorimeter is not equal to ΔH because the closed, constant-volume metal container prevents expansion work
from occurring. Chemists usually perform experiments under normal atmospheric conditions, at constant external pressure with
q = ΔH , which makes enthalpy the most convenient choice for determining heat.
The following conventions apply when we use ΔH :

1. Chemists use a thermochemical equation to represent the changes in both matter and energy. In a thermochemical equation, the
enthalpy change of a reaction is shown as a ΔH value following the equation for the reaction. This ΔH value indicates the
amount of heat associated with the reaction involving the number of moles of reactants and products as shown in the chemical
equation. For example, consider this equation:
1
H (g) + O (g) ⟶ H O(l) ΔH = −286 kJ (9.4.8)
2 2 2 2
This equation indicates that when 1 mole of hydrogen gas and 12 mole of oxygen gas at some temperature and pressure change
to 1 mole of liquid water at the same temperature and pressure, 286 kJ of heat are released to the surroundings. If the
coefficients of the chemical equation are multiplied by some factor, the enthalpy change must be multiplied by that same factor
(ΔH is an extensive property).
(two-fold increase in amounts)
2 H (g) + O (g) ⟶ 2 H O(l) ΔH = 2 × (−286 kJ) = −572 kJ

2 2 2
(two-fold decrease in amounts)
1 1 1 1
H (g) + O (g) ⟶ H O(l) ΔH = × (−286 kJ) = −143 kJ
2 2 2
2 4 2 2
2. The enthalpy change of a reaction depends on the physical state of the reactants and products of the reaction (whether we have
gases, liquids, solids, or aqueous solutions), so these must be shown. For example, when 1 mole of hydrogen gas and 12 mole
of oxygen gas change to 1 mole of liquid water at the same temperature and pressure, 286 kJ of heat are released. If gaseous
water forms, only 242 kJ of heat are released.
1
H (g) + O (g) ⟶ H O(g) ΔH = −242 kJ (9.4.9)
2 2 2 2
3. A negative value of an enthalpy change, ΔH, indicates an exothermic reaction; a positive value of ΔH indicates an endothermic
reaction. If the direction of a chemical equation is reversed, the arithmetic sign of its ΔH is changed (a process that is
endothermic in one direction is exothermic in the opposite direction).
 Example 9.4.1: Measurement of an Enthalpy Change
When 0.0500 mol of HCl(aq) reacts with 0.0500 mol of NaOH(aq) to form 0.0500 mol of NaCl(aq), 2.9 kJ of heat are
produced. What is ΔH, the enthalpy change, per mole of acid reacting, for the acid-base reaction run under the conditions
described ?
HCl(aq) + NaOH(aq) → NaCl(aq) + H O(l)

2
Solution
For the reaction of 0.0500 mol acid (HCl), q = −2.9 kJ. This ratio
−2.9 kJ
0.0500 mol HCl
can be used as a conversion factor to find the heat produced when 1 mole of HCl reacts:
−2.9 kJ
ΔH = 1 mol HCl × = −58 kJ
0.0500 mol HCl

The enthalpy change when 1 mole of HCl reacts is −58 kJ. Since that is the number of moles in the chemical equation, we
write the thermochemical equation as:
HCl(aq) + NaOH(aq) ⟶ NaCl(aq) + H O(l) ΔH = −58 kJ

2
 Exercise 9.4.1
When 1.34 g Zn(s) reacts with 60.0 mL of 0.750 M HCl(aq), 3.14 kJ of heat are produced. Determine the enthalpy change per
mole of zinc reacting for the reaction:
Zn(s) + 2 HCl(aq) ⟶ ZnCl(aq) + H2(g)
Answer
ΔH = −153 kJ
Be sure to take both stoichiometry and limiting reactants into account when determining the ΔH for a chemical reaction.
 Example 9.4.2: Another Example of the Measurement of an Enthalpy Change

A gummy bear contains 2.67 g sucrose, C12H22O11. When it reacts with 7.19 g potassium chlorate, KClO3, 43.7 kJ of heat are
produced. Determine the enthalpy change for the reaction
C H O (aq) + 8 KClO (aq) ⟶ 12 CO (g) + 11 H O(l) + 8 KCl(aq)

12 22 11 3 2 2
Solution
1 mol
We have 2.67 g × = 0.00780 mol C12 H22 O11 available, and
342.3 g
1 mol
7.19 g × = 0.0587 mol KCl O3 available.
122.5 g
Since
1 mol C H O
12 22 11
0.0587 mol KCl O3 × = 0.00734 mol C H O
12 22 11
8 mol KClO3
is needed, C12H22O11 is the excess reactant and KClO3 is the limiting reactant.
−43.7 kJ
The reaction uses 8 mol KClO3, and the conversion factor is , so we have
0.0587 mol KClO3
−43.7 kJ
ΔH = 8 mol × = −5960 kJ . The enthalpy change for this reaction is −5960 kJ, and the
0.0587 mol KClO3
thermochemical equation is:
C H O + 8 KClO ⟶ 12 CO + 11 H O + 8 KCl ΔH = −5960 kJ

12 22 11 3 2 2
 Exercise 9.4.2
When 1.42 g of iron reacts with 1.80 g of chlorine, 3.22 g of FeCl 2(s)
and 8.60 kJ of heat is produced. What is the enthalpy
change for the reaction when 1 mole of FeCl (s) is produced? 2
Answer
ΔH = −338 kJ

Enthalpy changes are typically tabulated for reactions in which both the reactants and products are at the same conditions. A
standard state is a commonly accepted set of conditions used as a reference point for the determination of properties under other
different conditions. For chemists, the IUPAC standard state refers to materials under a pressure of 1 bar and solutions at 1 M, and
does not specify a temperature (it used too). Many thermochemical tables list values with a standard state of 1 atm. Because the
ΔH of a reaction changes very little with such small changes in pressure (1 bar = 0.987 atm), ΔH values (except for the most
precisely measured values) are essentially the same under both sets of standard conditions. We will include a superscripted “o” in
the enthalpy change symbol to designate standard state. Since the usual (but not technically standard) temperature is 298.15 K, we
will use a subscripted “298” to designate this temperature. Thus, the symbol (ΔH ) is used to indicate an enthalpy change for a
298
∘
process occurring under these conditions. (The symbol ΔH is used to indicate an enthalpy change for a reaction occurring under
nonstandard conditions.)
The enthalpy changes for many types of chemical and physical processes are available in the reference literature, including those
for combustion reactions, phase transitions, and formation reactions. As we discuss these quantities, it is important to pay attention
to the extensive nature of enthalpy and enthalpy changes. Since the enthalpy change for a given reaction is proportional to the
amounts of substances involved, it may be reported on that basis (i.e., as the ΔH for specific amounts of reactants). However, we
often find it more useful to divide one extensive property (ΔH) by another (amount of substance), and report a per-amount intensive
value of ΔH, often “normalized” to a per-mole basis. (Note that this is similar to determining the intensive property specific heat
from the extensive property heat capacity, as seen previously.)
Enthalpy of Combustion
Standard enthalpy of combustion (ΔH ) is the enthalpy change when 1 mole of a substance burns (combines vigorously with
C
∘
oxygen) under standard state conditions; it is sometimes called “heat of combustion.” For example, the enthalpy of combustion of
ethanol, −1366.8 kJ/mol, is the amount of heat produced when one mole of ethanol undergoes complete combustion at 25 °C and 1
atmosphere pressure, yielding products also at 25 °C and 1 atm.
∘
C H OH(l) + 3 O (g) ⟶ 2 CO + 3 H O(l) ΔH = −1366.8 kJ (9.4.10)
2 5 2 2 2 298
Enthalpies of combustion for many substances have been measured; a few of these are listed in Table 9.4.1. Many readily available
substances with large enthalpies of combustion are used as fuels, including hydrogen, carbon (as coal or charcoal), and
hydrocarbons (compounds containing only hydrogen and carbon), such as methane, propane, and the major components of
gasoline.
Table 9.4.1 : Standard Molar Enthalpies of Combustion
Enthalpy of Combustion
Substance Combustion Reaction ∘
kJ
ΔHc ( at 25°C)
mol
carbon C(s) + O (g) ⟶ CO (g)

2 2
−393.5
hydrogen H (g) +
2
1
2
O (g) ⟶ H O(l)
2 2
−285.8
magnesium Mg(s) +
1
2
O (g) ⟶ MgO(s)
2
−601.6
sulfur S(s) + O (g) ⟶ SO (g)

2 2
−296.8
carbon monoxide CO(g) +

1
2
O (g) ⟶ CO (g)
2 2
−283.0
methane CH (g) + 2 O (g) ⟶ CO (g) + 2 H O(l)

4 2 2 2
−890.8
5
acetylene C H (g) +
2 2
O (g) ⟶ 2 CO (g) + H O(l)
2 2 2
−1301.1
2
ethanol C H OH(l) + 3 O (g) ⟶ CO (g) + 3 H O(l)

2 5 2 2 2
−1366.8
3
methanol CH OH(l) +
3
O (g) ⟶ CO (g) + 2 H O(l)
2 2 2
−726.1
2
25
isooctane C H
8 18
(l) + O (g) ⟶ 8 CO (g) + 9 H O(l)
2 2 2
−5461
2

 Example 9.4.3: Using Enthalpy of Combustion
As Figure 9.4.3 suggests, the combustion of gasoline is a highly exothermic process. Let us determine the approximate amount
of heat produced by burning 1.00 L of gasoline, assuming the enthalpy of combustion of gasoline is the same as that of
isooctane, a common component of gasoline. The density of isooctane is 0.692 g/mL.
Figure 9.4.3 : The combustion of gasoline is very exothermic. (credit: modification of work by “AlexEagle”/Flickr)
Solution
Starting with a known amount (1.00 L of isooctane), we can perform conversions between units until we arrive at the desired
amount of heat or energy. The enthalpy of combustion of isooctane provides one of the necessary conversions. Table 9.4.1
gives this value as −5460 kJ per 1 mole of isooctane (C8H18).
Using these data,
1000 mL C H 0.692 g C H 1 mol C H

8 18 8 18 8 18 −5460 kJ
4
1.00 LC H × × × × = −3.31 × 10 kJ
8 18
1 LC H 1 mL C H 114 g C H 1 mol C H
8 18 8 18 8 18 8 18
The combustion of 1.00 L of isooctane produces 33,100 kJ of heat. (This amount of energy is enough to melt 99.2 kg, or about
218 lbs, of ice.)
Note: If you do this calculation one step at a time, you would find:
3
1.00 L C H ⟶ 1.00 × 10 mL C H
8 18 8 18
3
1.00 × 10 mL C H ⟶ 692 g C H
8 18 8 18
692 g C H ⟶ 6.07 mol C H

8 18 8 18
4
692 g C H ⟶ −3.31 × 10 kJ
8 18
 Exercise 9.4.3
How much heat is produced by the combustion of 125 g of acetylene?
Answer
6.25 × 103 kJ
 Emerging Algae-Based Energy Technologies (Biofuels)
As reserves of fossil fuels diminish and become more costly to extract, the search is ongoing for replacement fuel sources for
the future. Among the most promising biofuels are those derived from algae (Figure 9.4.4). The species of algae used are
nontoxic, biodegradable, and among the world’s fastest growing organisms. About 50% of algal weight is oil, which can be
readily converted into fuel such as biodiesel. Algae can yield 26,000 gallons of biofuel per hectare—much more energy per
acre than other crops. Some strains of algae can flourish in brackish water that is not usable for growing other crops. Algae can
produce biodiesel, biogasoline, ethanol, butanol, methane, and even jet fuel.

Figure 9.4.4 : (a) Tiny algal organisms can be (b) grown in large quantities and eventually (c) turned into a useful fuel such as
biodiesel. (credit a: modification of work by Micah Sittig; credit b: modification of work by Robert Kerton; credit c:
modification of work by John F. Williams)
According to the US Department of Energy, only 39,000 square kilometers (about 0.4% of the land mass of the US or less than
1
of the area used to grow corn) can produce enough algal fuel to replace all the petroleum-based fuel used in the US. The
7
cost of algal fuels is becoming more competitive—for instance, the US Air Force is producing jet fuel from algae at a total cost
of under $5 per gallon. The process used to produce algal fuel is as follows: grow the algae (which use sunlight as their energy
source and CO2 as a raw material); harvest the algae; extract the fuel compounds (or precursor compounds); process as
necessary (e.g., perform a transesterification reaction to make biodiesel); purify; and distribute (Figure 9.4.5).
Figure 9.4.5 : Algae convert sunlight and carbon dioxide into oil that is harvested, extracted, purified, and transformed into a
variety of renewable fuels.
Standard Enthalpy of Formation

A standard enthalpy of formation ΔH is an enthalpy change for a reaction in which exactly 1 mole of a pure substance is formed
∘
f
from free elements in their most stable states under standard state conditions. These values are especially useful for computing or
predicting enthalpy changes for chemical reactions that are impractical or dangerous to carry out, or for processes for which it is
difficult to make measurements. If we have values for the appropriate standard enthalpies of formation, we can determine the
enthalpy change for any reaction, which we will practice in the next section on Hess’s law.
The standard enthalpy of formation of CO2(g) is −393.5 kJ/mol. This is the enthalpy change for the exothermic reaction:
∘ ∘
C(s) + O (g) ⟶ CO (g) ΔH = ΔH = −393.5 kJ (9.4.11)
2 2 f 298
starting with the reactants at a pressure of 1 atm and 25 °C (with the carbon present as graphite, the most stable form of carbon
under these conditions) and ending with one mole of CO2, also at 1 atm and 25 °C. For nitrogen dioxide, NO , ΔH is 33.2 2(g)
∘
f
kJ/mol. This is the enthalpy change for the reaction:

1
∘ ∘
N (g) + O (g) ⟶ NO (g) ΔH = ΔH = +33.2 kJ (9.4.12)
2 2 2 f 298
2
A reaction equation with mole of N2 and 1 mole of O2 is correct in this case because the standard enthalpy of formation always
1
refers to 1 mole of product, NO2(g).

You will find a table of standard enthalpies of formation of many common substances in Tables T1 and T2. These values indicate
that formation reactions range from highly exothermic (such as −2984 kJ/mol for the formation of P4O10) to strongly endothermic
(such as +226.7 kJ/mol for the formation of acetylene, C2H2). By definition, the standard enthalpy of formation of an element in its
most stable form is equal to zero under standard conditions, which is 1 atm for gases and 1 M for solutions.

 Example 9.4.4: Evaluating an Enthalpy of Formation
Ozone, O3(g), forms from oxygen, O2(g), by an endothermic process. Ultraviolet radiation is the source of the energy that
drives this reaction in the upper atmosphere. Assuming that both the reactants and products of the reaction are in their standard
states, determine the standard enthalpy of formation, ΔH of ozone from the following information:
∘
f
∘
3 O (g) ⟶ 2 O (g) ΔH = +286 kJ
2 3 298
Solution ΔH is the enthalpy change for the formation of one mole of a substance in its standard state from the elements in
f
∘
their standard states. Thus, ΔH for O3(g) is the enthalpy change for the reaction:
∘
f
3
O (g) ⟶ O (g)
2 3
2
286 kJ
For the formation of 2 mol of O3(g), ΔH ∘
298
= +286 kJ . This ratio, ( ), can be used as a conversion factor to find
2 mol O3
the heat produced when 1 mole of O3(g) is formed, which is the enthalpy of formation for O3(g):
286 kJ
∘
ΔH for 1 mole of O (g) = 1 mol O3 × = 143 kJ
3
2 mol O3
Therefore, ΔH f
∘
[ O (g)] = +143 kJ/mol
3
.
 Exercise 9.4.4
Hydrogen gas, H2, reacts explosively with gaseous chlorine, Cl2, to form hydrogen chloride, HCl(g). What is the enthalpy
change for the reaction of 1 mole of H2(g) with 1 mole of Cl2(g) if both the reactants and products are at standard state
conditions? The standard enthalpy of formation of HCl(g) is −92.3 kJ/mol.
Answer
For the reaction
∘
H (g) + Cl (g) ⟶ 2 HCl(g) ΔH = −184.6 kJ
2 2 298
 Example 9.4.5: Writing Reaction Equations for ΔH f

∘
Write the heat of formation reaction equations for:

a. C H OH
2 5 (l)
b. Ca (PO )
3 4 2(s)
Solution
Remembering that ΔH reaction equations are for forming 1 mole of the compound from its constituent elements under
∘
f
standard conditions, we have:

a. 2 C(s, graphite) + 3 H (g) + O (g) ⟶ C H OH(l)
2
1
2 2 2 5
b. 3 Ca(s) + P (s) + 4 O (g) ⟶ Ca (PO ) (s)

1
2 4 2 3 4 2
Note: The standard state of carbon is graphite, and phosphorus exists as P . 4
 Exercise 9.4.5
Write the heat of formation reaction equations for:
a. C H OC
2 5 2
H5(l)
b. Na CO2 3(s)

Answer a
4 C(s, graphite) + 5 H (g) +
2
1
2
O (g) ⟶ C H OC H (l)
2 2 5 2 5
;
Answer b
3
2 Na(s) + C(s, graphite) + O (g) ⟶ Na CO (s)
2 2 3
2
Hess’s Law
There are two ways to determine the amount of heat involved in a chemical change: measure it experimentally, or calculate it from
other experimentally determined enthalpy changes. Some reactions are difficult, if not impossible, to investigate and make accurate
measurements for experimentally. And even when a reaction is not hard to perform or measure, it is convenient to be able to
determine the heat involved in a reaction without having to perform an experiment.
This type of calculation usually involves the use of Hess’s law, which states: If a process can be written as the sum of several
stepwise processes, the enthalpy change of the total process equals the sum of the enthalpy changes of the various steps. Hess’s law
is valid because enthalpy is a state function: Enthalpy changes depend only on where a chemical process starts and ends, but not on
the path it takes from start to finish. For example, we can think of the reaction of carbon with oxygen to form carbon dioxide as
occurring either directly or by a two-step process. The direct process is written:
∘
C(s) + O2(g) ⟶ CO2(g) ΔH = −394 kJ (9.4.13)
298
In the two-step process, first carbon monoxide is formed:

1
∘
C(s) + O2(g) ⟶ CO(g) ΔH = −111 kJ (9.4.14)
298
2
Then, carbon monoxide reacts further to form carbon dioxide:

1
∘
CO(g) + O (g) ⟶ CO2 (g) ΔH = −283 kJ (9.4.15)
2 298
2
The equation describing the overall reaction is the sum of these two chemical changes:
1
Step 1: C(s) + O (g) ⟶ CO(g)
2
2
1
Step 2: CO(g) + O (g) ⟶ CO (g)
2 2
2
––––––––––––––––––––––––––––––––––––
1 1
Sum: C(s) + O (g) + CO(g) + O (g) ⟶ CO(g) + CO (g)
2 2 2
2 2
Because the CO produced in Step 1 is consumed in Step 2, the net change is:
C(s) + O2(g) ⟶ CO2(g) (9.4.16)
According to Hess’s law, the enthalpy change of the reaction will equal the sum of the enthalpy changes of the steps. We can apply
the data from the experimental enthalpies of combustion in Table 9.4.1 to find the enthalpy change of the entire reaction from its
two steps:
1
∘
C(s) + O (g) ⟶ CO(g) ΔH = −111 kJ
2 298
2
1
∘
CO(g) + O (g) ⟶ CO (g) ΔH = −283 kJ
2 2 298
2
¯
¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯
¯ ¯
¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯
¯
∘
C(s) + O (g) ⟶ CO (g) ΔH = −394 kJ
2 2 298
The result is shown in Figure 9.4.6. We see that ΔH of the overall reaction is the same whether it occurs in one step or two. This
finding (overall ΔH for the reaction = sum of ΔH values for reaction “steps” in the overall reaction) is true in general for chemical
and physical processes.

Figure 9.4.6 : The formation of CO2(g) from its elements can be thought of as occurring in two steps, which sum to the overall
reaction, as described by Hess’s law. The horizontal blue lines represent enthalpies. For an exothermic process, the products are at
lower enthalpy than are the reactants.
Before we further practice using Hess’s law, let us recall two important features of ΔH.
1. ΔH is directly proportional to the quantities of reactants or products. For example, the enthalpy change for the reaction forming
1 mole of NO2(g) is +33.2 kJ:
1
N (g) + O (g) ⟶ NO (g) ΔH = +33.2 kJ (9.4.17)
2 2 2
2
When 2 moles of NO2 (twice as much) are formed, the ΔH will be twice as large:
N (g) + 2 O (g) ⟶ 2 NO (g) ΔH = +66.4 kJ (9.4.18)
2 2 2
In general, if we multiply or divide an equation by a number, then the enthalpy change should also be multiplied or divided by
the same number.
2. ΔH for a reaction in one direction is equal in magnitude and opposite in sign to ΔH for the reaction in the reverse direction. For
example, given that:
H (g) + Cl (g) ⟶ 2 HCl(g) ΔH = −184.6 kJ (9.4.19)
2 2
Then, for the “reverse” reaction, the enthalpy change is also “reversed”:
2 HCl(g) ⟶ H (g) + Cl (g) ΔH = +184.6 kJ (9.4.20)
2 2
 Example 9.4.6: Stepwise Calculation of ΔH ∘

f
Using Hess’s Law Determine the enthalpy of formation, ΔH

f
∘
, of FeCl3(s) from the enthalpy changes of the following two-
step process that occurs under standard state conditions:
Fe(s) + Cl (g) ⟶ FeCl (s) ΔH ° = −341.8 kJ

2 2
1
FeCl (s) + Cl (g) ⟶ FeCl (s) ΔH ° = −57.7 kJ
2 2 3
2
Solution
We are trying to find the standard enthalpy of formation of FeCl3(s), which is equal to ΔH° for the reaction:
3
∘
Fe(s) + Cl (g) ⟶ FeCl (s) ΔH =?
2 3 f
2
Looking at the reactions, we see that the reaction for which we want to find ΔH° is the sum of the two reactions with known
ΔH values, so we must sum their ΔHs:

2 2
1
FeCl (s) +Cl (g) ⟶ FeCl (s) ΔH ° = −57.7 kJ
2 2 3
2
––––––––––––––––––––––––––––––––––––––––––––––––––––
1
2 3
2
The enthalpy of formation, ΔH , of FeCl3(s) is −399.5 kJ/mol.

∘
f
 Exercise 9.4.6
Calculate ΔH for the process:
N (g) + 2 O (g) ⟶ 2 NO (g)

2 2 2
from the following information:
N (g) + O (g) ⟶ 2 NO(g) ΔH = 180.5 kJ

2 2
1
NO(g) + O (g) ⟶ NO (g) ΔH = −57.06 kJ
2 2
2
Answer
66.4 kJ
Here is a less straightforward example that illustrates the thought process involved in solving many Hess’s law problems. It shows
how we can find many standard enthalpies of formation (and other values of ΔH) if they are difficult to determine experimentally.
 Example 9.4.7: A More Challenging Problem
Using Hess’s Law Chlorine monofluoride can react with fluorine to form chlorine trifluoride:
(i) ClF(g) + F 2
(g) ⟶ ClF (g)
3
ΔH ° = ?
Use the reactions here to determine the ΔH° for reaction (i):
(ii) 2 OF 2
(g) ⟶ O (g) + 2 F (g)
2 2
ΔH
∘
(ii)
= −49.4 kJ
(iii) 2 ClF(g) + O 2
(g) ⟶ Cl O(g) + OF (g)
2 2
ΔH
∘
(iii)
= +205.6 kJ
3
(iv) ClF 3
(g) + O (g) ⟶
2
1
2
Cl O(g) +
2
OF (g)
2
ΔH
∘
(iv)
= +266.7 kJ
2
Solution
Our goal is to manipulate and combine reactions (ii), (iii), and (iv) such that they add up to reaction (i). Going from left to right
in (i), we first see that ClF is needed as a reactant. This can be obtained by multiplying reaction (iii) by , which means that
(g)
1
the ΔH° change is also multiplied by : 1
1 1 1 1
ClF(g) + O (g) ⟶ Cl O(g) + OF (g) ΔH ° = (205.6) = +102.8 kJ
2 2 2
2 2 2 2
Next, we see that F is also needed as a reactant. To get this, reverse and halve reaction (ii), which means that the ΔH° changes
2
sign and is halved:

1
O (g) + F (g) ⟶ OF (g) ΔH ° = +24.7 kJ
2 2 2
2
To get ClF3 as a product, reverse (iv), changing the sign of ΔH°:

1 3
Cl O(g) + OF (g) ⟶ ClF (g) + O (g) ΔH ° = −266.7 kJ
2 2 3 2
2 2

Now check to make sure that these reactions add up to the reaction we want:
1 1 1
ClF(g) + O (g) ⟶ Cl O(g) + OF (g) ΔH ° = +102.8 kJ
2 2 2
2 2 2
1
O (g) + F (g) ⟶ OF (g) ΔH ° = +24.7 kJ
2 2 2
2
1 3
Cl O(g) + OF (g) ⟶ ClF (g) + O (g) ΔH ° = −266.7 kJ
2 2 3 2
2 2
¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯
¯ ¯
¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯
¯
ClF(g) + F ⟶ ClF (g) ΔH ° = −139.2 kJ
2 3
3
Reactants 1
2
O
2
and 1
2
O
2
cancel out product O2; product 1
2
Cl O
2
cancels reactant 1
2
Cl O
2
; and reactant OF
2
is cancelled by
2
products OF and OF2. This leaves only reactants ClF(g) and F2(g) and product ClF3(g), which are what we want. Since
1
2 2
summing these three modified reactions yields the reaction of interest, summing the three modified ΔH° values will give the
desired ΔH°:
ΔH ° = (+102.8 kJ) + (24.7 kJ) + (−266.7 kJ) = −139.2 kJ
 Exercise 9.4.7
Aluminum chloride can be formed from its elements:

(i) 2 Al(s) + 3 Cl 2
(g) ⟶ 2 AlCl (s)
3
ΔH ° = ?
Use the reactions here to determine the ΔH° for reaction (i):
(ii) HCl(g) ⟶ HCl(aq) ΔH
∘
(ii)
= −74.8 kJ
(iii) H 2
(g) + Cl (g) ⟶ 2 HCl(g)
2
ΔH
∘
(iii)
= −185 kJ
(iv) AlCl 3
(aq) ⟶ AlCl (s)
3
ΔH
∘
(iv)
= +323 kJ/mol
(v) 2 Al(s) + 6 HCl(aq) ⟶ 2 AlCl 3

(aq) + 3 H (g)
2
ΔH
∘
(v)
= −1049 kJ
Answer
−1407 kJ
We also can use Hess’s law to determine the enthalpy change of any reaction if the corresponding enthalpies of formation of the
reactants and products are available. The stepwise reactions we consider are: (i) decompositions of the reactants into their
component elements (for which the enthalpy changes are proportional to the negative of the enthalpies of formation of the
reactants), followed by (ii) re-combinations of the elements to give the products (with the enthalpy changes proportional to the
enthalpies of formation of the products). The standard enthalpy change of the overall reaction is therefore equal to: (ii) the sum of
the standard enthalpies of formation of all the products plus (i) the sum of the negatives of the standard enthalpies of formation of
the reactants. This is usually rearranged slightly to be written as follows, with ∑ representing “the sum of” and n standing for the
stoichiometric coefficients:
∘ ∘ ∘
ΔH = ∑ n × ΔH (products) − ∑ n × ΔH (reactants) (9.4.21)
reaction f f
The following example shows in detail why this equation is valid, and how to use it to calculate the enthalpy change for a reaction
of interest.
 Example 9.4.8: Using Hess’s Law

What is the standard enthalpy change for the reaction:
3 NO (g) + H O(l) ⟶ 2 HNO (aq) + NO(g) ΔH ° = ?

2 2 3
Solution 1: Using the Equation

Alternatively, we could use the special form of Hess’s law given previously:
∘ ∘ ∘
ΔH = ∑ n × ΔH (products) − ∑ n × ΔH (reactants)
reaction f f
⎡ −207.4 kJ +90.2 kJ ⎤
= 2 mol HNO3 × +1 mol NO (g) ×
⎣ mol HNO3 (aq) mol NO (g) ⎦
⎡ +33.2 kJ −285.8 kJ ⎤
− 3 mol NO2 (g) × +1 mol H2 O (l) ×
⎣ mol NO2 (g) mol H2 O (l) ⎦
= 2(−207.4 kJ) + 1(+90.2 kJ) − 3(+33.2 kJ) − 1(−285.8 kJ)
= −138.4 kJ
Solution 2: Supporting Why the General Equation Is Valid

We can write this reaction as the sum of the decompositions of 3NO2(g) and 1H2O(l) into their constituent elements, and the
formation of 2 HNO3(aq) and 1 NO(g) from their constituent elements. Writing out these reactions, and noting their
relationships to the ΔH values for these compounds (from Tables T1 and T2 ), we have:
∘
f
3
∘
3 NO (g) ⟶ N (g) + 3 O (g) ΔH = −99.6 kJ
2 2 2 1
2
1
∘ ∘
H O(l) ⟶ H (g) + O (g) ΔH = +285.8 kJ [−1 × ΔH (H O)]
2 2 2 2 f 2
2
∘ ∘
H (g) + N (g) + 3 O (g) ⟶ 2 HNO (aq) ΔH = −414.8 kJ [2 × ΔH (HNO )]
2 2 2 3 3 f 3
1 1
∘
N (g) + O (g) ⟶ NO(g) ΔH = +90.2 kJ [1 × (NO)]
2 2 4
2 2
Summing these reaction equations gives the reaction we are interested in:
3 NO (g) + H O(l) ⟶ 2 HNO (aq) + NO(g)

2 2 3
Summing their enthalpy changes gives the value we want to determine:

∘ ∘ ∘ ∘ ∘
ΔHrxn = ΔH + ΔH + ΔH + ΔH = (−99.6 kJ) + (+285.8 kJ) + (−414.8 kJ) + (+90.2 kJ)
1 2 3 4
= −138.4 kJ
So the standard enthalpy change for this reaction is ΔH° = −138.4 kJ.
Note that this result was obtained by:
1. multiplying the ΔH of each product by its stoichiometric coefficient and summing those values,
∘
f
2. multiplying the ΔH of each reactant by its stoichiometric coefficient and summing those values, and then
∘
f
3. subtracting the result found in step 2 from the result found in step 1.
This is also the procedure in using the general equation, as shown.
 Exercise 9.4.8
Calculate the heat of combustion of 1 mole of ethanol, C2H5OH(l), when H2O(l) and CO2(g) are formed. Use the following
enthalpies of formation: C2H5OH(l), −278 kJ/mol; H2O(l), −286 kJ/mol; and CO2(g), −394 kJ/mol.
Answer
−1368 kJ/mol

Summary
If a chemical change is carried out at constant pressure and the only work done is caused by expansion or contraction, q for the
change is called the enthalpy change with the symbol ΔH, or ΔH for reactions occurring under standard state conditions. The
∘
298
value of ΔH for a reaction in one direction is equal in magnitude, but opposite in sign, to ΔH for the reaction in the opposite
direction, and ΔH is directly proportional to the quantity of reactants and products. Examples of enthalpy changes include enthalpy
of combustion, enthalpy of fusion, enthalpy of vaporization, and standard enthalpy of formation. The standard enthalpy of
formation, ΔH , is the enthalpy change accompanying the formation of 1 mole of a substance from the elements in their most
∘
f
stable states at 1 bar (standard state). Many of the processes are carried out at 298.15 K. If the enthalpies of formation are available
for the reactants and products of a reaction, the enthalpy change can be calculated using Hess’s law: If a process can be written as
the sum of several stepwise processes, the enthalpy change of the total process equals the sum of the enthalpy changes of the
various steps.
Key Equations
ΔU = q + w
∘ ∘ ∘
ΔH = ∑ n × ΔH (products) − ∑ n × ΔH (reactants)
reaction f f
Footnotes
1. 1 For more on algal fuel, see www.theguardian.com/environme...n-fuel-problem.
Glossary
chemical thermodynamics
area of science that deals with the relationships between heat, work, and all forms of energy associated with chemical and
physical processes
enthalpy (H)
sum of a system’s internal energy and the mathematical product of its pressure and volume
enthalpy change (ΔH)

heat released or absorbed by a system under constant pressure during a chemical or physical process
expansion work (pressure-volume work)

work done as a system expands or contracts against external pressure
first law of thermodynamics

internal energy of a system changes due to heat flow in or out of the system or work done on or by the system
Hess’s law
if a process can be represented as the sum of several steps, the enthalpy change of the process equals the sum of the enthalpy
changes of the steps
hydrocarbon
compound composed only of hydrogen and carbon; the major component of fossil fuels
internal energy (U)

total of all possible kinds of energy present in a substance or substances
standard enthalpy of combustion (ΔH ) ∘

c
heat released when one mole of a compound undergoes complete combustion under standard conditions
standard enthalpy of formation (ΔH ) ∘

f
enthalpy change of a chemical reaction in which 1 mole of a pure substance is formed from its elements in their most stable
states under standard state conditions

standard state
set of physical conditions as accepted as common reference conditions for reporting thermodynamic properties; 1 bar of
pressure, and solutions at 1 molar concentrations, usually at a temperature of 298.15 K
state function
property depending only on the state of a system, and not the path taken to reach that state
This page titled 9.4: Enthalpy is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
5.3: Enthalpy is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

5.1: Energy Basics
Q5.1.1
A burning match and a bonfire may have the same temperature, yet you would not sit around a burning match on a fall evening to
stay warm. Why not?
S5.1.1
The temperature of 1 gram of burning wood is approximately the same for both a match and a bonfire. This is an intensive property
and depends on the material (wood). However, the overall amount of produced heat depends on the amount of material; this is an
extensive property. The amount of wood in a bonfire is much greater than that in a match; the total amount of produced heat is also
much greater, which is why we can sit around a bonfire to stay warm, but a match would not provide enough heat to keep us from
getting cold.
Q5.1.2
Prepare a table identifying several energy transitions that take place during the typical operation of an automobile.
Q5.1.3
Explain the difference between heat capacity and specific heat of a substance.
S5.1.3
Heat capacity refers to the heat required to raise the temperature of the mass of the substance 1 degree; specific heat refers to the
heat required to raise the temperature of 1 gram of the substance 1 degree. Thus, heat capacity is an extensive property, and specific
heat is an intensive one.
Q5.1.4
Calculate the heat capacity, in joules and in calories per degree, of the following:
a. 28.4 g of water
b. 1.00 oz of lead
Q5.1.5
Calculate the heat capacity, in joules and in calories per degree, of the following:
a. 45.8 g of nitrogen gas
b. 1.00 pound of aluminum metal
S5.1.5
a. 47.6 J/°C; 11.38 cal °C−1;
b. 407 J/°C; 97.3 cal °C−1
Q5.1.6
How much heat, in joules and in calories, must be added to a 75.0–g iron block with a specific heat of 0.449 J/g °C to increase its
temperature from 25 °C to its melting temperature of 1535 °C?
S5.1.6
q = mC Δ°T
0.449 J
q = (75.0g) × ( ) × (1, 510°K) = 50, 800J
g °C
50,800J ; 12,200cal

Q5.1.7
How much heat, in joules and in calories, is required to heat a 28.4-g (1-oz) ice cube from −23.0 °C to −1.0 °C?
S5.1.7
1310 J; 313 cal
Q5.1.8
How much would the temperature of 275 g of water increase if 36.5 kJ of heat were added?
S5.1.8
ΔT° = 31.7° C
Q5.1.9
If 14.5 kJ of heat were added to 485 g of liquid water, how much would its temperature increase?
S5.1.9
7.15 °C
Q5.1.10
A piece of unknown substance weighs 44.7 g and requires 2110 J to increase its temperature from 23.2 °C to 89.6 °C.
a. What is the specific heat of the substance?
b. If it is one of the substances found in Table, what is its likely identity?
S5.1.10
a.) Solve for the specific heat C and compare the values with the chart
q = mC Δ°T
2110J = (44.7 g)(C )(66.4°C )
2110 J
C =
2970 g °C
0.711 J
C =
g °C
b.) Silicon
Q5.1.11
A piece of unknown solid substance weighs 437.2 g, and requires 8460 J to increase its temperature from 19.3 °C to 68.9 °C.
a. What is the specific heat of the substance?
b. If it is one of the substances found in Table, what is its likely identity?
S5.1.11
a. 0.390 J/g °C;
b. Copper is a likely candidate.
Q5.1.12
An aluminum kettle weighs 1.05 kg.
a. What is the heat capacity of the kettle?
b. How much heat is required to increase the temperature of this kettle from 23.0 °C to 99.0 °C?
c. How much heat is required to heat this kettle from 23.0 °C to 99.0 °C if it contains 1.25 L of water (density of 0.997 g/mL and a
specific heat of 4.184 J/g °C)?

Q5.1.13
Most people find waterbeds uncomfortable unless the water temperature is maintained at about 85 °F. Unless it is heated, a
waterbed that contains 892 L of water cools from 85 °F to 72 °F in 24 hours. Estimate the amount of electrical energy required over
24 hours, in kWh, to keep the bed from cooling. Note that 1 kilowatt-hour (kWh) = 3.6 × 106 J, and assume that the density of
water is 1.0 g/mL (independent of temperature). What other assumptions did you make? How did they affect your calculated result
(i.e., were they likely to yield “positive” or “negative” errors)?
S5.1.13
We assume that the density of water is 1.0 g/cm3(1 g/mL) and that it takes as much energy to keep the water at 85 °F as to heat it
from 72 °F to 85 °F. We also assume that only the water is going to be heated. Energy required = 7.47 kWh
5.2: Calorimetry
Q5.2.1
A 500-mL bottle of water at room temperature and a 2-L bottle of water at the same temperature were placed in a refrigerator. After
30 minutes, the 500-mL bottle of water had cooled to the temperature of the refrigerator. An hour later, the 2-L of water had cooled
to the same temperature. When asked which sample of water lost the most heat, one student replied that both bottles lost the same
amount of heat because they started at the same temperature and finished at the same temperature. A second student thought that
the 2-L bottle of water lost more heat because there was more water. A third student believed that the 500-mL bottle of water lost
more heat because it cooled more quickly. A fourth student thought that it was not possible to tell because we do not know the
initial temperature and the final temperature of the water. Indicate which of these answers is correct and describe the error in each
of the other answers.
Q5.2.2
Would the amount of heat measured for the reaction in Example be greater, lesser, or remain the same if we used a calorimeter that
was a poorer insulator than a coffee cup calorimeter? Explain your answer.
S5.2.2
lesser; more heat would be lost to the coffee cup and the environment and so ΔT for the water would be lesser and the calculated q
would be lesser
Q5.2.3
Would the amount of heat absorbed by the dissolution in Example appear greater, lesser, or remain the same if the experimenter
used a calorimeter that was a poorer insulator than a coffee cup calorimeter? Explain your answer.
Q5.2.4
Would the amount of heat absorbed by the dissolution in Example appear greater, lesser, or remain the same if the heat capacity of
the calorimeter were taken into account? Explain your answer.
S5.2.4
greater, since taking the calorimeter’s heat capacity into account will compensate for the thermal energy transferred to the solution
from the calorimeter; this approach includes the calorimeter itself, along with the solution, as “surroundings”: qrxn = −(qsolution +
qcalorimeter); since both qsolution and qcalorimeter are negative, including the latter term (qrxn) will yield a greater value for the heat of
the dissolution
Q5.2.5
How many milliliters of water at 23 °C with a density of 1.00 g/mL must be mixed with 180 mL (about 6 oz) of coffee at 95 °C so
that the resulting combination will have a temperature of 60 °C? Assume that coffee and water have the same density and the same
specific heat.
Q5.2.6
How much will the temperature of a cup (180 g) of coffee at 95 °C be reduced when a 45 g silver spoon (specific heat 0.24 J/g °C)
at 25 °C is placed in the coffee and the two are allowed to reach the same temperature? Assume that the coffee has the same density

and specific heat as water.
S5.2.6
The temperature of the coffee will drop 1 degree.
Q5.2.7
A 45-g aluminum spoon (specific heat 0.88 J/g °C) at 24 °C is placed in 180 mL (180 g) of coffee at 85 °C and the temperature of
the two become equal.
a. What is the final temperature when the two become equal? Assume that coffee has the same specific heat as water.
b. The first time a student solved this problem she got an answer of 88 °C. Explain why this is clearly an incorrect answer.
Q5.2.8
The temperature of the cooling water as it leaves the hot engine of an automobile is 240 °F. After it passes through the radiator it
has a temperature of 175 °F. Calculate the amount of heat transferred from the engine to the surroundings by one gallon of water
with a specific heat of 4.184 J/g °C.
S5.2.8
2
5.7 × 10 kJ
Q5.2.8
A 70.0-g piece of metal at 80.0 °C is placed in 100 g of water at 22.0 °C contained in a calorimeter like that shown in Figure. The
metal and water come to the same temperature at 24.6 °C. How much heat did the metal give up to the water? What is the specific
heat of the metal?
Q5.2.9
If a reaction produces 1.506 kJ of heat, which is trapped in 30.0 g of water initially at 26.5 °C in a calorimeter like that in Figure,
what is the resulting temperature of the water?
S5.2.9
38.5 °C
Q5.2.10
A 0.500-g sample of KCl is added to 50.0 g of water in a calorimeter (Figure). If the temperature decreases by 1.05 °C, what is the
approximate amount of heat involved in the dissolution of the KCl, assuming the heat capacity of the resulting solution is 4.18 J/g
°C? Is the reaction exothermic or endothermic?
Q5.2.11
Dissolving 3.0 g of CaCl2(s) in 150.0 g of water in a calorimeter (Figure) at 22.4 °C causes the temperature to rise to 25.8 °C. What
is the approximate amount of heat involved in the dissolution, assuming the heat capacity of the resulting solution is 4.18 J/g °C? Is
the reaction exothermic or endothermic?
S5.2.11
2.2 kJ; The heat produced shows that the reaction is exothermic.
Q5.2.12
When 50.0 g of 0.200 M NaCl(aq) at 24.1 °C is added to 100.0 g of 0.100 M AgNO3(aq) at 24.1 °C in a calorimeter, the
temperature increases to 25.2 °C as AgCl(s) forms. Assuming the specific heat of the solution and products is 4.20 J/g °C, calculate
the approximate amount of heat in joules produced.
Q5.2.13
The addition of 3.15 g of Ba(OH)2•8H2O to a solution of 1.52 g of NH4SCN in 100 g of water in a calorimeter caused the
temperature to fall by 3.1 °C. Assuming the specific heat of the solution and products is 4.20 J/g °C, calculate the approximate
amount of heat absorbed by the reaction, which can be represented by the following equation:

Ba(OH )2 ⋅ 8 H2 O(s) + 2N H4 SC N(aq) → Ba(SC N )2(aq) + 2N H3(aq) + 10 H2 O(l) (9.E.1)
S5.2.13
1.4 kJ
Q5.2.14
The reaction of 50 mL of acid and 50 mL of base described in Example increased the temperature of the solution by 6.9 degrees.
How much would the temperature have increased if 100 mL of acid and 100 mL of base had been used in the same calorimeter
starting at the same temperature of 22.0 °C? Explain your answer.
Q5.2.15
If the 3.21 g of NH4NO3 in Example were dissolved in 100.0 g of water under the same conditions, how much would the
temperature change? Explain your answer.
S5.2.15
22.6. Since the mass and the heat capacity of the solution is approximately equal to that of the water, the two-fold increase in the
amount of water leads to a two-fold decrease of the temperature change.
Q5.2.16
When 1.0 g of fructose, C6H12O6(s), a sugar commonly found in fruits, is burned in oxygen in a bomb calorimeter, the temperature
of the calorimeter increases by 1.58 °C. If the heat capacity of the calorimeter and its contents is 9.90 kJ/°C, what is q for this
combustion?
Q5.2.17
When a 0.740-g sample of trinitrotoluene (TNT), C7H5N2O6, is burned in a bomb calorimeter, the temperature increases from 23.4
°C to 26.9 °C. The heat capacity of the calorimeter is 534 J/°C, and it contains 675 mL of water. How much heat was produced by
the combustion of the TNT sample?
S5.2.17
11.7 kJ
Q5.2.18
One method of generating electricity is by burning coal to heat water, which produces steam that drives an electric generator. To
determine the rate at which coal is to be fed into the burner in this type of plant, the heat of combustion per ton of coal must be
determined using a bomb calorimeter. When 1.00 g of coal is burned in a bomb calorimeter, the temperature increases by 1.48 °C.
If the heat capacity of the calorimeter is 21.6 kJ/°C, determine the heat produced by combustion of a ton of coal (2.000 × 103
pounds).
Q5.2.19
The amount of fat recommended for someone with a daily diet of 2000 Calories is 65 g. What percent of the calories in this diet
would be supplied by this amount of fat if the average number of Calories for fat is 9.1 Calories/g?
S5.2.19
30%
Q5.2.20
A teaspoon of the carbohydrate sucrose (common sugar) contains 16 Calories (16 kcal). What is the mass of one teaspoon of
sucrose if the average number of Calories for carbohydrates is 4.1 Calories/g?
Q5.2.21
What is the maximum mass of carbohydrate in a 6-oz serving of diet soda that contains less than 1 Calorie per can if the average
number of Calories for carbohydrates is 4.1 Calories/g?

S5.2.21
0.24 g
Q5.2.22
A pint of premium ice cream can contain 1100 Calories. What mass of fat, in grams and pounds, must be produced in the body to
store an extra 1.1 × 103 Calories if the average number of Calories for fat is 9.1 Calories/g?
Q5.2.23
A serving of a breakfast cereal contains 3 g of protein, 18 g of carbohydrates, and 6 g of fat. What is the Calorie content of a
serving of this cereal if the average number of Calories for fat is 9.1 Calories/g, for carbohydrates is 4.1 Calories/g, and for protein
is 4.1 Calories/g?
S5.2.23
1.4 × 102 Calories
Q5.2.24
Which is the least expensive source of energy in kilojoules per dollar: a box of breakfast cereal that weighs 32 ounces and costs
$4.23, or a liter of isooctane (density, 0.6919 g/mL) that costs $0.45? Compare the nutritional value of the cereal with the heat
produced by combustion of the isooctane under standard conditions. A 1.0-ounce serving of the cereal provides 130 Calories.
5.3: Enthalpy
Q5.3.1
Explain how the heat measured in [link] differs from the enthalpy change for the exothermic reaction described by the following
equation:
HCl(aq) + NaOH(aq) ⟶ NaCl(aq) + H O(l) (9.E.2)

2
The enthalpy change of the indicated reaction is for exactly 1 mol HCL and 1 mol NaOH; the heat in the example is produced by
0.0500 mol HCl and 0.0500 mol NaOH. Using the data in the check your learning section of [link], calculate ΔH in kJ/mol of
AgNO3(aq) for the reaction:
NaCl(aq) + AgNO (aq) ⟶ AgCl(s) + NaNO (aq) (9.E.3)

3 3
Q5.3.2
Calculate the enthalpy of solution (ΔH for the dissolution) per mole of NH4NO3 under the conditions described in [link].
S5.3.2
25 kJ mol−1
Q5.3.3
Calculate ΔH for the reaction described by the equation.
Ba (OH) ⋅ 8 H O(s) + 2 NH SCN(aq) ⟶ Ba (SCN) (aq) + 2 NH (aq) + 10 H O(l)
2 2 4 2 3 2
Q5.3.4
Calculate the enthalpy of solution (ΔH for the dissolution) per mole of CaCl2.
S5.3.4
81 kJ mol−1
Q5.3.5
Although the gas used in an oxyacetylene torch is essentially pure acetylene, the heat produced by combustion of one mole of
acetylene in such a torch is likely not equal to the enthalpy of combustion of acetylene listed in Table. Considering the conditions
for which the tabulated data are reported, suggest an explanation.

Q5.3.6
How much heat is produced by burning 4.00 moles of acetylene under standard state conditions?
S5.3.6
5204.4 kJ
Q5.3.7
How much heat is produced by combustion of 125 g of methanol under standard state conditions?
Q5.3.8
How many moles of isooctane must be burned to produce 100 kJ of heat under standard state conditions?
S5.3.8
1.83 × 10−2 mol
Q5.3.9
What mass of carbon monoxide must be burned to produce 175 kJ of heat under standard state conditions?
Q5.3.10
When 2.50 g of methane burns in oxygen, 125 kJ of heat is produced. What is the enthalpy of combustion per mole of methane
under these conditions?
S5.3.10
802 kJ mol−1
Q5.3.11
How much heat is produced when 100 mL of 0.250 M HCl (density, 1.00 g/mL) and 200 mL of 0.150 M NaOH (density, 1.00
g/mL) are mixed?
∘
HCl(aq) + NaOH(aq) ⟶ NaCl(aq) + H O(l) ΔH = −58 kJ (9.E.4)
2 298
If both solutions are at the same temperature and the heat capacity of the products is 4.19 J/g °C, how much will the temperature
increase? What assumption did you make in your calculation?
Q5.3.12
A sample of 0.562 g of carbon is burned in oxygen in a bomb calorimeter, producing carbon dioxide. Assume both the reactants
and products are under standard state conditions, and that the heat released is directly proportional to the enthalpy of combustion of
graphite. The temperature of the calorimeter increases from 26.74 °C to 27.93 °C. What is the heat capacity of the calorimeter and
its contents?
S5.3.12
15.5 kJ/ºC
Q5.3.13
Before the introduction of chlorofluorocarbons, sulfur dioxide (enthalpy of vaporization, 6.00 kcal/mol) was used in household
refrigerators. What mass of SO2 must be evaporated to remove as much heat as evaporation of 1.00 kg of CCl2F2 (enthalpy of
vaporization is 17.4 kJ/mol)?
The vaporization reactions for SO2 and CCl2F2 are
SO (l) ⟶ SO (g)
2 2
and CCl 2
F(l) ⟶ CCl F (g)
2 2
, respectively.
Q5.3.14
Homes may be heated by pumping hot water through radiators. What mass of water will provide the same amount of heat when
cooled from 95.0 to 35.0 °C, as the heat provided when 100 g of steam is cooled from 110 °C to 100 °C.

S5.3.14
7.43 g
Q5.3.15
Which of the enthalpies of combustion in Table the table are also standard enthalpies of formation?
Q5.3.16
Does the standard enthalpy of formation of H2O(g) differ from ΔH° for the reaction 2 H 2
(g) + O (g) ⟶ 2 H O(g)
2 2
?
S5.3.16
No.
Q5.3.17
Joseph Priestly prepared oxygen in 1774 by heating red mercury(II) oxide with sunlight focused through a lens. How much heat is
required to decompose exactly 1 mole of red HgO(s) to Hg(l) and O2(g) under standard conditions?
Q5.3.18
How many kilojoules of heat will be released when exactly 1 mole of manganese, Mn, is burned to form Mn3O4(s) at standard state
conditions?
S5.3.18
459.6 kJ
Q5.3.19
How many kilojoules of heat will be released when exactly 1 mole of iron, Fe, is burned to form Fe2O3(s) at standard state
conditions?
Q5.3.20
The following sequence of reactions occurs in the commercial production of aqueous nitric acid:
4 NH (g) + 5 O (g) ⟶ 4 NO(g) + 6 H O(l) ΔH = −907 kJ
3 2 2
2 NO(g) + O (g) ⟶ 2 NO (g) ΔH = −113 kJ

2 2
3 NO + H O(l) ⟶ 2 HNO (aq) + NO(g) ΔH = −139 kJ

2 2 2
Determine the total energy change for the production of one mole of aqueous nitric acid by this process.
S5.3.20
495 kJ/mol
Q5.3.21
Both graphite and diamond burn.
C(s, diamond) + O (g) ⟶ CO (g)
2 2
For the conversion of graphite to diamond:

∘
C(s, graphite) ⟶ C(s, diamond) ΔH = 1.90 kJ
298
Which produces more heat, the combustion of graphite or the combustion of diamond?
Q5.3.22
From the molar heats of formation in Appendix G, determine how much heat is required to evaporate one mole of water:
H O(l) ⟶ H O(g)
2 2
S5.3.22
44.01 kJ/mol

Q5.3.23
Which produces more heat?
Os(s) ⟶ 2 O (g) ⟶ OsO (s)
2 4
or
Os(s) ⟶ 2 O (g) ⟶ OsO (g)
2 4
for the phase change OsO 4

(s) ⟶ OsO (g)
4
ΔH = 56.4 kJ
Q5.3.24
Calculate ΔH ∘
298
for the process
5
Sb(s) + Cl (g) ⟶ SbCl (g)
2 5
2

3
∘
Sb(s) + Cl (g) ⟶ SbCl (g) ΔH = −314 kJ
2 3 298
2
∘
SbCl (s) + Cl (g) ⟶ SbCl (g) ΔH = −80 kJ
3 2 5 298
S5.3.24
394 kJ
Q5.3.25
Calculate ΔH ∘
298
for the process Zn(s) + S(s) + 2 O 2
(g) ⟶ ZnSO (s)
4

∘
Zn(s) + S(s) ⟶ ZnS(s) ΔH = −206.0 kJ
298
∘
ZnS(s) + 2 O (g) ⟶ ZnSO (s) ΔH = −776.8 kJ
2 4 298
Q5.3.26
Calculate ΔH for the process
Hg Cl (s) ⟶ 2 Hg(l) + Cl (g)
2 2 2

Hg(l) + Cl (g) ⟶ HgCl (s) ΔH = −224 kJ
2 2
Hg(l) + HgCl (s) ⟶ Hg Cl (s) ΔH = −41.2 kJ

2 2 2
S5.3.26
265 kJ
Q5.3.27
Calculate ΔH ∘
298
for the process
Co O (s) ⟶ 3 Co(s) + 2 O (g)
3 4 2

1
∘
Co(s) + O (g) ⟶ CoO(s) ΔH = −237.9 kJ
2 298
2
∘
3 Co(s) + O (g) ⟶ Co O (s) ΔH = −177.5 kJ
2 3 4 298
Q5.3.28
Calculate the standard molar enthalpy of formation of NO(g) from the following data:
∘
N (g) + 2 O ⟶ 2 NO (g) ΔH = 66.4 kJ
2 2 2 298

∘
2 NO(g) + O ⟶ 2 NO (g) ΔH = −114.1 kJ
2 2 298
S5.3.28
90.3 mol−1 of NO
Q5.3.29
Using the data in Appendix G, calculate the standard enthalpy change for each of the following reactions:
a. N (g) + O (g) ⟶ 2 NO(g)
2 2
b. Si(s) + 2 Cl (g) ⟶ SiCl (g)

2 4
c. Fe O (s) + 3 H (g) ⟶ 2 Fe(s) + 3 H O(l)

2 3 2 2
d. 2 LiOH(s) + CO (g) ⟶ Li CO (s) + H O(g) 2 2 3 2
Q5.3.30
Using the data in Appendix G, calculate the standard enthalpy change for each of the following reactions:
a. Si(s) + 2 F (g) ⟶ SiF (g)
2 4
b. 2 C(s) + 2 H (g) + O (g) ⟶ CH CO H(l)

2 2 3 2
c. CH (g) + N (g) ⟶ HCN(g) + NH (g) ;

4 2 3
d. CS (g) + 3 Cl (g) ⟶ CCl (g) + S Cl (g)

2 2 4 2 2
S5.3.30
a. −1615.0 kJ mol−1;
b. −484.3 kJ mol−1;
c. 164.2 kJ;
d. −232.1 kJ
Q5.3.31
The following reactions can be used to prepare samples of metals. Determine the enthalpy change under standard state conditions
for each.
a. 2 Ag O(s) ⟶ 4 Ag(s) + O (g)
2 2
b. SnO(s) + CO(g) ⟶ Sn(s) + CO (g) 2
c. Cr O (s) + 3 H (g) ⟶ 2 Cr(s) + 3 H O(l)

2 3 2 2
d. 2 Al(s) + Fe O (s) ⟶ Al O (s) + 2 Fe(s)

2 3 2 3
Q5.3.32
The decomposition of hydrogen peroxide, H2O2, has been used to provide thrust in the control jets of various space vehicles. Using
the data in Appendix G, determine how much heat is produced by the decomposition of exactly 1 mole of H2O2 under standard
conditions.
2 H O (l) ⟶ 2 H O(g) + O (g)
2 2 2 2
S5.3.32
−54.04 kJ mol−1
Q5.3.33
Calculate the enthalpy of combustion of propane, C3H8(g), for the formation of H2O(g) and CO2(g). The enthalpy of formation of
propane is −104 kJ/mol.
Q5.3.34
Calculate the enthalpy of combustion of butane, C4H10(g) for the formation of H2O(g) and CO2(g). The enthalpy of formation of
butane is −126 kJ/mol.

S5.3.34
2660 kJ mol−1
Q5.3.35
Both propane and butane are used as gaseous fuels. Which compound produces more heat per gram when burned?
Q5.3.36
The white pigment TiO2 is prepared by the reaction of titanium tetrachloride, TiCl4, with water vapor in the gas phase:
TiCl (g) + 2 H O(g) ⟶ TiO (s) + 4 HCl(g)
4 2 2
.
How much heat is evolved in the production of exactly 1 mole of TiO2(s) under standard state conditions?
S5.3.36
67.1 kJ
Q5.3.37
Water gas, a mixture of H2 and CO, is an important industrial fuel produced by the reaction of steam with red hot coke, essentially
pure carbon:
C(s) + H O(g) ⟶ CO(g) + H (g)
2 2
.
a. Assuming that coke has the same enthalpy of formation as graphite, calculate ΔH for this reaction.∘
298
b. Methanol, a liquid fuel that could possibly replace gasoline, can be prepared from water gas and additional hydrogen at high
temperature and pressure in the presence of a suitable catalyst:
2 H (g) + CO(g) ⟶ CH OH(g). (9.E.5)
2 3
Under the conditions of the reaction, methanol forms as a gas. Calculate ΔH for this reaction and for the condensation of
∘
298
gaseous methanol to liquid methanol.

c. Calculate the heat of combustion of 1 mole of liquid methanol to H2O(g) and CO2(g).
Q5.3.38
In the early days of automobiles, illumination at night was provided by burning acetylene, C2H2. Though no longer used as auto
headlamps, acetylene is still used as a source of light by some cave explorers. The acetylene is (was) prepared in the lamp by the
reaction of water with calcium carbide, CaC2:
CaC (s) + H O(l) ⟶ Ca (OH) (s) + C H (g)
2 2 2 2 2
.
Calculate the standard enthalpy of the reaction. The ΔH of CaC2 is −15.14 kcal/mol.
f
∘
S5.3.38
122.8 kJ
Q5.3.39
From the data in Table, determine which of the following fuels produces the greatest amount of heat per gram when burned under
standard conditions: CO(g), CH4(g), or C2H2(g).
Q5.3.40
The enthalpy of combustion of hard coal averages −35 kJ/g, that of gasoline, 1.28 × 105 kJ/gal. How many kilograms of hard coal
provide the same amount of heat as is available from 1.0 gallon of gasoline? Assume that the density of gasoline is 0.692 g/mL (the
same as the density of isooctane).
S5.3.40
3.7 kg

Q5.3.41
Ethanol, C2H5OH, is used as a fuel for motor vehicles, particularly in Brazil.
a. Write the balanced equation for the combustion of ethanol to CO2(g) and H2O(g), and, using the data in Appendix G, calculate
the enthalpy of combustion of 1 mole of ethanol.
b. The density of ethanol is 0.7893 g/mL. Calculate the enthalpy of combustion of exactly 1 L of ethanol.
c. Assuming that an automobile’s mileage is directly proportional to the heat of combustion of the fuel, calculate how much
farther an automobile could be expected to travel on 1 L of gasoline than on 1 L of ethanol. Assume that gasoline has the heat
of combustion and the density of n–octane, C8H18 (ΔH = −208.4 kJ/mol; density = 0.7025 g/mL).
∘
f
Q5.3.42
Among the substances that react with oxygen and that have been considered as potential rocket fuels are diborane [B2H6, produces
B2O3(s) and H2O(g)], methane [CH4, produces CO2(g) and H2O(g)], and hydrazine [N2H4, produces N2(g) and H2O(g)]. On the
basis of the heat released by 1.00 g of each substance in its reaction with oxygen, which of these compounds offers the best
possibility as a rocket fuel? The ΔH of B2H6(g), CH4(g), and N2H4(l) may be found in Appendix G.
f
∘
S5.3.42
On the assumption that the best rocket fuel is the one that gives off the most heat, B2H6 is the prime candidate.
Q5.3.43
How much heat is produced when 1.25 g of chromium metal reacts with oxygen gas under standard conditions?
Ethylene, C2H2, a byproduct from the fractional distillation of petroleum, is fourth among the 50 chemical compounds produced
commercially in the largest quantities. About 80% of synthetic ethanol is manufactured from ethylene by its reaction with water in
the presence of a suitable catalyst.
C H (g) + H O(g) ⟶ C H OH(l)
2 4 2 2 5
Using the data in the table in Appendix G, calculate ΔH° for the reaction.
S5.3.43
88.2 kJ
Q5.3.44
The oxidation of the sugar glucose, C6H12O6, is described by the following equation:
C H O (s) + 6 O (g) ⟶ 6 CO (g) + 6 H O(l) ΔH = −2816 kJ
6 12 6 2 2 2
The metabolism of glucose gives the same products, although the glucose reacts with oxygen in a series of steps in the body.
a. How much heat in kilojoules can be produced by the metabolism of 1.0 g of glucose?
b. How many Calories can be produced by the metabolism of 1.0 g of glucose?
Q5.3.45
Propane, C3H8, is a hydrocarbon that is commonly used as a fuel.
a. Write a balanced equation for the complete combustion of propane gas.
b. Calculate the volume of air at 25 °C and 1.00 atmosphere that is needed to completely combust 25.0 grams of propane. Assume
that air is 21.0 percent O2 by volume. (Hint: we will see how to do this calculation in a later chapter on gases—for now use the
information that 1.00 L of air at 25 °C and 1.00 atm contains 0.275 g of O2 per liter.)
c. The heat of combustion of propane is −2,219.2 kJ/mol. Calculate the heat of formation, ΔH of propane given that ΔH of
∘
f f
∘
H2O(l) = −285.8 kJ/mol and ΔH of CO2(g) = −393.5 kJ/mol.

∘
f
d. Assuming that all of the heat released in burning 25.0 grams of propane is transferred to 4.00 kilograms of water, calculate the
increase in temperature of the water.
S5.3.45
a. C H (g) + 5 O
3 8 2
(g) ⟶ 3 CO (g) + 4 H O(l)
2 2
;
b. 330 L;

c. −104.5 kJ mol−1;
d. 75.4 °C
Q5.3.46
During a recent winter month in Sheboygan, Wisconsin, it was necessary to obtain 3500 kWh of heat provided by a natural gas
furnace with 89% efficiency to keep a small house warm (the efficiency of a gas furnace is the percent of the heat produced by
combustion that is transferred into the house).
a. Assume that natural gas is pure methane and determine the volume of natural gas in cubic feet that was required to heat the
house. The average temperature of the natural gas was 56 °F; at this temperature and a pressure of 1 atm, natural gas has a
density of 0.681 g/L.
b. How many gallons of LPG (liquefied petroleum gas) would be required to replace the natural gas used? Assume the LPG is
liquid propane [C3H8: density, 0.5318 g/mL; enthalpy of combustion, 2219 kJ/mol for the formation of CO2(g) and H2O(l)] and
the furnace used to burn the LPG has the same efficiency as the gas furnace.
c. What mass of carbon dioxide is produced by combustion of the methane used to heat the house?
d. What mass of water is produced by combustion of the methane used to heat the house?
e. What volume of air is required to provide the oxygen for the combustion of the methane used to heat the house? Air contains
23% oxygen by mass. The average density of air during the month was 1.22 g/L.
f. How many kilowatt–hours (1 kWh = 3.6 × 106 J) of electricity would be required to provide the heat necessary to heat the
house? Note electricity is 100% efficient in producing heat inside a house.
g. Although electricity is 100% efficient in producing heat inside a house, production and distribution of electricity is not 100%
efficient. The efficiency of production and distribution of electricity produced in a coal-fired power plant is about 40%. A
certain type of coal provides 2.26 kWh per pound upon combustion. What mass of this coal in kilograms will be required to
produce the electrical energy necessary to heat the house if the efficiency of generation and distribution is 40%?
This page titled 9.E: Thermochemistry (Exercises) is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.

CHAPTER OVERVIEW
10: Liquids and Solids

General Chemistry
The great distances between atoms and molecules in a gaseous phase, and the corresponding absence of any significant interactions
between them, allows for simple descriptions of many physical properties that are the same for all gases, regardless of their
chemical identities. As described in the final module of the chapter on gases, this situation changes at high pressures and low
temperatures—conditions that permit the atoms and molecules to interact to a much greater extent. In the liquid and solid states,
these interactions are of considerable strength and play an important role in determining a number of physical properties that do
depend on the chemical identity of the substance. In this chapter, the nature of these interactions and their effects on various
physical properties of liquid and solid phases will be examined.
Contributors
[email protected]).
This page titled 10: Liquids and Solids is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
1
The great distances between atoms and molecules in a gaseous phase, and the corresponding absence of any significant interactions
between them, allows for simple descriptions of many physical properties that are the same for all gases, regardless of their
chemical identities. As described in the final module of the chapter on gases, this situation changes at high pressures and low
temperatures—conditions that permit the atoms and molecules to interact to a much greater extent.
Figure 10.1.1 : Solid carbon dioxide (“dry ice”, left) sublimes vigorously when placed in a liquid (right), cooling the liquid and
generating a fog of condensed water vapor above the cylinder. (credit: modification of work by Paul Flowers)
This figure shows pieces of a white substance which appear to be sublimating. To the right of these pieces are three graduated
cylinders. Each cylinder holds a different color liquid, and above the liquid, the cylinders are filled with a fog-like substance. This
fog-like substance swirls out of the top and around the outside of the cylinders.
In the liquid and solid states, these interactions are of considerable strength and play an important role in determining a number of
physical properties that do depend on the chemical identity of the substance. In this chapter, the nature of these interactions and
their effects on various physical properties of liquid and solid phases will be examined.
This page titled 10.1: Prelude to Liquids and Solids is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
10.0: Prelude to Liquids and Solids is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

Describe the types of intermolecular forces possible between atoms or molecules in condensed phases (dispersion forces,
dipole-dipole attractions, and hydrogen bonding)
Identify the types of intermolecular forces experienced by specific molecules based on their structures
Explain the relation between the intermolecular forces present within a substance and the temperatures associated with
changes in its physical state
As was the case for gaseous substances, the kinetic molecular theory may be used to explain the behavior of solids and liquids. In
the following description, the term particle will be used to refer to an atom, molecule, or ion. Note that we will use the popular
phrase “intermolecular attraction” to refer to attractive forces between the particles of a substance, regardless of whether these
particles are molecules, atoms, or ions.
Consider these two aspects of the molecular-level environments in solid, liquid, and gaseous matter:
Particles in a solid are tightly packed together and often arranged in a regular pattern; in a liquid, they are close together with no
regular arrangement; in a gas, they are far apart with no regular arrangement.
Particles in a solid vibrate about fixed positions and do not generally move in relation to one another; in a liquid, they move
past each other but remain in essentially constant contact; in a gas, they move independently of one another except when they
collide.
The differences in the properties of a solid, liquid, or gas reflect the strengths of the attractive forces between the atoms, molecules,
or ions that make up each phase. The phase in which a substance exists depends on the relative extents of its intermolecular forces
(IMFs) and the kinetic energies (KE) of its molecules. IMFs are the various forces of attraction that may exist between the atoms
and molecules of a substance due to electrostatic phenomena, as will be detailed in this module. These forces serve to hold particles
close together, whereas the particles’ KE provides the energy required to overcome the attractive forces and thus increase the
distance between particles. Figure 10.2.1 illustrates how changes in physical state may be induced by changing the temperature,
hence, the average KE, of a given substance.
Figure 10.2.1 : Transitions between solid, liquid, and gaseous states of a substance occur when conditions of temperature or
pressure favor the associated changes in intermolecular forces. (Note: The space between particles in the gas phase is much greater
than shown.)
Three sealed flasks are labeled, “Crystalline solid,” “Liquid,” and “Gas,” from left to right. The first flask holds a cube composed
of small spheres sitting on the bottom while the second flask shows a lot of small spheres in the bottom that are spaced a small
distance apart from one another and have lines around them to indicate motion. The third flask shows a few spheres spread far from
one another with larger lines to indicate motion. There is a right-facing arrow that spans the top of all three flasks. The arrow is
labeled, “Increasing K E ( temperature ).” There is a left-facing arrow that spans the bottom of all three flasks. The arrow is
labeled, “Increasing I M F.”
As an example of the processes depicted in this figure, consider a sample of water. When gaseous water is cooled sufficiently, the
attractions between H2O molecules will be capable of holding them together when they come into contact with each other; the gas
condenses, forming liquid H2O. For example, liquid water forms on the outside of a cold glass as the water vapor in the air is
cooled by the cold glass, as seen in Figure 10.2.2.

Figure 10.2.2 : Condensation forms when water vapor in the air is cooled enough to form liquid water, such as (a) on the outside of
a cold beverage glass or (b) in the form of fog. (credit a: modification of work by Jenny Downing; credit b: modification of work
by Cory Zanker)
Image a shows a brown colored beverage in a glass with condensation on the outside. Image b shows a body of water with fog
hovering above the surface of the water.
We can also liquefy many gases by compressing them, if the temperature is not too high. The increased pressure brings the
molecules of a gas closer together, such that the attractions between the molecules become strong relative to their KE.
Consequently, they form liquids. Butane, C4H10, is the fuel used in disposable lighters and is a gas at standard temperature and
pressure. Inside the lighter’s fuel compartment, the butane is compressed to a pressure that results in its condensation to the liquid
state, as shown in Figure 10.2.3.
Figure 10.2.3 : Gaseous butane is compressed within the storage compartment of a disposable lighter, resulting in its condensation
to the liquid state. (credit: modification of work by “Sam-Cat”/Flickr)
Finally, if the temperature of a liquid becomes sufficiently low, or the pressure on the liquid becomes sufficiently high, the
molecules of the liquid no longer have enough KE to overcome the IMF between them, and a solid forms. A more thorough
discussion of these and other changes of state, or phase transitions, is provided in a later module of this chapter.
Forces between Molecules

Under appropriate conditions, the attractions between all gas molecules will cause them to form liquids or solids. This is due to
intermolecular forces, not intramolecular forces. Intramolecular forces are those within the molecule that keep the molecule
together, for example, the bonds between the atoms. Intermolecular forces are the attractions between molecules, which determine
many of the physical properties of a substance. Figure 10.2.4 illustrates these different molecular forces. The strengths of these
attractive forces vary widely, though usually the IMFs between small molecules are weak compared to the intramolecular forces

that bond atoms together within a molecule. For example, to overcome the IMFs in one mole of liquid HCl and convert it into
gaseous HCl requires only about 17 kilojoules. However, to break the covalent bonds between the hydrogen and chlorine atoms in
one mole of HCl requires about 25 times more energy—430 kilojoules.
Figure 10.2.4 : Intramolecular forces keep a molecule intact. Intermolecular forces hold multiple molecules together and determine
many of a substance’s properties.
An image is shown in which two molecules composed of a green sphere labeled “C l” connected on the right to a white sphere
labeled “H” are near one another with a dotted line labeled “Intermolecular force ( weak )” drawn between them. A line connects
the two spheres in each molecule and the line is labeled “Intramolecular force ( strong ).”
All of the attractive forces between neutral atoms and molecules are known as van der Waals forces, although they are usually
referred to more informally as intermolecular attraction. We will consider the various types of IMFs in the next three sections of
this module.
Dispersion Forces
One of the three van der Waals forces is present in all condensed phases, regardless of the nature of the atoms or molecules
composing the substance. This attractive force is called the London dispersion force in honor of German-born American physicist
Fritz London who, in 1928, first explained it. This force is often referred to as simply the dispersion force. Because the electrons of
an atom or molecule are in constant motion (or, alternatively, the electron’s location is subject to quantum-mechanical variability),
at any moment in time, an atom or molecule can develop a temporary, instantaneous dipole if its electrons are distributed
asymmetrically. The presence of this dipole can, in turn, distort the electrons of a neighboring atom or molecule, producing an
induced dipole. These two rapidly fluctuating, temporary dipoles thus result in a relatively weak electrostatic attraction between the
species—a so-called dispersion force like that illustrated in Figure 10.2.5.
Figure 10.2.5 : Dispersion forces result from the formation of temporary dipoles, as illustrated here for two nonpolar diatomic
molecules.
Two pairs of molecules are shown where each molecule has one larger blue side labeled “delta sign, negative sign” and a smaller
red side labeled “delta sign, positive sign.” Toward the middle of the both molecules, but still on each distinct side, is a black dot.
Between the two images is a dotted line labeled, “Attractive force.” In the first image, the red and blue sides are labeled, “Unequal
distribution of electrons.” Below both images are brackets. The brackets are labeled, “Temporary dipoles.”
Dispersion forces that develop between atoms in different molecules can attract the two molecules to each other. The forces are
relatively weak, however, and become significant only when the molecules are very close. Larger and heavier atoms and molecules
exhibit stronger dispersion forces than do smaller and lighter atoms and molecules. F2 and Cl2 are gases at room temperature
(reflecting weaker attractive forces); Br2 is a liquid, and I2 is a solid (reflecting stronger attractive forces). Trends in observed
melting and boiling points for the halogens clearly demonstrate this effect, as seen in Table 10.2.1.
Table 10.2.1 : Melting and Boiling Points of the Halogens
Halogen Molar Mass Atomic Radius Melting Point Boiling Point
fluorine, F2 38 g/mol 72 pm 53 K 85 K

Halogen Molar Mass Atomic Radius Melting Point Boiling Point
chlorine, Cl2 71 g/mol 99 pm 172 K 238 K
bromine, Br2 160 g/mol 114 pm 266 K 332 K
iodine, I2 254 g/mol 133 pm 387 K 457 K
astatine, At2 420 g/mol 150 pm 575 K 610 K
The increase in melting and boiling points with increasing atomic/molecular size may be rationalized by considering how the
strength of dispersion forces is affected by the electronic structure of the atoms or molecules in the substance. In a larger atom, the
valence electrons are, on average, farther from the nuclei than in a smaller atom. Thus, they are less tightly held and can more
easily form the temporary dipoles that produce the attraction. The measure of how easy or difficult it is for another electrostatic
charge (for example, a nearby ion or polar molecule) to distort a molecule’s charge distribution (its electron cloud) is known as
polarizability. A molecule that has a charge cloud that is easily distorted is said to be very polarizable and will have large
dispersion forces; one with a charge cloud that is difficult to distort is not very polarizable and will have small dispersion forces.
 Example 10.2.1: London Forces and Their Effects
Order the following compounds of a group 14 element and hydrogen from lowest to highest boiling point: CH4, SiH4, GeH4,
and SnH4. Explain your reasoning.
Solution
Applying the skills acquired in the chapter on chemical bonding and molecular geometry, all of these compounds are predicted
to be nonpolar, so they may experience only dispersion forces: the smaller the molecule, the less polarizable and the weaker the
dispersion forces; the larger the molecule, the larger the dispersion forces. The molar masses of CH4, SiH4, GeH4, and SnH4
are approximately 16 g/mol, 32 g/mol, 77 g/mol, and 123 g/mol, respectively. Therefore, CH4 is expected to have the lowest
boiling point and SnH4 the highest boiling point. The ordering from lowest to highest boiling point is expected to be
CH4 < SiH4 < GeH4 < SnH4
A graph of the actual boiling points of these compounds versus the period of the group 14 elements shows this prediction to be
correct:
A line graph, titled “Carbon Family,” is shown where the y-axis is labeled “Temperature, ( degree sign C )” and has values of
“negative 200” to “negative 40” from bottom to top in increments of 20. The x-axis is labeled “Period” and has values of “0” to
“5” in increments of 1. The first point on the graph is labeled “C H subscript 4” and is at point “2, negative 160.” The second
point on the graph is labeled “S i H subscript 4” and is at point “3, negative 120” while the third point on the graph is labeled
“G e H subscript 4” and is at point “4, negative 100.” The fourth point on the graph is labeled “S n H subscript 4” and is at
point “5, negative 60.”

 Exercise 10.2.1
Order the following hydrocarbons from lowest to highest boiling point: C2H6, C3H8, and C4H10.
Answer
All of these compounds are nonpolar and only have London dispersion forces: the larger the molecule, the larger the
dispersion forces and the higher the boiling point. The ordering from lowest to highest boiling point is therefore
C2H6 < C3H8 < C4H10.
The shapes of molecules also affect the magnitudes of the dispersion forces between them. For example, boiling points for the
isomers n-pentane, isopentane, and neopentane (shown in Figure 10.2.6) are 36 °C, 27 °C, and 9.5 °C, respectively. Even though
these compounds are composed of molecules with the same chemical formula, C5H12, the difference in boiling points suggests that
dispersion forces in the liquid phase are different, being greatest for n-pentane and least for neopentane. The elongated shape of n-
pentane provides a greater surface area available for contact between molecules, resulting in correspondingly stronger dispersion
forces. The more compact shape of isopentane offers a smaller surface area available for intermolecular contact and, therefore,
weaker dispersion forces. Neopentane molecules are the most compact of the three, offering the least available surface area for
intermolecular contact and, hence, the weakest dispersion forces. This behavior is analogous to the connections that may be formed
between strips of VELCRO brand fasteners: the greater the area of the strip’s contact, the stronger the connection.
Figure 10.2.6 : The strength of the dispersion forces increases with the contact area between molecules, as demonstrated by the
boiling points of these pentane isomers.
Three images of molecules are shown. The first shows a cluster of large, gray spheres each bonded together and to several smaller,
white spheres. There is a gray, jagged line and then the mirror image of the first cluster of spheres is shown. Above these two
clusters is the label, “Small contact area, weakest attraction,” and below is the label, “neopentane boiling point: 9.5 degrees C.” The
second shows a chain of three gray spheres bonded by the middle sphere to a fourth gray sphere. Each gray sphere is bonded to
several smaller, white spheres. There is a jagged, gray line and then the mirror image of the first chain appears. Above these two
chains is the label, “Less surface area, less attraction,” and below is the label, “isopentane boiling point: 27 degrees C.” The third
image shows a chain of five gray spheres bonded together and to several smaller, white spheres. There is a jagged gray line and
then the mirror image of the first chain appears. Above these chains is the label, “Large contact area, strong attraction,” and below
is the label, “n-pentane boiling point 36 degrees C.”
 Applications: Geckos and Intermolecular Forces
Geckos have an amazing ability to adhere to most surfaces. They can quickly run up smooth walls and across ceilings that have
no toe-holds, and they do this without having suction cups or a sticky substance on their toes. And while a gecko can lift its
feet easily as it walks along a surface, if you attempt to pick it up, it sticks to the surface. How are geckos (as well as spiders
and some other insects) able to do this? Although this phenomenon has been investigated for hundreds of years, scientists only
recently uncovered the details of the process that allows geckos’ feet to behave this way.

Figure 10.2.7 : Geckos’ toes contain large numbers of tiny hairs (setae), which branch into many triangular tips (spatulae).
Geckos adhere to surfaces because of van der Waals attractions between the surface and a gecko’s millions of spatulae. By
changing how the spatulae contact the surface, geckos can turn their stickiness “on” and “off.” (credit photo: modification of
work by “JC*+A!”/Flickr)
Three figures are shown. The first is a photo of the bottom of a gecko’s foot. The second is bigger version which shows the
setae. The third is a bigger version of the setae and shows the spatulae.
Geckos’ toes are covered with hundreds of thousands of tiny hairs known as setae, with each seta, in turn, branching into
hundreds of tiny, flat, triangular tips called spatulae. The huge numbers of spatulae on its setae provide a gecko, shown in
Figure 10.2.7, with a large total surface area for sticking to a surface. In 2000, Kellar Autumn, who leads a multi-institutional
gecko research team, found that geckos adhered equally well to both polar silicon dioxide and nonpolar gallium arsenide. This
proved that geckos stick to surfaces because of dispersion forces—weak intermolecular attractions arising from temporary,
synchronized charge distributions between adjacent molecules. Although dispersion forces are very weak, the total attraction
over millions of spatulae is large enough to support many times the gecko’s weight.
In 2014, two scientists developed a model to explain how geckos can rapidly transition from “sticky” to “non-sticky.” Alex
Greaney and Congcong Hu at Oregon State University described how geckos can achieve this by changing the angle between
their spatulae and the surface. Geckos’ feet, which are normally nonsticky, become sticky when a small shear force is applied.
By curling and uncurling their toes, geckos can alternate between sticking and unsticking from a surface, and thus easily move
across it. Further investigations may eventually lead to the development of better adhesives and other applications.
Smart materials (1 of 5): Gecko Adhes…

Adhes…
Watch this video to learn more about Kellar Autumn’s research that determined that van der Waals forces are responsible for a
gecko’s ability to cling and climb.
Dipole-Dipole Attractions
Recall from the chapter on chemical bonding and molecular geometry that polar molecules have a partial positive charge on one
side and a partial negative charge on the other side of the molecule—a separation of charge called a dipole. Consider a polar
molecule such as hydrogen chloride, HCl. In the HCl molecule, the more electronegative Cl atom bears the partial negative charge,
whereas the less electronegative H atom bears the partial positive charge. An attractive force between HCl molecules results from
the attraction between the positive end of one HCl molecule and the negative end of another. This attractive force is called a dipole-
dipole attraction—the electrostatic force between the partially positive end of one polar molecule and the partially negative end of
another, as illustrated in Figure 10.2.8.

Figure 10.2.8 : This image shows two arrangements of polar molecules, such as HCl, that allow an attraction between the partial
negative end of one molecule and the partial positive end of another.
Two pairs of molecules are shown where each molecule has one larger blue side labeled “delta sign, negative sign” and a smaller
red side labeled “delta sign, positive sign. In the first pair, the red sides of the two molecules both face to the left and the blue side
to the right. A horizontal dotted line lies in between the two. In the second pair, the molecules face up and down, with the red and
blue ends aligning. A horizontal dotted line lies between the red and blue ends facing upward and another lies between the red and
blue ends facing downward.
The effect of a dipole-dipole attraction is apparent when we compare the properties of HCl molecules to nonpolar F2 molecules.
Both HCl and F2 consist of the same number of atoms and have approximately the same molecular mass. At a temperature of 150
K, molecules of both substances would have the same average KE. However, the dipole-dipole attractions between HCl molecules
are sufficient to cause them to “stick together” to form a liquid, whereas the relatively weaker dispersion forces between nonpolar
F2 molecules are not, and so this substance is gaseous at this temperature. The higher normal boiling point of HCl (188 K)
compared to F2 (85 K) is a reflection of the greater strength of dipole-dipole attractions between HCl molecules, compared to the
attractions between nonpolar F2 molecules. We will often use values such as boiling or freezing points, or enthalpies of
vaporization or fusion, as indicators of the relative strengths of IMFs of attraction present within different substances.
 Example 10.2.2: Dipole-Dipole Forces and Their Effects

Predict which will have the higher boiling point: N2 or CO. Explain your reasoning.
Solution
CO and N2 are both diatomic molecules with masses of about 28 amu, so they experience similar London dispersion forces.
Because CO is a polar molecule, it experiences dipole-dipole attractions. Because N2 is nonpolar, its molecules cannot exhibit
dipole-dipole attractions. The dipole-dipole attractions between CO molecules are comparably stronger than the dispersion
forces between nonpolar N2 molecules, so CO is expected to have the higher boiling point.
A common method for preparing oxygen is the decomposition
 Exercise 10.2.2
Predict which will have the higher boiling point: ICl or Br . Explain your reasoning.
2
Answer
ICl. ICl and Br2 have similar masses (~160 amu) and therefore experience similar London dispersion forces. ICl is polar
and thus also exhibits dipole-dipole attractions; Br2 is nonpolar and does not. The relatively stronger dipole-dipole
attractions require more energy to overcome, so ICl will have the higher boiling point.
Hydrogen Bonding
Nitrosyl fluoride (ONF, molecular mass 49 amu) is a gas at room temperature. Water (H2O, molecular mass 18 amu) is a liquid,
even though it has a lower molecular mass. We clearly cannot attribute this difference between the two compounds to dispersion
forces. Both molecules have about the same shape and ONF is the heavier and larger molecule. It is, therefore, expected to
experience more significant dispersion forces. Additionally, we cannot attribute this difference in boiling points to differences in
the dipole moments of the molecules. Both molecules are polar and exhibit comparable dipole moments. The large difference
between the boiling points is due to a particularly strong dipole-dipole attraction that may occur when a molecule contains a
hydrogen atom bonded to a fluorine, oxygen, or nitrogen atom (the three most electronegative elements). The very large difference
in electronegativity between the H atom (2.1) and the atom to which it is bonded (4.0 for an F atom, 3.5 for an O atom, or 3.0 for a

N atom), combined with the very small size of a H atom and the relatively small sizes of F, O, or N atoms, leads to highly
concentrated partial charges with these atoms. Molecules with F-H, O-H, or N-H moieties are very strongly attracted to similar
moieties in nearby molecules, a particularly strong type of dipole-dipole attraction called hydrogen bonding. Examples of hydrogen
bonds include HF⋯HF, H2O⋯HOH, and H3N⋯HNH2, in which the hydrogen bonds are denoted by dots. Figure 10.2.9 illustrates
hydrogen bonding between water molecules.
Figure 10.2.9 : Water molecules participate in multiple hydrogen-bonding interactions with nearby water molecules.
Five water molecules are shown near one another, but not touching. A dotted line lies between many of the hydrogen atoms on one
molecule and the oxygen atom on another molecule.
Despite use of the word “bond,” keep in mind that hydrogen bonds are intermolecular attractive forces, not intramolecular
attractive forces (covalent bonds). Hydrogen bonds are much weaker than covalent bonds, only about 5 to 10% as strong, but are
generally much stronger than other dipole-dipole attractions and dispersion forces.
Hydrogen bonds have a pronounced effect on the properties of condensed phases (liquids and solids). For example, consider the
trends in boiling points for the binary hydrides of group 15 (NH3, PH3, AsH3, and SbH3), group 16 hydrides (H2O, H2S, H2Se, and
H2Te), and group 17 hydrides (HF, HCl, HBr, and HI). The boiling points of the heaviest three hydrides for each group are plotted
in Figure 10.2.10. As we progress down any of these groups, the polarities of the molecules decrease slightly, whereas the sizes of
the molecules increase substantially. The effect of increasingly stronger dispersion forces dominates that of increasingly weaker
dipole-dipole attractions, and the boiling points are observed to increase steadily. For the group 15, 16, and 17 hydrides, the boiling
points for each class of compounds increase with increasing molecular mass for elements in periods 3, 4, and 5.

Figure 10.2.10: In comparison to periods 3−5, the binary hydrides of period 2 elements in groups 17, 16 and 15 (F, O and N,
respectively) exhibit anomalously high boiling points due to hydrogen bonding.
A line graph is shown where the y-axis is labeled “Boiling point (, degree sign, C )” and has values of “ negative 150” to “150”
from bottom to top in increments of 50. The x-axis is labeled “Period” and has values of “0” to “5” in increments of 1. Three lines
are shown on the graph and are labeled in the legend. The red line is labeled as “halogen family,” the blue is “oxygen family” and
the green is “nitrogen family.” The first point on the red line is labeled “question mark” and is at point “2, negative 120”. The
second point on the line is labeled “H C l” and is at point “3, negative 80” while the third point on the line is labeled “H B r” and is
at point “4, negative 60”. The fourth point on the line is labeled “H I” and is at point “5, negative 40.” The first point on the green
line is labeled “question mark” and is at point “2, negative 125.” The second point on the line is labeled “P H, subscript 3” and is at
point “3, negative 80” while the third point on the line is labeled “A s H, subscript 3” and is at point “4, negative 55.” The fourth
point on the line is labeled “S b H, subscript 3” and is at point “5, negative 10.” The first point on the blue line is labeled “question
mark” and is at point “2, negative 80.” The second point on the line is labeled “H, subscript 2, S” and is at point “3, negative 55”
while the third point on the line is labeled “H, subscript 2, S e” and is at point “4, negative 45.” The fourth point on the line is
labeled “H, subscript 2, T e” and is at point “5, negative 3.”
If we use this trend to predict the boiling points for the lightest hydride for each group, we would expect NH3 to boil at about −120
°C, H2O to boil at about −80 °C, and HF to boil at about −110 °C. However, when we measure the boiling points for these
compounds, we find that they are dramatically higher than the trends would predict, as shown in Figure 10.2.10. The stark contrast
between our naïve predictions and reality provides compelling evidence for the strength of hydrogen bonding.
 Example 10.2.3: Effect of Hydrogen Bonding on Boiling Points
Consider the compounds dimethylether (CH3OCH3), ethanol (CH3CH2OH), and propane (CH3CH2CH3). Their boiling points,
not necessarily in order, are −42.1 °C, −24.8 °C, and 78.4 °C. Match each compound with its boiling point. Explain your
reasoning.
Solution
The VSEPR-predicted shapes of CH3OCH3, CH3CH2OH, and CH3CH2CH3 are similar, as are their molar masses (46 g/mol,
46 g/mol, and 44 g/mol, respectively), so they will exhibit similar dispersion forces. Since CH3CH2CH3 is nonpolar, it may
exhibit only dispersion forces. Because CH3OCH3 is polar, it will also experience dipole-dipole attractions. Finally,
CH3CH2OH has an −OH group, and so it will experience the uniquely strong dipole-dipole attraction known as hydrogen
bonding. So the ordering in terms of strength of IMFs, and thus boiling points, is CH3CH2CH3 < CH3OCH3 < CH3CH2OH.
The boiling point of propane is −42.1 °C, the boiling point of dimethylether is −24.8 °C, and the boiling point of ethanol is
78.5 °C.

 Exercise 10.2.3
Ethane (CH3CH3) has a melting point of −183 °C and a boiling point of −89 °C. Predict the melting and boiling points for
methylamine (CH3NH2). Explain your reasoning.
Answer
The melting point and boiling point for methylamine are predicted to be significantly greater than those of ethane. CH3CH3
and CH3NH2 are similar in size and mass, but methylamine possesses an −NH group and therefore may exhibit hydrogen
bonding. This greatly increases its IMFs, and therefore its melting and boiling points. It is difficult to predict values, but the
known values are a melting point of −93 °C and a boiling point of −6 °C.
Hydrogen Bonding and DNA

Deoxyribonucleic acid (DNA) is found in every living organism and contains the genetic information that determines the
organism’s characteristics, provides the blueprint for making the proteins necessary for life, and serves as a template to pass this
information on to the organism’s offspring. A DNA molecule consists of two (anti-)parallel chains of repeating nucleotides, which
form its well-known double helical structure, as shown in Figure 10.2.10.

Figure 10.2.11: Two separate DNA molecules form a double-stranded helix in which the molecules are held together via hydrogen
bonding. (credit: modification of work by Jerome Walker, Dennis Myts)
Two images are shown. The first lies on the left side of the page and shows a helical structure like a twisted ladder where the rungs
of the ladder, labeled “Base pair” are red, yellow, green and blue paired bars. The red and yellow bars, which are always paired
together, are labeled in the legend, which is titled “Nitrogenous bases” as “adenine” and “thymine,” respectively. The blue and
green bars, which are always paired together, are labeled in the legend as “guanine” and “cytosine,” respectively. At the top of the
helical structure, the left-hand side rail, or “Sugar, dash, phosphate backbone,” is labeled as “3, prime” while the right is labeled as
“5, prime.” These labels are reversed at the bottom of the helix. To the right of the page is a large Lewis structure. The top left
corner of this structure, labeled “5, prime,” shows a phosphorus atom single bonded to three oxygen atoms, one of which has a
superscripted negative charge, and double bonded to a fourth oxygen atom. One of the single bonded oxygen atoms is single
bonded to the left corner of a five-membered ring with an oxygen atom at its top point and which is single bonded to an oxygen
atom on the bottom left. This oxygen atom is single bonded to a phosphorus atom that is single bonded to two other hydrogen
atoms and double bonded to a fourth oxygen atom. The lower left of these oxygen atoms is single bonded to another oxygen atom
that is single bonded to a five-membered ring with an oxygen in the upper bonding site. The bottom left of this ring has a hydroxyl
group attached to it while the upper right carbon is single bonded to a nitrogen atom that is part of a five-membered ring bonded to
a six-membered ring. Both of these rings have points of unsaturation and nitrogen atoms bonded into their structures. On the right
side of the six-membered ring are two single bonded amine groups and a double bonded oxygen. Three separate dotted lines extend
from these sites to corresponding sites on a second six-membered ring. This ring has points of unsaturation and a nitrogen atom in
the bottom right bonding position that is single bonded to a five-membered ring on the right side of the image. This ring is single
bonded to a carbon that is single bonded to an oxygen that is single bonded to a phosphorus. The phosphorus is single bonded to
two other oxygen atoms and double bonded to a fourth oxygen atom. This group is labeled “5, prime.” The five-membered ring is
also bonded on the top side to an oxygen that is bonded to a phosphorus single bonded to two other oxygen atoms and double
bonded to a fourth oxygen atom. The upper left oxygen of this group is single bonded to a carbon that is single bonded to a five-
membered ring with an oxygen in the bottom bonding position. This ring has a hydroxyl group on its upper right side that is labeled
“3, prime” and is bonded on the left side to a nitrogen that is a member of a five-membered ring. This ring is bonded to a six-
membered ring and both have points of unsaturation. This ring has a nitrogen on the left side, as well as an amine group, that have
two dotted lines leading from them to an oxygen and amine group on a six membered ring. These dotted lines are labeled
“Hydrogen bonds.” The six membered ring also has a double bonded oxygen on its lower side and a nitrogen atom on its left side
that is single bonded to a five-membered ring. This ring connects to the two phosphate groups mentioned at the start of this to form
a large circle. The name “guanine” is written below the lower left side of this image while the name “cytosine” is written on the
lower right. The name “thymine” is written above the right side of the image and “adenine” is written on the top right. Three
sections are indicated below the images where the left is labeled “Sugar, dash, phosphate backbone,” the middle is labeled “Bases”
and the right is labeled “Sugar, dash, phosphate backbone.”
Each nucleotide contains a (deoxyribose) sugar bound to a phosphate group on one side, and one of four nitrogenous bases on the
other. Two of the bases, cytosine (C) and thymine (T), are single-ringed structures known as pyrimidines. The other two, adenine
(A) and guanine (G), are double-ringed structures called purines. These bases form complementary base pairs consisting of one
purine and one pyrimidine, with adenine pairing with thymine, and cytosine with guanine. Each base pair is held together by
hydrogen bonding. A and T share two hydrogen bonds, C and G share three, and both pairings have a similar shape and structure
Figure 10.2.12

Figure 10.2.12: The geometries of the base molecules result in maximum hydrogen bonding between adenine and thymine (AT)
and between guanine and cytosine (GC), so-called “complementary base pairs.”
A large Lewis structure is shown. The top left corner of this structure, labeled “5, prime,” shows a phosphorus atom single bonded
to three oxygen atoms, one of which has a superscripted negative charge, and double bonded to a fourth oxygen atom. One of the
single bonded oxygen atoms is single bonded to the left corner of a five-membered ring with an oxygen atom at its top point and
which is single bonded to an oxygen atom on the bottom left. This oxygen atom is single bonded to a phosphorus atom that is
single bonded to two other hydrogen atoms and double bonded to a fourth oxygen atom. The lower left of these oxygen atoms is
single bonded to another oxygen atom that is single bonded to a five-membered ring with an oxygen in the upper bonding site. The
bottom left of this ring has a hydroxyl group attached to it while the upper right carbon is single bonded to a nitrogen atom that is
part of a five-membered ring bonded to a six-membered ring. Both of these rings have points of unsaturation and nitrogen atoms
bonded into their structures. On the right side of the six-membered ring are two single bonded amine groups and a double bonded
oxygen. Three separate dotted lines extend from these sites to corresponding sites on a second six-membered ring. This ring has
points of unsaturation and a nitrogen atom in the bottom right bonding position that is single bonded to a five-membered ring on
the right side of the image. This ring is single bonded to a carbon that is single bonded to an oxygen that is single bonded to a
phosphorus. The phosphorus is single bonded to two other oxygen atoms and double bonded to a fourth oxygen atom. This group is
labeled “5, prime.” The five-membered ring is also bonded on the top side to an oxygen that is bonded to a phosphorus single
bonded to two other oxygen atoms and double bonded to a fourth oxygen atom. The upper left oxygen of this group is single
bonded to a carbon that is single bonded to a five-membered ring with an oxygen in the bottom bonding position. This ring has a
hydroxyl group on its upper right side that is labeled “3, prime” and is bonded on the left side to a nitrogen that is a member of a
five-membered ring. This ring is bonded to a six-membered ring and both have points of unsaturation. This ring has a nitrogen on
the left side, as well as an amine group, that have two dotted lines leading from them to an oxygen and amine group on a six
membered ring. These dotted lines are labeled “Hydrogen bonds.” The six membered ring also has a double bonded oxygen on its
lower side and a nitrogen atom on its left side that is single bonded to a five-membered ring. This ring connects to the two
phosphate groups mentioned at the start of this to form a large circle. The name “guanine” is written below the lower left side of
this image while the name “cytosine” is written on the lower right. The name “thymine” is written above the right side of the image
and “adenine” is written on the top right. Three sections are indicated below the images where the left is labeled “Sugar, dash,
phosphate backbone,” the middle is labeled “Bases” and the right is labeled “Sugar, dash, phosphate backbone.”
The cumulative effect of millions of hydrogen bonds effectively holds the two strands of DNA together. Importantly, the two
strands of DNA can relatively easily “unzip” down the middle since hydrogen bonds are relatively weak compared to the covalent
bonds that hold the atoms of the individual DNA molecules together. This allows both strands to function as a template for
replication.
Summary
The physical properties of condensed matter (liquids and solids) can be explained in terms of the kinetic molecular theory. In a
liquid, intermolecular attractive forces hold the molecules in contact, although they still have sufficient kinetic energy to move past
each other. Intermolecular attractive forces, collectively referred to as van der Waals forces, are responsible for the behavior of
liquids and solids and are electrostatic in nature. Dipole-dipole attractions result from the electrostatic attraction of the partial
negative end of one dipolar molecule for the partial positive end of another. The temporary dipole that results from the motion of
the electrons in an atom can induce a dipole in an adjacent atom and give rise to the London dispersion force. London forces
increase with increasing molecular size. Hydrogen bonds are a special type of dipole-dipole attraction that results when hydrogen is
bonded to one of the three most electronegative elements: F, O, or N.

Glossary
dipole-dipole attraction
intermolecular attraction between two permanent dipoles
dispersion force
(also, London dispersion force) attraction between two rapidly fluctuating, temporary dipoles; significant only when particles
are very close together
hydrogen bonding
occurs when exceptionally strong dipoles attract; bonding that exists when hydrogen is bonded to one of the three most
electronegative elements: F, O, or N
induced dipole
temporary dipole formed when the electrons of an atom or molecule are distorted by the instantaneous dipole of a neighboring
atom or molecule
instantaneous dipole
temporary dipole that occurs for a brief moment in time when the electrons of an atom or molecule are distributed
asymmetrically
intermolecular force
noncovalent attractive force between atoms, molecules, and/or ions
polarizability
measure of the ability of a charge to distort a molecule’s charge distribution (electron cloud)
van der Waals force

attractive or repulsive force between molecules, including dipole-dipole, dipole-induced dipole, and London dispersion forces;
does not include forces due to covalent or ionic bonding, or the attraction between ions and molecules
This page titled 10.2: Intermolecular Forces is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
10.1: Intermolecular Forces is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

Distinguish between adhesive and cohesive forces
Define viscosity, surface tension, and capillary rise
Describe the roles of intermolecular attractive forces in each of these properties/phenomena
When you pour a glass of water, or fill a car with gasoline, you observe that water and gasoline flow freely. But when you pour
syrup on pancakes or add oil to a car engine, you note that syrup and motor oil do not flow as readily. The viscosity of a liquid is a
measure of its resistance to flow. Water, gasoline, and other liquids that flow freely have a low viscosity. Honey, syrup, motor oil,
and other liquids that do not flow freely, like those shown in Figure 10.3.1, have higher viscosities. We can measure viscosity by
measuring the rate at which a metal ball falls through a liquid (the ball falls more slowly through a more viscous liquid) or by
measuring the rate at which a liquid flows through a narrow tube (more viscous liquids flow more slowly).
Figure 10.3.1 : (a) Honey and (b) motor oil are examples of liquids with high viscosities; they flow slowly. (credit a: modification
of work by Scott Bauer; credit b: modification of work by David Nagy)
Two photographs are shown and labeled “a” and “b.” Photo a shows a jar of honey with a dipper drizzling it onto a biscuit. More
biscuits are shown in a basket in the background. Photo b shows the engine of a car and a person adding motor oil to the engine.
The IMFs between the molecules of a liquid, the size and shape of the molecules, and the temperature determine how easily a
liquid flows. As Table 10.3.1 shows, the more structurally complex are the molecules in a liquid and the stronger the IMFs between
them, the more difficult it is for them to move past each other and the greater is the viscosity of the liquid. As the temperature
increases, the molecules move more rapidly and their kinetic energies are better able to overcome the forces that hold them
together; thus, the viscosity of the liquid decreases.
Table 10.3.1 : Viscosities of Common Substances at 25 °C
Substance Formula Viscosity (mPa·s)
water H2O 0.890
mercury Hg 1.526
ethanol C2H5OH 1.074
octane C8H18 0.508
ethylene glycol CH2(OH)CH2(OH) 16.1
honey variable ~2,000–10,000
motor oil variable ~50–500
The various IMFs between identical molecules of a substance are examples of cohesive forces. The molecules within a liquid are
surrounded by other molecules and are attracted equally in all directions by the cohesive forces within the liquid. However, the
molecules on the surface of a liquid are attracted only by about one-half as many molecules. Because of the unbalanced molecular
attractions on the surface molecules, liquids contract to form a shape that minimizes the number of molecules on the surface—that
is, the shape with the minimum surface area. A small drop of liquid tends to assume a spherical shape, as shown in Figure 10.3.2,

because in a sphere, the ratio of surface area to volume is at a minimum. Larger drops are more greatly affected by gravity, air
resistance, surface interactions, and so on, and as a result, are less spherical.
Figure 10.3.2 : Attractive forces result in a spherical water drop that minimizes surface area; cohesive forces hold the sphere
together; adhesive forces keep the drop attached to the web. (credit photo: modification of work by “OliBac”/Flickr)
A photo of a spider’s web with droplets of water attached to it is shown. Two images are shown the right of the photo and arrows
lead from the photo to the images. The upper image shows twenty eight blue spheres stacked one atop the other in the bottom of a
circular background. Five arrows are drawn pointing to the sides and downward from the sphere in the top middle of the drawing.
The lower image shows another circular background of the same size as the first, but this time the blue spheres fill the image and
are packed closely together. A sphere in the middle has six arrows pointing in all directions away from it.
Surface tension is defined as the energy required to increase the surface area of a liquid, or the force required to increase the length
of a liquid surface by a given amount. This property results from the cohesive forces between molecules at the surface of a liquid,
and it causes the surface of a liquid to behave like a stretched rubber membrane. Surface tensions of several liquids are presented in
Table 10.3.2.
Table 10.3.2 : Surface Tensions of Common Substances at 25 °C
Substance Formula Surface Tension (mN/m)
water H2O 71.99
mercury Hg 458.48
ethanol C2H5OH 21.97
octane C8H18 21.14
ethylene glycol CH2(OH)CH2(OH) 47.99
Among common liquids, water exhibits a distinctly high surface tension due to strong hydrogen bonding between its molecules. As
a result of this high surface tension, the surface of water represents a relatively “tough skin” that can withstand considerable force
without breaking. A steel needle carefully placed on water will float. Some insects, like the one shown in Figure 10.3.3, even
though they are denser than water, move on its surface because they are supported by the surface tension.
Figure 10.3.3 : Surface tension (right) prevents this insect, a “water strider,” from sinking into the water.
A photo and a diagram as shown and a right-facing arrow leads from the photo to the image. The photo shows an insect standing on
the surface of a sample of water. The image shows a square background that is two thirds covered in blue spheres that are closely
packet together. A brown line starts at the upper left corner of the background and rests on top of the first row of spheres. The
sphere directly under this low point of the line has four arrows drawn on it that face to both sides and downward. A sphere in the
bottom center of the image has six arrows drawn on it that all face outward in different directions.
The IMFs of attraction between two different molecules are called adhesive forces. Consider what happens when water comes into
contact with some surface. If the adhesive forces between water molecules and the molecules of the surface are weak compared to
the cohesive forces between the water molecules, the water does not “wet” the surface. For example, water does not wet waxed
surfaces or many plastics such as polyethylene. Water forms drops on these surfaces because the cohesive forces within the drops

are greater than the adhesive forces between the water and the plastic. Water spreads out on glass because the adhesive force
between water and glass is greater than the cohesive forces within the water. When water is confined in a glass tube, its meniscus
(surface) has a concave shape because the water wets the glass and creeps up the side of the tube. On the other hand, the cohesive
forces between mercury atoms are much greater than the adhesive forces between mercury and glass. Mercury therefore does not
wet glass, and it forms a convex meniscus when confined in a tube because the cohesive forces within the mercury tend to draw it
into a drop (Figure 10.3.4).
Figure 10.3.4 : Differences in the relative strengths of cohesive and adhesive forces result in different meniscus shapes for mercury
(left) and water (right) in glass tubes. (credit: Mark Ott)
This figure shows two test tubes. The test tube on the left contains mercury with a meniscus that rounds up. The test tube on the
right contains water with a meniscus that rounds down.
If you place one end of a paper towel in spilled wine, as shown in Figure 10.3.5, the liquid wicks up the paper towel. A similar
process occurs in a cloth towel when you use it to dry off after a shower. These are examples of capillary action—when a liquid
flows within a porous material due to the attraction of the liquid molecules to the surface of the material and to other liquid
molecules. The adhesive forces between the liquid and the porous material, combined with the cohesive forces within the liquid,
may be strong enough to move the liquid upward against gravity.
Figure 10.3.5 : Wine wicks up a paper towel (left) because of the strong attractions of water (and ethanol) molecules to the −OH
groups on the towel’s cellulose fibers and the strong attractions of water molecules to other water (and ethanol) molecules (right).
(credit photo: modification of work by Mark Blaser)
A photo and a diagram are shown. In the photo, a paper towel is dipped into a bowl full of a red liquid sitting on a countertop. The
red liquid is traveling up the lower part of the paper towel, and this section of the photo has a square drawn around it. A right-
facing arrow leads from this square to the image. The image is square and has a background of two types of molecules, mixed
together. The first type of molecule is composed of two bonded black spheres, one of which is single bonded to three white spheres
and one of which is single bonded to two white spheres and a red sphere that is itself bonded to a white sphere. The other type of
molecule is composed of six black spheres bonded together in a row and bonded to other red and white spheres. Six upward-facing
arrows are drawn on top of this background. They have positive signs on their lower ends and negative signs on their heads. Four
upward-facing arrows are drawn with their signs reversed.
Towels soak up liquids like water because the fibers of a towel are made of molecules that are attracted to water molecules. Most
cloth towels are made of cotton, and paper towels are generally made from paper pulp. Both consist of long molecules of cellulose
that contain many −OH groups. Water molecules are attracted to these −OH groups and form hydrogen bonds with them, which
draws the H2O molecules up the cellulose molecules. The water molecules are also attracted to each other, so large amounts of
water are drawn up the cellulose fibers.
Capillary action can also occur when one end of a small diameter tube is immersed in a liquid, as illustrated in Figure 10.3.6. If the
liquid molecules are strongly attracted to the tube molecules, the liquid creeps up the inside of the tube until the weight of the liquid
and the adhesive forces are in balance. The smaller the diameter of the tube is, the higher the liquid climbs. It is partly by capillary

action occurring in plant cells called xylem that water and dissolved nutrients are brought from the soil up through the roots and
into a plant. Capillary action is the basis for thin layer chromatography, a laboratory technique commonly used to separate small
quantities of mixtures. You depend on a constant supply of tears to keep your eyes lubricated and on capillary action to pump tear
fluid away.
Figure 10.3.6 : Depending upon the relative strengths of adhesive and cohesive forces, a liquid may rise (such as water) or fall
(such as mercury) in a glass capillary tube. The extent of the rise (or fall) is directly proportional to the surface tension of the liquid
and inversely proportional to the density of the liquid and the radius of the tube.
An image of two beakers and a tube is shown. The first beaker, drawn on the left and labeled “Water,” is drawn half-full of a blue
liquid. Two tubes are placed vertically in the beaker and inserted into the liquid. The liquid is shown higher in the tubes than in the
beaker and is labeled “Capillary attraction.” The second beaker, drawn in the middle and labeled “Mercury,” is drawn half-full of a
gray liquid. Two tubes are placed vertically in the beaker and inserted into the liquid. The liquid is shown lower in the tubes than in
the beaker and is labeled “Capillary repulsion.” Lines point to the vertical tubes and label them “Capillary tubes.” A separate
drawing of one of the vertical tubes from the first beaker is shown on the right. A right-facing arrow leads from the liquid in the
tube to a square call-out box that shows a close-up view of the liquid’s surface. The distance across the tube is labeled “2 r” in this
image.
The height to which a liquid will rise in a capillary tube is determined by several factors as shown in the following equation:
2T cos θ
h = (10.3.1)
rρg
where
h is the height of the liquid inside the capillary tube relative to the surface of the liquid outside the tube,
T is the surface tension of the liquid,
θ is the contact angle between the liquid and the tube,
r is the radius of the tube, ρ is the density of the liquid, and
g is the acceleration due to gravity, 9.8 m/s2.
When the tube is made of a material to which the liquid molecules are strongly attracted, they will spread out completely on the
surface, which corresponds to a contact angle of 0°. This is the situation for water rising in a glass tube.
 Example 10.3.1: Capillary Rise

At 25 °C, how high will water rise in a glass capillary tube with an inner diameter of 0.25 mm?
For water, T = 71.99 mN/m and ρ = 1.0 g/cm3.
Solution
The liquid will rise to a height h given by Equation 10.3.1 :
2T cos θ
h =
rρg
The Newton is defined as a kg m/s2, and so the provided surface tension is equivalent to 0.07199 kg/s2. The provided density
must be converted into units that will cancel appropriately: ρ = 1000 kg/m3. The diameter of the tube in meters is 0.00025 m,
so the radius is 0.000125 m. For a glass tube immersed in water, the contact angle is θ = 0°, so cos θ = 1. Finally, acceleration
due to gravity on the earth is g = 9.8 m/s2. Substituting these values into the equation, and cancelling units, we have:

2
2(0.07199 kg/ s )
h = = 0.12 m = 12 cm
3 2
(0.000125 m)(1000 kg/ m )(9.8 m/ s )
 Exercise 10.3.1
Water rises in a glass capillary tube to a height of 8.4 cm. What is the diameter of the capillary tube?
Answer
diameter = 0.36 mm
 Applications: Capillary Action is Used to Draw Blood
Many medical tests require drawing a small amount of blood, for example to determine the amount of glucose in someone with
diabetes or the hematocrit level in an athlete. This procedure can be easily done because of capillary action, the ability of a
liquid to flow up a small tube against gravity, as shown in Figure 10.3.7. When your finger is pricked, a drop of blood forms
and holds together due to surface tension—the unbalanced intermolecular attractions at the surface of the drop. Then, when the
open end of a narrow-diameter glass tube touches the drop of blood, the adhesive forces between the molecules in the blood
and those at the glass surface draw the blood up the tube. How far the blood goes up the tube depends on the diameter of the
tube (and the type of fluid). A small tube has a relatively large surface area for a given volume of blood, which results in larger
(relative) attractive forces, allowing the blood to be drawn farther up the tube. The liquid itself is held together by its own
cohesive forces. When the weight of the liquid in the tube generates a downward force equal to the upward force associated
with capillary action, the liquid stops rising.
Figure 10.3.7 :: Blood is collected for medical analysis by capillary action, which draws blood into a small diameter glass tube.
(credit: modification of work by Centers for Disease Control and Prevention)
A photograph shows a person’s hand being held by a person wearing medical gloves. A thin glass tube is pressed against the
persons finger and blood is moving up the tube.

The intermolecular forces between molecules in the liquid state vary depending upon their chemical identities and result in
corresponding variations in various physical properties. Cohesive forces between like molecules are responsible for a liquid’s
viscosity (resistance to flow) and surface tension (elasticity of a liquid surface). Adhesive forces between the molecules of a liquid
and different molecules composing a surface in contact with the liquid are responsible for phenomena such as surface wetting and
capillary rise.
Key Equations
2T cos θ
h =
rρg
Glossary
adhesive force
force of attraction between molecules of different chemical identities
capillary action

flow of liquid within a porous material due to the attraction of the liquid molecules to the surface of the material and to other
liquid molecules
cohesive force
force of attraction between identical molecules
surface tension
energy required to increase the area, or length, of a liquid surface by a given amount
viscosity
measure of a liquid’s resistance to flow
This page titled 10.3: Properties of Liquids is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
10.2: Properties of Liquids is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

Define phase transitions and phase transition temperatures
Explain the relation between phase transition temperatures and intermolecular attractive forces
Describe the processes represented by typical heating and cooling curves, and compute heat flows and enthalpy changes
accompanying these processes
We witness and utilize changes of physical state, or phase transitions, in a great number of ways. As one example of global
significance, consider the evaporation, condensation, freezing, and melting of water. These changes of state are essential aspects of
our earth’s water cycle as well as many other natural phenomena and technological processes of central importance to our lives. In
this module, the essential aspects of phase transitions are explored.
Vaporization and Condensation

When a liquid vaporizes in a closed container, gas molecules cannot escape. As these gas phase molecules move randomly about,
they will occasionally collide with the surface of the condensed phase, and in some cases, these collisions will result in the
molecules re-entering the condensed phase. The change from the gas phase to the liquid is called condensation. When the rate of
condensation becomes equal to the rate of vaporization, neither the amount of the liquid nor the amount of the vapor in the
container changes. The vapor in the container is then said to be in equilibrium with the liquid. Keep in mind that this is not a static
situation, as molecules are continually exchanged between the condensed and gaseous phases. Such is an example of a dynamic
equilibrium, the status of a system in which reciprocal processes (for example, vaporization and condensation) occur at equal rates.
The pressure exerted by the vapor in equilibrium with a liquid in a closed container at a given temperature is called the liquid’s
vapor pressure (or equilibrium vapor pressure). The area of the surface of the liquid in contact with a vapor and the size of the
vessel have no effect on the vapor pressure, although they do affect the time required for the equilibrium to be reached. We can
measure the vapor pressure of a liquid by placing a sample in a closed container, like that illustrated in Figure 10.4.1, and using a
manometer to measure the increase in pressure that is due to the vapor in equilibrium with the condensed phase.
Figure 10.4.1 : In a closed container, dynamic equilibrium is reached when (a) the rate of molecules escaping from the liquid to
become the gas (b) increases and eventually (c) equals the rate of gas molecules entering the liquid. When this equilibrium is
reached, the vapor pressure of the gas is constant, although the vaporization and condensation processes continue.
Three images are shown and labeled “a,” “b,” and “c.” Each image shows a round bulb connected on the right to a tube that is
horizontal, then is bent vertically, curves, and then is vertical again to make a u-shape. A valve is located in the horizontal portion
of the tube. Image a depicts a liquid in the bulb, labeled, “Liquid,” and upward-facing arrows leading away from the surface of the
liquid. The phrase, “Molecules escape surface and form vapor” is written below the bulb, and a gray liquid in the u-shaped portion
of the tube is shown at equal heights on the right and left sides. Image b depicts a liquid in the bulb, labeled, “Liquid,” and upward-
facing arrows leading away from the surface of the liquid to molecules drawn in the upper portion of the bulb. A gray liquid in the
u-shaped portion of the tube is shown slightly higher on the right side than on the left side. Image c depicts a liquid in the bulb,
labeled, “Liquid,” and upward-facing arrows leading away from the surface of the liquid to molecules drawn in the upper portion of
the bulb. There are more molecules present in c than in b. The phrase “Equilibrium reached, vapor pressure determined,” is written
below the bulb and a gray liquid in the u-shaped portion of the tube is shown higher on the right side. A horizontal line is drawn
level with each of these liquid levels and the distance between the lines is labeled with a double-headed arrow. This section is
labeled with the phrase, “Vapor pressure.”
The chemical identities of the molecules in a liquid determine the types (and strengths) of intermolecular attractions possible;
consequently, different substances will exhibit different equilibrium vapor pressures. Relatively strong intermolecular attractive
forces will serve to impede vaporization as well as favoring “recapture” of gas-phase molecules when they collide with the liquid
surface, resulting in a relatively low vapor pressure. Weak intermolecular attractions present less of a barrier to vaporization, and a

reduced likelihood of gas recapture, yielding relatively high vapor pressures. The following example illustrates this dependence of
vapor pressure on intermolecular attractive forces.
 Example 10.4.1: Explaining Vapor Pressure in Terms of IMFs
Given the shown structural formulas for these four compounds, explain their relative vapor pressures in terms of types and
extents of IMFs:
Solution
Diethyl ether has a very small dipole and most of its intermolecular attractions are London forces. Although this molecule is
the largest of the four under consideration, its IMFs are the weakest and, as a result, its molecules most readily escape from the
liquid. It also has the highest vapor pressure. Due to its smaller size, ethanol exhibits weaker dispersion forces than diethyl
ether. However, ethanol is capable of hydrogen bonding and, therefore, exhibits stronger overall IMFs, which means that fewer
molecules escape from the liquid at any given temperature, and so ethanol has a lower vapor pressure than diethyl ether. Water
is much smaller than either of the previous substances and exhibits weaker dispersion forces, but its extensive hydrogen
bonding provides stronger intermolecular attractions, fewer molecules escaping the liquid, and a lower vapor pressure than for
either diethyl ether or ethanol. Ethylene glycol has two −OH groups, so, like water, it exhibits extensive hydrogen bonding. It
is much larger than water and thus experiences larger London forces. Its overall IMFs are the largest of these four substances,
which means its vaporization rate will be the slowest and, consequently, its vapor pressure the lowest.
 Exercise 10.4.1
At 20 °C, the vapor pressures of several alcohols are given in this table. Explain these vapor pressures in terms of types and
extents of IMFs for these alcohols:
At 20 °C, the vapor pressures of several alcohols
Compound methanol CH3OH ethanol C2H5OH propanol C3H7OH butanol C4H9OH
Vapor Pressure at 20 °C 11.9 kPa 5.95 kPa 2.67 kPa 0.56 kPa
Answer
All these compounds exhibit hydrogen bonding; these strong IMFs are difficult for the molecules to overcome, so the vapor
pressures are relatively low. As the size of molecule increases from methanol to butanol, dispersion forces increase, which
means that the vapor pressures decrease as observed:
Pmethanol > Pethanol > Ppropanol > Pbutanol
As temperature increases, the vapor pressure of a liquid also increases due to the increased average KE of its molecules. Recall that
at any given temperature, the molecules of a substance experience a range of kinetic energies, with a certain fraction of molecules
having a sufficient energy to overcome IMF and escape the liquid (vaporize). At a higher temperature, a greater fraction of
molecules have enough energy to escape from the liquid, as shown in Figure 10.4.2. The escape of more molecules per unit of time
and the greater average speed of the molecules that escape both contribute to the higher vapor pressure.

Figure 10.4.2 : Temperature affects the distribution of kinetic energies for the molecules in a liquid. At the higher temperature, more
molecules have the necessary kinetic energy, KE, to escape from the liquid into the gas phase.
A graph is shown where the y-axis is labeled “Number of molecules” and the x-axis is labeled “Kinetic Energy.” Two lines are
graphed and a vertical dotted line, labeled “Minimum K E needed to escape,” is drawn halfway across the x-axis. The first line
move sharply upward and has a high peak near the left side of the x-axis. It drops just as steeply and ends about 60 percent of the
way across the x-axis. This line is labeled “Low T.” A second line, labeled “High T,” begins at the same point as the first, but does
not go to such a high point, is wider, and ends slightly further to the right on the x-axis.
Boiling Points
When the vapor pressure increases enough to equal the external atmospheric pressure, the liquid reaches its boiling point. The
boiling point of a liquid is the temperature at which its equilibrium vapor pressure is equal to the pressure exerted on the liquid by
its gaseous surroundings. For liquids in open containers, this pressure is that due to the earth’s atmosphere. The normal boiling
point of a liquid is defined as its boiling point when surrounding pressure is equal to 1 atm (101.3 kPa). Figure 10.4.3 shows the
variation in vapor pressure with temperature for several different substances. Considering the definition of boiling point, these
curves may be seen as depicting the dependence of a liquid’s boiling point on surrounding pressure.
Figure 10.4.3: The boiling points of liquids are the temperatures at which their equilibrium vapor pressures equal the pressure of
the surrounding atmosphere. Normal boiling points are those corresponding to a pressure of 1 atm (101.3 kPa.)
A graph is shown where the x-axis is labeled “Temperature ( degree sign, C )” and has values of 200 to 1000 in increments of 200
and the y-axis is labeled “Pressure ( k P a )” and has values of 20 to 120 in increments of 20. A horizontal dotted line extends
across the graph at point 780 on the y-axis while three vertical dotted lines extend from points 35, 78, and 100 to meet the
horizontal dotted line. Four lines are graphed. The first line, labeled “ethyl ether,” begins at the point “0 , 200” and extends in a
slight curve to point “45, 1000” while the second line, labeled “ethanol”, extends from point “0, 20” to point “88, 1000” in a more
extreme curve. The third line, labeled “water,” begins at the point “0, 0” and extends in a curve to point “108, 1000” while the
fourth line, labeled “ethylene glycol,” extends from point “80, 0” to point “140, 100” in a very shallow curve.
 Example 10.4.2: A Boiling Point at Reduced Pressure
A typical atmospheric pressure in Leadville, Colorado (elevation 10,200 feet) is 68 kPa. Use the graph in Figure 10.4.3 to
determine the boiling point of water at this elevation.

Solution
The graph of the vapor pressure of water versus temperature in Figure 10.4.3 indicates that the vapor pressure of water is 68
kPa at about 90 °C. Thus, at about 90 °C, the vapor pressure of water will equal the atmospheric pressure in Leadville, and
water will boil.
 Exercise 10.4.2
The boiling point of ethyl ether was measured to be 10 °C at a base camp on the slopes of Mount Everest. Use Figure 10.4.3 to
determine the approximate atmospheric pressure at the camp.
Answer
Approximately 40 kPa (0.4 atm)
The quantitative relation between a substance’s vapor pressure and its temperature is described by the Clausius-Clapeyron
equation:
−Δ Hva p /RT
P = Ae (10.4.1)
where
ΔHvap is the enthalpy of vaporization for the liquid,
R is the gas constant, and
ln A is a constant whose value depends on the chemical identity of the substance.
Equation 10.4.1 is often rearranged into logarithmic form to yield the linear equation:
ΔHvap
ln P = − + ln A (10.4.2)
RT
This linear equation may be expressed in a two-point format that is convenient for use in various computations, as demonstrated in
the examples and exercises that follow. If at temperature T , the vapor pressure is P , and at temperature T , the vapor pressure is
1 1 2
T , the corresponding linear equations are:

2
ΔHvap
ln P1 = − + ln A
RT1
and
ΔHvap
ln P2 = − + ln A (10.4.3)
RT2
Since the constant, ln A, is the same, these two equations may be rearranged to isolate ln A and then set them equal to one another:
ΔHvap ΔHvap
ln P1 + = ln P2 +
RT1 RT2
which can be combined into:
P2 ΔHvap 1 1
ln( ) = ( − ) (10.4.4)
P1 R T1 T2
 Example 10.4.3: Estimating Enthalpy of Vaporization
Isooctane (2,2,4-trimethylpentane) has an octane rating of 100. It is used as one of the standards for the octane-rating system
for gasoline. At 34.0 °C, the vapor pressure of isooctane is 10.0 kPa, and at 98.8 °C, its vapor pressure is 100.0 kPa. Use this
information to estimate the enthalpy of vaporization for isooctane.

Solution
The enthalpy of vaporization, ΔH vap , can be determined by using the Clausius-Clapeyron equation (Equation 10.4.4):
P2 ΔHvap 1 1
ln( ) = ( − )
P1 R T1 T2
Since we have two vapor pressure-temperature values

o
T1 = 34.0 C = 307.2 K
P1 = 10.0 kP a and
o
T2 = 98.8 C = 372.0 K
P2 = 100 kP a
we can substitute them into this equation and solve for ΔHvap . Rearranging the Clausius-Clapeyron equation and solving for
ΔH vapyields:
P2
R ⋅ ln( )
P1
ΔHvap =
1 1
( − )
T1 T2
100 kP a
(8.3145 J/mol ⋅ K) ⋅ ln( )
10.0 kP a
=
1 1
( − )
307.2 K 372.0 K
= 33, 800 J/mol = 33.8 kJ/mol
Note that the pressure can be in any units, so long as they agree for both P values, but the temperature must be in kelvin for the
Clausius-Clapeyron equation to be valid.
 Exercise 10.4.3
At 20.0 °C, the vapor pressure of ethanol is 5.95 kPa, and at 63.5 °C, its vapor pressure is 53.3 kPa. Use this information to
estimate the enthalpy of vaporization for ethanol.
Answer
47,782 J/mol = 47.8 kJ/mol
 Example 10.4.4: Estimating Temperature (or Vapor Pressure)
For benzene (C6H6), the normal boiling point is 80.1 °C and the enthalpy of vaporization is 30.8 kJ/mol. What is the boiling
point of benzene in Denver, where atmospheric pressure = 83.4 kPa?
Solution
If the temperature and vapor pressure are known at one point, along with the enthalpy of vaporization, ΔHvap, then the
temperature that corresponds to a different vapor pressure (or the vapor pressure that corresponds to a different temperature)
can be determined by using the Clausius-Clapeyron equation (Equation 10.4.1) :
P2 ΔHvap 1 1
ln( ) = ( − )
P1 R T1 T2
Since the normal boiling point is the temperature at which the vapor pressure equals atmospheric pressure at sea level, we
know one vapor pressure-temperature value (T = 80.1 °C = 353.3 K, P = 101.3 kPa, ΔH = 30.8 kJ/mol) and want to find
1 1 vap

the temperature (T ) that corresponds to vapor pressure P2 = 83.4 kPa. We can substitute these values into the Clausius-
2
Clapeyron equation and then solve for T . Rearranging the Clausius-Clapeyron equation and solving for T yields:
2 2
−1
P2
⎛ ⎞
−R ⋅ ln( )
⎜ P1 1 ⎟
T2 = ⎜ + ⎟
⎜ ΔHvap T1 ⎟
⎝ ⎠
−1
83.4 kPa
⎛ −(8.3145 J/mol ⋅ K) ⋅ ln( ) ⎞
⎜ 101.3 kPa 1 ⎟
= ⎜ + ⎟
⎜ 30, 800 J/mol 353.3 K ⎟
⎝ ⎠
∘
= 346.9 K or 73.8 C
 Exercise 10.4.4
For acetone (CH ) CO, the normal boiling point is 56.5 °C and the enthalpy of vaporization is 31.3 kJ/mol. What is the vapor
3 2
pressure of acetone at 25.0 °C?
Answer
30.1 kPa
Enthalpy of Vaporization
Vaporization is an endothermic process. The cooling effect can be evident when you leave a swimming pool or a shower. When the
water on your skin evaporates, it removes heat from your skin and causes you to feel cold. The energy change associated with the
vaporization process is the enthalpy of vaporization, ΔH . For example, the vaporization of water at standard temperature is
vap
represented by:
H O(l) ⟶ H O(g) ΔHvap = 44.01 kJ/mol

2 2
As described in the chapter on thermochemistry, the reverse of an endothermic process is exothermic. And so, the condensation of
a gas releases heat:
H O(g) ⟶ H O(l) ΔHcon = −ΔHvap = −44.01 kJ/mol
2 2
 Example 10.4.5: Using Enthalpy of Vaporization

One way our body is cooled is by evaporation of the water in sweat (Figure 10.4.4). In very hot climates, we can lose as much
as 1.5 L of sweat per day. Although sweat is not pure water, we can get an approximate value of the amount of heat removed
by evaporation by assuming that it is. How much heat is required to evaporate 1.5 L of water (1.5 kg) at T = 37 °C (normal
body temperature); ΔH = 43.46 kJ/mol at 37 °C.
vap

Figure 10.4.4 : Evaporation of sweat helps cool the body. (credit: “Kullez”/Flickr)
Solution We start with the known volume of sweat (approximated as just water) and use the given information to convert to the
amount of heat needed:
1000 g 1 mol 43.46 kJ 3
1.5 L × × × = 3.6 × 10 kJ
1 L 18 g 1 mol
Thus, 3600 kJ of heat are removed by the evaporation of 1.5 L of water.
 Exercise 10.4.5: Boiling Ammonia
How much heat is required to evaporate 100.0 g of liquid ammonia, NH , at its boiling point if its enthalpy of vaporization is
3
4.8 kJ/mol?
Answer
28 kJ
Melting and Freezing

When we heat a crystalline solid, we increase the average energy of its atoms, molecules, or ions and the solid gets hotter. At some
point, the added energy becomes large enough to partially overcome the forces holding the molecules or ions of the solid in their
fixed positions, and the solid begins the process of transitioning to the liquid state, or melting. At this point, the temperature of the
solid stops rising, despite the continual input of heat, and it remains constant until all of the solid is melted. Only after all of the
solid has melted will continued heating increase the temperature of the liquid (Figure 10.4.5.
Figure 10.4.5 : (a) This beaker of ice has a temperature of −12.0 °C. (b) After 10 minutes the ice has absorbed enough heat from the
air to warm to 0 °C. A small amount has melted. (c) Thirty minutes later, the ice has absorbed more heat, but its temperature is still
0 °C. The ice melts without changing its temperature. (d) Only after all the ice has melted does the heat absorbed cause the
temperature to increase to 22.2 °C. (credit: modification of work by Mark Ott).
This figure shows four photos each labeled, “a,” “b,” “c,” and, “d.” Each photo shows a beaker with ice and a digital thermometer.
The first photo shows ice cubes in the beaker, and the thermometer reads negative 12.0 degrees C. The second photo shows slightly
melted ice, and the thermometer reads 0.0 degrees C. The third photo shows more water than ice in the beaker. The thermometer
reads 0.0 degrees C. The fourth photo shows the ice completely melted, and the thermometer reads 22.2 degrees C.
If we stop heating during melting and place the mixture of solid and liquid in a perfectly insulated container so no heat can enter or
escape, the solid and liquid phases remain in equilibrium. This is almost the situation with a mixture of ice and water in a very good

thermos bottle; almost no heat gets in or out, and the mixture of solid ice and liquid water remains for hours. In a mixture of solid
and liquid at equilibrium, the reciprocal processes of melting and freezing occur at equal rates, and the quantities of solid and liquid
therefore remain constant. The temperature at which the solid and liquid phases of a given substance are in equilibrium is called the
melting point of the solid or the freezing point of the liquid. Use of one term or the other is normally dictated by the direction of the
phase transition being considered, for example, solid to liquid (melting) or liquid to solid (freezing).
The enthalpy of fusion and the melting point of a crystalline solid depend on the strength of the attractive forces between the units
present in the crystal. Molecules with weak attractive forces form crystals with low melting points. Crystals consisting of particles
with stronger attractive forces melt at higher temperatures.
The amount of heat required to change one mole of a substance from the solid state to the liquid state is the enthalpy of fusion,
ΔHfus of the substance. The enthalpy of fusion of ice is 6.0 kJ/mol at 0 °C. Fusion (melting) is an endothermic process:
H O(s) → H O(l) ΔHfus = 6.01 kJ/mol (10.4.5)
2 2
The reciprocal process, freezing, is an exothermic process whose enthalpy change is −6.0 kJ/mol at 0 °C:
H O(l) → H O(s) ΔHfrz = −ΔHfus = −6.01 kJ/mol (10.4.6)
2 2
Sublimation and Deposition

Some solids can transition directly into the gaseous state, bypassing the liquid state, via a process known as sublimation. At room
temperature and standard pressure, a piece of dry ice (solid CO2) sublimes, appearing to gradually disappear without ever forming
any liquid. Snow and ice sublime at temperatures below the melting point of water, a slow process that may be accelerated by
winds and the reduced atmospheric pressures at high altitudes. When solid iodine is warmed, the solid sublimes and a vivid purple
vapor forms (Figure 10.4.6). The reverse of sublimation is called deposition, a process in which gaseous substances condense
directly into the solid state, bypassing the liquid state. The formation of frost is an example of deposition.
Figure 10.4.6 : Sublimation of solid iodine in the bottom of the tube produces a purple gas that subsequently deposits as solid
iodine on the colder part of the tube above. (credit: modification of work by Mark Ott)
This figure shows a test tube. In the bottom is a dark substance which breaks up into a purple gas at the top.
Like vaporization, the process of sublimation requires an input of energy to overcome intermolecular attractions. The enthalpy of
sublimation, ΔHsub, is the energy required to convert one mole of a substance from the solid to the gaseous state. For example, the
sublimation of carbon dioxide is represented by:
CO (s) ⟶ CO (g) ΔHsub = 26.1 kJ/mol

2 2
Likewise, the enthalpy change for the reverse process of deposition is equal in magnitude but opposite in sign to that for
sublimation:
CO (g) ⟶ CO (s) ΔHdep = −ΔHsub = −26.1 kJ/mol

2 2
Consider the extent to which intermolecular attractions must be overcome to achieve a given phase transition. Converting a solid
into a liquid requires that these attractions be only partially overcome; transition to the gaseous state requires that they be
completely overcome. As a result, the enthalpy of fusion for a substance is less than its enthalpy of vaporization. This same logic
can be used to derive an approximate relation between the enthalpies of all phase changes for a given substance. Though not an
entirely accurate description, sublimation may be conveniently modeled as a sequential two-step process of melting followed by
vaporization in order to apply Hess’s Law.

solid ⟶ liquid ΔHfus
liquid ⟶ gas ΔHvap

–––––––––––––––––––––––
solid ⟶ gas ΔHsub = ΔHfus + ΔHvap
Viewed in this manner, the enthalpy of sublimation for a substance may be estimated as the sum of its enthalpies of fusion and
vaporization, as illustrated in Figure 10.4.7. For example:
Figure 10.4.7 : For a given substance, the sum of its enthalpy of fusion and enthalpy of vaporization is approximately equal to its
enthalpy of sublimation.
A diagram is shown with a vertical line drawn on the left side and labeled “Energy” and three horizontal lines drawn near the
bottom, lower third and top of the diagram. These three lines are labeled, from bottom to top, “Solid,” “Liquid” and “Gas.” Near
the middle of the diagram, a vertical, upward-facing arrow is drawn from the solid line to the gas line and labeled “Sublimation,
delta sign, H, subscript sub.” To the right of this arrow is a second vertical, upward-facing arrow that is drawn from the solid line to
the liquid line and labeled “Fusion, delta sign, H, subscript fus.” Above the second arrow is a third arrow drawn from the liquid line
to the gas line and labeled, “Vaporization, delta sign, H, subscript vap.”
Heating and Cooling Curves

In the chapter on thermochemistry, the relation between the amount of heat absorbed or related by a substance, q, and its
accompanying temperature change, ΔT, was introduced:
q = mcΔT
where m is the mass of the substance and c is its specific heat. The relation applies to matter being heated or cooled, but not
undergoing a change in state. When a substance being heated or cooled reaches a temperature corresponding to one of its phase
transitions, further gain or loss of heat is a result of diminishing or enhancing intermolecular attractions, instead of increasing or
decreasing molecular kinetic energies. While a substance is undergoing a change in state, its temperature remains constant. Figure
10.4.8 shows a typical heating curve.

Figure 10.4.8 : A typical heating curve for a substance depicts changes in temperature that result as the substance absorbs
increasing amounts of heat. Plateaus in the curve (regions of constant temperature) are exhibited when the substance undergoes
phase transitions.
A graph is shown where the x-axis is labeled “Amount of heat added” and the y-axis is labeled “Temperature ( degree sign C )” and
has values of negative 10 to 100 in increments of 20. A right-facing horizontal arrow extends from point “0, 0” to the right side of
the graph. A line graph begins at the lower left of the graph and moves to point “0” on the y-axis. This segment of the line is
labeled “H, subscript 2, O ( s ).” The line then flattens and travels horizontally for a small distance. This segment is labeled “Solid
begins to melt” on its left side and “All solid melted” on its right side. The line then goes steeply upward in a linear fashion until it
hits point “100” on the y-axis. This segment of the line is labeled “H, subscript 2, O,( l ).” The line then flattens and travels
horizontally for a moderate distance. This segment is labeled “Liquid begins to boil” on its left side and “All liquid evaporated” on
its right side. The line then rises to a point above “100” on the y-axis. This segment of the line is labeled “H, subscript 2, O ( g ).”
Consider the example of heating a pot of water to boiling. A stove burner will supply heat at a roughly constant rate; initially, this
heat serves to increase the water’s temperature. When the water reaches its boiling point, the temperature remains constant despite
the continued input of heat from the stove burner. This same temperature is maintained by the water as long as it is boiling. If the
burner setting is increased to provide heat at a greater rate, the water temperature does not rise, but instead the boiling becomes
more vigorous (rapid). This behavior is observed for other phase transitions as well: For example, temperature remains constant
while the change of state is in progress.
 Example 10.4.6: Total Heat Needed to Change Temperature and Phase for a Substance
How much heat is required to convert 135 g of ice at −15 °C into water vapor at 120 °C?
Solution
The transition described involves the following steps:
1. Heat ice from −15 °C to 0 °C
2. Melt ice
3. Heat water from 0 °C to 100 °C
4. Boil water
5. Heat steam from 100 °C to 120 °C
The heat needed to change the temperature of a given substance (with no change in phase) is: q = m × c × ΔT (see previous
chapter on thermochemistry). The heat needed to induce a given change in phase is given by q = n × ΔH.
Using these equations with the appropriate values for specific heat of ice, water, and steam, and enthalpies of fusion and
vaporization, we have:

qtotal = (m ⋅ c ⋅ ΔT )ice + n ⋅ ΔHfus + (m ⋅ c ⋅ ΔT )water + n ⋅ ΔHvap + (m ⋅ c ⋅ ΔT )steam
1 mol
= (135 g ⋅ 2.09 J/g ⋅ °C ⋅ 15°C) + (135 ⋅ ⋅ 6.01 kJ/mol)
18.02 g
1 mol
+(135 g ⋅ 4.18 J/g ⋅ °C ⋅ 100°C) + (135 g ⋅ ⋅ 40.67 kJ/mol)
18.02 g
+(135 g ⋅ 1.84 J/g ⋅ °C ⋅ 20°C)
= 4230 J + 45.0 kJ + 56, 500 J + 305 kJ + 4970 J
Converting the quantities in J to kJ permits them to be summed, yielding the total heat required:
= 4.23 kJ + 45.0 kJ + 56.5 kJ + 305 kJ + 4.97 kJ = 416 kJ
 Exercise 10.4.6
What is the total amount of heat released when 94.0 g water at 80.0 °C cools to form ice at −30.0 °C?
Answer
40.5 kJ
Summary
Phase transitions are processes that convert matter from one physical state into another. There are six phase transitions between the
three phases of matter. Melting, vaporization, and sublimation are all endothermic processes, requiring an input of heat to overcome
intermolecular attractions. The reciprocal transitions of freezing, condensation, and deposition are all exothermic processes,
involving heat as intermolecular attractive forces are established or strengthened. The temperatures at which phase transitions occur
are determined by the relative strengths of intermolecular attractions and are, therefore, dependent on the chemical identity of the
substance.
Key Equations
−Δ Hv ap /RT
P = Ae
ΔHvap
ln P = − + ln A
RT
P2 ΔHvap 1 1
ln( ) = ( − )
P1 R T1 T2
Glossary
boiling point
temperature at which the vapor pressure of a liquid equals the pressure of the gas above it
Clausius-Clapeyron equation
mathematical relationship between the temperature, vapor pressure, and enthalpy of vaporization for a substance
condensation
change from a gaseous to a liquid state
deposition
change from a gaseous state directly to a solid state
dynamic equilibrium
state of a system in which reciprocal processes are occurring at equal rates
freezing

change from a liquid state to a solid state
freezing point
temperature at which the solid and liquid phases of a substance are in equilibrium; see also melting point
melting
change from a solid state to a liquid state
melting point
temperature at which the solid and liquid phases of a substance are in equilibrium; see also freezing point
normal boiling point

temperature at which a liquid’s vapor pressure equals 1 atm (760 torr)
sublimation
change from solid state directly to gaseous state
vapor pressure
(also, equilibrium vapor pressure) pressure exerted by a vapor in equilibrium with a solid or a liquid at a given temperature
vaporization
change from liquid state to gaseous state
This page titled 10.4: Phase Transitions is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
10.3: Phase Transitions is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

Explain the construction and use of a typical phase diagram
Use phase diagrams to identify stable phases at given temperatures and pressures, and to describe phase transitions
resulting from changes in these properties
Describe the supercritical fluid phase of matter
In the previous module, the variation of a liquid’s equilibrium vapor pressure with temperature was described. Considering the
definition of boiling point, plots of vapor pressure versus temperature represent how the boiling point of the liquid varies with
pressure. Also described was the use of heating and cooling curves to determine a substance’s melting (or freezing) point. Making
such measurements over a wide range of pressures yields data that may be presented graphically as a phase diagram. A phase
diagram combines plots of pressure versus temperature for the liquid-gas, solid-liquid, and solid-gas phase-transition equilibria of a
substance. These diagrams indicate the physical states that exist under specific conditions of pressure and temperature, and also
provide the pressure dependence of the phase-transition temperatures (melting points, sublimation points, boiling points). A typical
phase diagram for a pure substance is shown in Figure 10.5.1.
Figure 10.5.1 : The physical state of a substance and its phase-transition temperatures are represented graphically in a phase
diagram.
A graph is shown where the x-axis is labeled “Temperature” and the y-axis is labeled “Pressure.” A line extends from the lower left
bottom of the graph sharply upward to a point that is a third across the x-axis. A second line begins at the lower third of the first
line at a point labeled “triple point” and extends to the upper right corner of the graph where it is labeled “critical point.” The two
lines bisect the graph area to create three sections, labeled “solid” near the top left, “liquid” in the top middle and “gas” near the
bottom right. A pair of horizontal arrows, one left-facing and labeled “deposition” and one right-facing and labeled” sublimation,”
are drawn on top of the bottom section of the first line. A second pair of horizontal arrows, one left-facing and labeled “freezing”
and one right-facing and labeled “melting”, are drawn on top of the upper section of the first line. A third pair of horizontal arrows,
one left-facing and labeled “condensation” and one right-facing and labeled ”vaporization,” are drawn on top of the middle section
of the second line.
To illustrate the utility of these plots, consider the phase diagram for water shown in Figure 10.5.2.

Figure 10.5.2 : The pressure and temperature axes on this phase diagram of water are not drawn to constant scale in order to
illustrate several important properties.
A graph is shown where the x-axis is labeled “Temperature in degrees Celsius” and the y-axis is labeled “Pressure ( k P a ).” A line
extends from the origin of the graph which is labeled “A” sharply upward to a point in the bottom third of the diagram labeled “B”
where it branches into a line that slants slightly backward until it hits the highest point on the y-axis labeled “D” and a second line
that extends to the upper right corner of the graph labeled “C”. C is labeled “Critical point, with a dotted line extending downward
to the x-axis labeled 374 degrees Celsius, and another dotted line extending to the y-axis labeled 22,089 k P a. The two lines bisect
the graph area to create three sections, labeled “Ice (solid)” near the middle left, “Water (liquid)” in the top middle and “Water
vapor (gas)” near the bottom middle. Point B is labeled “Triple point” and has a dotted line extending downward to the x-axis
labeled 0.01, and another dotted line extending to the y-axis labeled 0.6. Halfway between points B and C a dotted line extends
from the originally discussed line downward to the point 100 degrees Celsius on the x-axis, and another dotted line extends to the
y-axis at 101 k P a. Another dotted line extends from this dotted line downward at 0 degrees Celsius.
We can use the phase diagram to identify the physical state of a sample of water under specified conditions of pressure and
temperature. For example, a pressure of 50 kPa and a temperature of −10 °C correspond to the region of the diagram labeled “ice.”
Under these conditions, water exists only as a solid (ice). A pressure of 50 kPa and a temperature of 50 °C correspond to the
“water” region—here, water exists only as a liquid. At 25 kPa and 200 °C, water exists only in the gaseous state. Note that on the
H2O phase diagram, the pressure and temperature axes are not drawn to a constant scale in order to permit the illustration of several
important features as described here.
The curve BC in Figure 10.5.2 is the plot of vapor pressure versus temperature as described in the previous module of this chapter.
This “liquid-vapor” curve separates the liquid and gaseous regions of the phase diagram and provides the boiling point for water at
any pressure. For example, at 1 atm, the boiling point is 100 °C. Notice that the liquid-vapor curve terminates at a temperature of
374 °C and a pressure of 218 atm, indicating that water cannot exist as a liquid above this temperature, regardless of the pressure.
The physical properties of water under these conditions are intermediate between those of its liquid and gaseous phases. This
unique state of matter is called a supercritical fluid, a topic that will be described in the next section of this module.
The solid-vapor curve, labeled AB in Figure 10.5.2, indicates the temperatures and pressures at which ice and water vapor are in
equilibrium. These temperature-pressure data pairs correspond to the sublimation, or deposition, points for water. If we could zoom
in on the solid-gas line in Figure 10.5.2, we would see that ice has a vapor pressure of about 0.20 kPa at −10 °C. Thus, if we place
a frozen sample in a vacuum with a pressure less than 0.20 kPa, ice will sublime. This is the basis for the “freeze-drying” process
often used to preserve foods, such as the ice cream shown in Figure 10.5.3.

Figure 10.5.3 : Freeze-dried foods, like this ice cream, are dehydrated by sublimation at pressures below the triple point for water.
(credit: ʺlwaoʺ/Flickr)
The solid-liquid curve labeled BD shows the temperatures and pressures at which ice and liquid water are in equilibrium,
representing the melting/freezing points for water. Note that this curve exhibits a slight negative slope (greatly exaggerated for
clarity), indicating that the melting point for water decreases slightly as pressure increases. Water is an unusual substance in this
regard, as most substances exhibit an increase in melting point with increasing pressure. This behavior is partly responsible for the
movement of glaciers, like the one shown in Figure 10.5.4. The bottom of a glacier experiences an immense pressure due to its
weight that can melt some of the ice, forming a layer of liquid water on which the glacier may more easily slide.
Figure 10.5.4 : The immense pressures beneath glaciers result in partial melting to produce a layer of water that provides lubrication
to assist glacial movement. This satellite photograph shows the advancing edge of the Perito Moreno glacier in Argentina. (credit:
NASA)
A photograph shows an aerial view of a land mass. The white mass of a glacier is shown near the top left quadrant of the photo and
leads to two branching blue rivers. The open land is shown in brown.
The point of intersection of all three curves is labeled B in Figure 10.5.2. At the pressure and temperature represented by this point,
all three phases of water coexist in equilibrium. This temperature-pressure data pair is called the triple point. At pressures lower
than the triple point, water cannot exist as a liquid, regardless of the temperature.
 Example 10.5.1: Determining the State of Water
Using the phase diagram for water given in Figure 10.4.2, determine the state of water at the following temperatures and
pressures:
a. −10 °C and 50 kPa
b. 25 °C and 90 kPa
c. 50 °C and 40 kPa
d. 80 °C and 5 kPa
e. −10 °C and 0.3 kPa
f. 50 °C and 0.3 kPa
Solution
Using the phase diagram for water, we can determine that the state of water at each temperature and pressure given are as
follows: (a) solid; (b) liquid; (c) liquid; (d) gas; (e) solid; (f) gas.

 Exercise 10.5.1
What phase changes can water undergo as the temperature changes if the pressure is held at 0.3 kPa? If the pressure is held at
50 kPa?
Answer
At 0.3 kPa: s⟶ g at −58 °C. At 50 kPa: s⟶ l at 0 °C, l ⟶ g at 78 °C
Consider the phase diagram for carbon dioxide shown in Figure 10.5.5 as another example. The solid-liquid curve exhibits a
positive slope, indicating that the melting point for CO2 increases with pressure as it does for most substances (water being a
notable exception as described previously). Notice that the triple point is well above 1 atm, indicating that carbon dioxide cannot
exist as a liquid under ambient pressure conditions. Instead, cooling gaseous carbon dioxide at 1 atm results in its deposition into
the solid state. Likewise, solid carbon dioxide does not melt at 1 atm pressure but instead sublimes to yield gaseous CO2. Finally,
notice that the critical point for carbon dioxide is observed at a relatively modest temperature and pressure in comparison to water.
Figure 10.5.5 : The pressure and temperature axes on this phase diagram of carbon dioxide are not drawn to constant scale in order
to illustrate several important properties.
A graph is shown where the x-axis is labeled “Temperature ( degree sign, C )” and has values of negative 100 to 100 in increments
of 25 and the y-axis is labeled “Pressure ( k P a )” and has values of 10 to 1,000,000. A line extends from the lower left bottom of
the graph upward to a point around“27, 9000,” where it ends. The space under this curve is labeled “Gas.” A second line extends in
a curve from point around “-73, 100” to “27, 1,000,000.” The area to the left of this line and above the first line is labeled “Solid”
while the area to the right is labeled “Liquid.” A section on the graph under the second line and past the point “28” on the x-axis is
labeled “S C F.”
 Example 10.5.2: Determining the State of Carbon Dioxide
Using the phase diagram for carbon dioxide shown in Figure 10.4.5, determine the state of CO2 at the following temperatures
and pressures:
a. −30 °C and 2000 kPa
b. −60 °C and 1000 kPa
c. −60 °C and 100 kPa
d. 20 °C and 1500 kPa
e. 0 °C and 100 kPa
f. 20 °C and 100 kPa
Solution
Using the phase diagram for carbon dioxide provided, we can determine that the state of CO2 at each temperature and pressure
given are as follows: (a) liquid; (b) solid; (c) gas; (d) liquid; (e) gas; (f) gas.

 Exercise 10.5.2
Determine the phase changes carbon dioxide undergoes when its temperature is varied, thus holding its pressure constant at
1500 kPa? At 500 kPa? At what approximate temperatures do these phase changes occur?
Answer
at 1500 kPa: s⟶ l at −45 °C, l⟶ g at −10 °C; at 500 kPa: s⟶ g at −58 °C
Supercritical Fluids
If we place a sample of water in a sealed container at 25 °C, remove the air, and let the vaporization-condensation equilibrium
establish itself, we are left with a mixture of liquid water and water vapor at a pressure of 0.03 atm. A distinct boundary between
the more dense liquid and the less dense gas is clearly observed. As we increase the temperature, the pressure of the water vapor
increases, as described by the liquid-gas curve in the phase diagram for water (Figure 10.5.2), and a two-phase equilibrium of
liquid and gaseous phases remains. At a temperature of 374 °C, the vapor pressure has risen to 218 atm, and any further increase in
temperature results in the disappearance of the boundary between liquid and vapor phases. All of the water in the container is now
present in a single phase whose physical properties are intermediate between those of the gaseous and liquid states. This phase of
matter is called a supercritical fluid, and the temperature and pressure above which this phase exists is the critical point (Figure
10.5.5). Above its critical temperature, a gas cannot be liquefied no matter how much pressure is applied. The pressure required to
liquefy a gas at its critical temperature is called the critical pressure. The critical temperatures and critical pressures of some
common substances are given in Table 10.5.1.
Table 10.5.1 : Critical Temperatures and Critical Pressures of select substances
Substance Critical Temperature (K) Critical Pressure (atm)
hydrogen 33.2 12.8
nitrogen 126.0 33.5
oxygen 154.3 49.7
carbon dioxide 304.2 73.0
ammonia 405.5 111.5
sulfur dioxide 430.3 77.7
water 647.1 217.7
Like a gas, a supercritical fluid will expand and fill a container, but its density is much greater than typical gas densities, typically
being close to those for liquids. Similar to liquids, these fluids are capable of dissolving nonvolatile solutes. They exhibit
essentially no surface tension and very low viscosities, however, so they can more effectively penetrate very small openings in a
solid mixture and remove soluble components. These properties make supercritical fluids extremely useful solvents for a wide
range of applications. For example, supercritical carbon dioxide has become a very popular solvent in the food industry, being used
to decaffeinate coffee, remove fats from potato chips, and extract flavor and fragrance compounds from citrus oils. It is nontoxic,
relatively inexpensive, and not considered to be a pollutant. After use, the CO2 can be easily recovered by reducing the pressure
and collecting the resulting gas.

Figure 10.5.6 : (a) A sealed container of liquid carbon dioxide slightly below its critical point is heated, resulting in (b) the
formation of the supercritical fluid phase. Cooling the supercritical fluid lowers its temperature and pressure below the critical
point, resulting in the reestablishment of separate liquid and gaseous phases (c and d). Colored floats illustrate differences in
density between the liquid, gaseous, and supercritical fluid states. (credit: modification of work by “mrmrobin”/YouTube)
Four photographs are shown where each shows a circular container with a green and red float in each. In the left diagram, the
container is half filled with a colorless liquid and the floats sit on the surface of the liquid. In the second photo, the green float is
near the top and the red float lies near the bottom of the container. In the third photo, the fluid is darker and the green float sits
halfway up the container while the red is sitting at the bottom. In the right photo, the liquid is colorless again and the two floats sit
on the surface.
 Example 10.5.3: The Critical Temperature of Carbon Dioxide
If we shake a carbon dioxide fire extinguisher on a cool day (18 °C), we can hear liquid CO2 sloshing around inside the
cylinder. However, the same cylinder appears to contain no liquid on a hot summer day (35 °C). Explain these observations.
Solution
On the cool day, the temperature of the CO2 is below the critical temperature of CO2, 304 K or 31 °C (Table 10.5.1), so liquid
CO2 is present in the cylinder. On the hot day, the temperature of the CO2 is greater than its critical temperature of 31 °C.
Above this temperature no amount of pressure can liquefy CO2 so no liquid CO2 exists in the fire extinguisher.
 Exercise 10.5.3
Ammonia can be liquefied by compression at room temperature; oxygen cannot be liquefied under these conditions. Why do
the two gases exhibit different behavior?
Answer
The critical temperature of ammonia is 405.5 K, which is higher than room temperature. The critical temperature of oxygen
is below room temperature; thus oxygen cannot be liquefied at room temperature.
Decaffeinating Coffee Using Supercritical CO2

Coffee is the world’s second most widely traded commodity, following only petroleum. Across the globe, people love coffee’s
aroma and taste. Many of us also depend on one component of coffee—caffeine—to help us get going in the morning or stay alert
in the afternoon. But late in the day, coffee’s stimulant effect can keep you from sleeping, so you may choose to drink decaffeinated
coffee in the evening.
Since the early 1900s, many methods have been used to decaffeinate coffee. All have advantages and disadvantages, and all depend
on the physical and chemical properties of caffeine. Because caffeine is a somewhat polar molecule, it dissolves well in water, a
polar liquid. However, since many of the other 400-plus compounds that contribute to coffee’s taste and aroma also dissolve in
H2O, hot water decaffeination processes can also remove some of these compounds, adversely affecting the smell and taste of the
decaffeinated coffee. Dichloromethane (CH2Cl2) and ethyl acetate (CH3CO2C2H5) have similar polarity to caffeine, and are
therefore very effective solvents for caffeine extraction, but both also remove some flavor and aroma components, and their use
requires long extraction and cleanup times. Because both of these solvents are toxic, health concerns have been raised regarding the
effect of residual solvent remaining in the decaffeinated coffee.

Figure 10.5.7 : (a) Caffeine molecules have both polar and nonpolar regions, making it soluble in solvents of varying polarities. (b)
The schematic shows a typical decaffeination process involving supercritical carbon dioxide.
Two images are shown and labeled “a” and “b.” Image a shows a molecule composed of a five member ring composed of two blue
spheres and three black spheres. One of the blue spheres is bonded to a black sphere bonded to three white spheres and one of the
black spheres is bonded to a white sphere. The other two black spheres are double bonded together and make up one side of a six-
membered ring that is also composed of two more black spheres and two blue spheres, both of which are bonded to a black sphere
bonded to three white spheres. The black spheres are each double bonded to red spheres. Image b shows a diagram of two vertical
tubes that lie next to one another. The left-hand tube is labeled “Extraction vessel.” A small tube labeled “Soaked beans” leads into
the top of the tube and a label at the bottom of the tube reads “Decaffeinated beans.” The right tube is labeled “Absorption vessel.”
A tube near the top of this tube is labeled “Water” and another tube leads from the right tube to the left. This tube is labeled with a
left-facing arrow and the phrase “supercritical carbon dioxide.” There is a tube leading away from the bottom which is labeled,
“Caffeine and water.” There is another tube that leads from the extraction vessel to the absorption vessel which is labeled,
“supercritical C O subscript 2 plus caffeine.”
Supercritical fluid extraction using carbon dioxide is now being widely used as a more effective and environmentally friendly
decaffeination method (Figure 10.5.7). At temperatures above 304.2 K and pressures above 7376 kPa, CO2 is a supercritical fluid,
with properties of both gas and liquid. Like a gas, it penetrates deep into the coffee beans; like a liquid, it effectively dissolves
certain substances. Supercritical carbon dioxide extraction of steamed coffee beans removes 97−99% of the caffeine, leaving
coffee’s flavor and aroma compounds intact. Because CO2 is a gas under standard conditions, its removal from the extracted coffee
beans is easily accomplished, as is the recovery of the caffeine from the extract. The caffeine recovered from coffee beans via this
process is a valuable product that can be used subsequently as an additive to other foods or drugs.
Summary
The temperature and pressure conditions at which a substance exists in solid, liquid, and gaseous states are summarized in a phase
diagram for that substance. Phase diagrams are combined plots of three pressure-temperature equilibrium curves: solid-liquid,
liquid-gas, and solid-gas. These curves represent the relationships between phase-transition temperatures and pressures. The point
of intersection of all three curves represents the substance’s triple point—the temperature and pressure at which all three phases are
in equilibrium. At pressures below the triple point, a substance cannot exist in the liquid state, regardless of its temperature. The
terminus of the liquid-gas curve represents the substance’s critical point, the pressure and temperature above which a liquid phase
cannot exist.
Glossary
critical point
temperature and pressure above which a gas cannot be condensed into a liquid
phase diagram
pressure-temperature graph summarizing conditions under which the phases of a substance can exist
supercritical fluid
substance at a temperature and pressure higher than its critical point; exhibits properties intermediate between those of gaseous
and liquid states

triple point
temperature and pressure at which the vapor, liquid, and solid phases of a substance are in equilibrium
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Define and describe the bonding and properties of ionic, molecular, metallic, and covalent network crystalline solids
Describe the main types of crystalline solids: ionic solids, metallic solids, covalent network solids, and molecular solids
Explain the ways in which crystal defects can occur in a solid
When most liquids are cooled, they eventually freeze and form crystalline solids, solids in which the atoms, ions, or molecules are
arranged in a definite repeating pattern. It is also possible for a liquid to freeze before its molecules become arranged in an orderly
pattern. The resulting materials are called amorphous solids or noncrystalline solids (or, sometimes, glasses). The particles of such
solids lack an ordered internal structure and are randomly arranged (Figure 10.6.1).
Figure 10.6.1 : The entities of a solid phase may be arranged in a regular, repeating pattern (crystalline solids) or randomly
(amorphous).
The crystalline arrangement shows many circles drawn in rows and stacked together tightly. The amorphous arrangement shows
many circles spread slightly apart and in no organized pattern.
Metals and ionic compounds typically form ordered, crystalline solids. Substances that consist of large molecules, or a mixture of
molecules whose movements are more restricted, often form amorphous solids. For examples, candle waxes are amorphous solids
composed of large hydrocarbon molecules. Some substances, such as boron oxide (Figure 10.6.2), can form either crystalline or
amorphous solids, depending on the conditions under which it is produced. Also, amorphous solids may undergo a transition to the
crystalline state under appropriate conditions.
Figure 10.6.2 : (a) Diboron trioxide, B2O3, is normally found as a white, amorphous solid (a glass), which has a high degree of
disorder in its structure. (b) By careful, extended heating, it can be converted into a crystalline form of B2O3, which has a very
ordered arrangement.
The first structure of diboron trioxide shows five identical and separated hexagonal rings. The second structure of diboron trioxide
shows a more interconnected structure with four large rings forming a more stable structure.
Crystalline solids are generally classified according the nature of the forces that hold its particles together. These forces are
primarily responsible for the physical properties exhibited by the bulk solids. The following sections provide descriptions of the

major types of crystalline solids: ionic, metallic, covalent network, and molecular.
Ionic Solids
Ionic solids, such as sodium chloride and nickel oxide, are composed of positive and negative ions that are held together by
electrostatic attractions, which can be quite strong (Figure 10.6.3). Many ionic crystals also have high melting points. This is due to
the very strong attractions between the ions—in ionic compounds, the attractions between full charges are (much) larger than those
between the partial charges in polar molecular compounds. This will be looked at in more detail in a later discussion of lattice
energies. Although they are hard, they also tend to be brittle, and they shatter rather than bend. Ionic solids do not conduct
electricity; however, they do conduct when molten or dissolved because their ions are free to move. Many simple compounds
formed by the reaction of a metallic element with a nonmetallic element are ionic.
Figure 10.6.3 : Sodium chloride is an ionic solid.

A cube composed of purple and green spheres is shown. The cube has dimensions of three by three spheres. The purple spheres are
slightly larger than the green spheres.
Metallic Solids
Metallic solids such as crystals of copper, aluminum, and iron are formed by metal atoms Figure 10.6.4. The structure of metallic
crystals is often described as a uniform distribution of atomic nuclei within a “sea” of delocalized electrons. The atoms within such
a metallic solid are held together by a unique force known as metallic bonding that gives rise to many useful and varied bulk
properties. All exhibit high thermal and electrical conductivity, metallic luster, and malleability. Many are very hard and quite
strong. Because of their malleability (the ability to deform under pressure or hammering), they do not shatter and, therefore, make
useful construction materials. The melting points of the metals vary widely. Mercury is a liquid at room temperature, and the alkali
metals melt below 200 °C. Several post-transition metals also have low melting points, whereas the transition metals melt at
temperatures above 1000 °C. These differences reflect differences in strengths of metallic bonding among the metals.
Figure 10.6.4 : Copper is a metallic solid.
Covalent Network Solids

Covalent network solids include crystals of diamond, silicon, some other nonmetals, and some covalent compounds such as silicon
dioxide (sand) and silicon carbide (carborundum, the abrasive on sandpaper). Many minerals have networks of covalent bonds. The
atoms in these solids are held together by a network of covalent bonds, as shown in Figure 10.6.5. To break or to melt a covalent
network solid, covalent bonds must be broken. Because covalent bonds are relatively strong, covalent network solids are typically
characterized by hardness, strength, and high melting points. For example, diamond is one of the hardest substances known and
melts above 3500 °C.

Figure 10.6.5 . A covalent crystal contains a three-dimensional network of covalent bonds, as illustrated by the structures of
diamond, silicon dioxide, silicon carbide, and graphite. Graphite is an exceptional example, composed of planar sheets of covalent
crystals that are held together in layers by noncovalent forces. Unlike typical covalent solids, graphite is very soft and electrically
conductive.
The complex three dimensional structure of diamond, silicon dioxide, silicon carbide and graphite is shown along with a a smaller
repeating unit of the structure shown above each structure.
Molecular Solids
Molecular solids, such as ice, sucrose (table sugar), and iodine, as shown in Figure 10.6.6, are composed of neutral molecules. The
strengths of the attractive forces between the units present in different crystals vary widely, as indicated by the melting points of the
crystals. Small symmetrical molecules (nonpolar molecules), such as H2, N2, O2, and F2, have weak attractive forces and form
molecular solids with very low melting points (below −200 °C). Substances consisting of larger, nonpolar molecules have larger
attractive forces and melt at higher temperatures. Molecular solids composed of molecules with permanent dipole moments (polar
molecules) melt at still higher temperatures. Examples include ice (melting point, 0 °C) and table sugar (melting point, 185 °C).
Figure 10.6.6 : Carbon dioxide (CO2) consists of small, nonpolar molecules and forms a molecular solid with a melting point of
−78 °C. Iodine (I2) consists of larger, nonpolar molecules and forms a molecular solid that melts at 114 °C.
On the left, many red and grey molecules are densely stacked in a 3-D drawing to represent carbon dioxide. On the right, purple
molecules are scattered randomly to represent iodine.
Properties of Solids
A crystalline solid, like those listed in Table 10.6.1 has a precise melting temperature because each atom or molecule of the same
type is held in place with the same forces or energy. Thus, the attractions between the units that make up the crystal all have the
same strength and all require the same amount of energy to be broken. The gradual softening of an amorphous material differs
dramatically from the distinct melting of a crystalline solid. This results from the structural nonequivalence of the molecules in the
amorphous solid. Some forces are weaker than others, and when an amorphous material is heated, the weakest intermolecular
attractions break first. As the temperature is increased further, the stronger attractions are broken. Thus amorphous materials soften
over a range of temperatures.
Table 10.6.1 : Types of Crystalline Solids and Their Properties

Type of Solid Type of Particles Type of Attractions Properties Examples
hard, brittle, conducts

electricity as a liquid but
ionic ions ionic bonds NaCl, Al2O3
not as a solid, high to very
high melting points
shiny, malleable, ductile,

conducts heat and
atoms of electropositive
metallic metallic bonds electricity well, variable Cu, Fe, Ti, Pb, U
elements
hardness and melting
temperature
atoms of electronegative very hard, not conductive,

covalent network covalent bonds C (diamond), SiO2, SiC
elements very high melting points
variable hardness, variable

molecular molecules (or atoms) IMFs brittleness, not conductive, H2O, CO2, I2, C12H22O11
low melting points
 Graphene: Material of the Future
Carbon is an essential element in our world. The unique properties of carbon atoms allow the existence of carbon-based life
forms such as ourselves. Carbon forms a huge variety of substances that we use on a daily basis, including those shown in
Figure 10.6.7. You may be familiar with diamond and graphite, the two most common allotropes of carbon. (Allotropes are
different structural forms of the same element.) Diamond is one of the hardest-known substances, whereas graphite is soft
enough to be used as pencil lead. These very different properties stem from the different arrangements of the carbon atoms in
the different allotropes.
Figure 10.6.7 : Diamond is extremely hard because of the strong bonding between carbon atoms in all directions. Graphite (in
pencil lead) rubs off onto paper due to the weak attractions between the carbon layers. An image of a graphite surface shows
the distance between the centers of adjacent carbon atoms. (credit left photo: modification of work by Steve Jurvetson; credit
middle photo: modification of work by United States Geological Survey)
A close up of a piece of diamond shows a three dimensional sturcture of a complex network of well bonded carbon atoms. A
close up of a graphite shows several layers of carbon sheets. Each sheet is composed of a repeated and connected hexagonal
structure of carbon atoms. The third diagram shows that the distance between the center of atoms is 1.4 times 10 to the power
of negative 10 meters.
You may be less familiar with a recently discovered form of carbon: graphene. Graphene was first isolated in 2004 by using
tape to peel off thinner and thinner layers from graphite. It is essentially a single sheet (one atom thick) of graphite. Graphene,
illustrated in Figure 10.6.8, is not only strong and lightweight, but it is also an excellent conductor of electricity and heat.

These properties may prove very useful in a wide range of applications, such as vastly improved computer chips and circuits,
better batteries and solar cells, and stronger and lighter structural materials. The 2010 Nobel Prize in Physics was awarded to
Andre Geim and Konstantin Novoselov for their pioneering work with graphene.
Figure 10.6.8 : Graphene sheets can be formed into buckyballs, nanotubes, and stacked layers.
A sheet of interconnected hexagonal rings is shown at the top. Below it, a bukcyball is shown which is a sphere is composed of
hexagonal rings. In the lower middle image, a nanotube is shown that is made by rolling a graphene sheet into a tube. In the
lower right image, stacked sheets made up of four horizontal sheets composed of joined, hexagonal rings is shown.
Crystal Defects
In a crystalline solid, the atoms, ions, or molecules are arranged in a definite repeating pattern, but occasional defects may occur in
the pattern. Several types of defects are known, as illustrated in Figure 10.6.9. Vacancies are defects that occur when positions that
should contain atoms or ions are vacant. Less commonly, some atoms or ions in a crystal may occupy positions, called interstitial
sites, located between the regular positions for atoms. Other distortions are found in impure crystals, as, for example, when the
cations, anions, or molecules of the impurity are too large to fit into the regular positions without distorting the structure. Trace
amounts of impurities are sometimes added to a crystal (a process known as doping) in order to create defects in the structure that
yield desirable changes in its properties. For example, silicon crystals are doped with varying amounts of different elements to
yield suitable electrical properties for their use in the manufacture of semiconductors and computer chips.
Figure 10.6.9 : Types of crystal defects include vacancies, interstitial atoms, and substitutions impurities.

Summary
Some substances form crystalline solids consisting of particles in a very organized structure; others form amorphous
(noncrystalline) solids with an internal structure that is not ordered. The main types of crystalline solids are ionic solids, metallic
solids, covalent network solids, and molecular solids. The properties of the different kinds of crystalline solids are due to the types
of particles of which they consist, the arrangements of the particles, and the strengths of the attractions between them. Because
their particles experience identical attractions, crystalline solids have distinct melting temperatures; the particles in amorphous
solids experience a range of interactions, so they soften gradually and melt over a range of temperatures. Some crystalline solids
have defects in the definite repeating pattern of their particles. These defects (which include vacancies, atoms or ions not in the
regular positions, and impurities) change physical properties such as electrical conductivity, which is exploited in the silicon
crystals used to manufacture computer chips.
Glossary
amorphous solid
(also, noncrystalline solid) solid in which the particles lack an ordered internal structure
covalent network solid

solid whose particles are held together by covalent bonds
crystalline solid
solid in which the particles are arranged in a definite repeating pattern
interstitial sites
spaces between the regular particle positions in any array of atoms or ions
ionic solid
solid composed of positive and negative ions held together by strong electrostatic attractions
metallic solid
solid composed of metal atoms
molecular solid
solid composed of neutral molecules held together by intermolecular forces of attraction
vacancy
defect that occurs when a position that should contain an atom or ion is vacant
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Describe the arrangement of atoms and ions in crystalline structures
Compute ionic radii using unit cell dimensions
Explain the use of X-ray diffraction measurements in determining crystalline structures
Over 90% of naturally occurring and man-made solids are crystalline. Most solids form with a regular arrangement of their
particles because the overall attractive interactions between particles are maximized, and the total intermolecular energy is
minimized, when the particles pack in the most efficient manner. The regular arrangement at an atomic level is often reflected at a
macroscopic level. In this module, we will explore some of the details about the structures of metallic and ionic crystalline solids,
and learn how these structures are determined experimentally.
The Structures of Metals

We will begin our discussion of crystalline solids by considering elemental metals, which are relatively simple because each
contains only one type of atom. A pure metal is a crystalline solid with metal atoms packed closely together in a repeating pattern.
Some of the properties of metals in general, such as their malleability and ductility, are largely due to having identical atoms
arranged in a regular pattern. The different properties of one metal compared to another partially depend on the sizes of their atoms
and the specifics of their spatial arrangements. We will explore the similarities and differences of four of the most common metal
crystal geometries in the sections that follow.
Unit Cells of Metals

The structure of a crystalline solid, whether a metal or not, is best described by considering its simplest repeating unit, which is
referred to as its unit cell. The unit cell consists of lattice points that represent the locations of atoms or ions. The entire structure
then consists of this unit cell repeating in three dimensions, as illustrated in Figure 10.7.1.
Figure 10.7.1 : A unit cell shows the locations of lattice points repeating in all directions.
A diagram of two images is shown. In the first image, a cube with a sphere at each corner is shown. The cube is labeled “Unit cell”
and the spheres at the corners are labeled “Lattice points.” The second image shows the same cube, but this time it is one cube
amongst eight that make up a larger cube. The original cube is shaded a color while the other cubes are not.
Let us begin our investigation of crystal lattice structure and unit cells with the most straightforward structure and the most basic
unit cell. To visualize this, imagine taking a large number of identical spheres, such as tennis balls, and arranging them uniformly in
a container. The simplest way to do this would be to make layers in which the spheres in one layer are directly above those in the
layer below, as illustrated in Figure 10.7.2. This arrangement is called simple cubic structure, and the unit cell is called the simple
cubic unit cell or primitive cubic unit cell.

Figure 10.7.2 : .When metal atoms are arranged with spheres in one layer directly above or below spheres in another layer, the
lattice structure is called simple cubic. Note that the spheres are in contact.
A diagram of three images is shown. In the first image, a cube with a sphere at each corner is shown. The spheres at the corners are
circled. The second image shows the same cube, but this time the spheres at the corners are larger and shaded in. In the third image,
the cube is one cube amongst eight that make up a larger cube. The original cube is shaded a color while the other cubes are not.
In a simple cubic structure, the spheres are not packed as closely as they could be, and they only “fill” about 52% of the volume of
the container. This is a relatively inefficient arrangement, and only one metal (polonium, Po) crystallizes in a simple cubic
structure. As shown in Figure 10.7.3, a solid with this type of arrangement consists of planes (or layers) in which each atom
contacts only the four nearest neighbors in its layer; one atom directly above it in the layer above; and one atom directly below it in
the layer below. The number of other particles that each particle in a crystalline solid contacts is known as its coordination number.
For a polonium atom in a simple cubic array, the coordination number is, therefore, six.
<div data-mt-source="1"
""
" height="200" width="463" src="/@api/deki/files/61021/CNX_Chem_10_06_SimpleCub2.jpg">
Figure 10.7.3 : An atom in a simple cubic lattice structure contacts six other atoms, so it has a coordination number of six.
In a simple cubic lattice, the unit cell that repeats in all directions is a cube defined by the centers of eight atoms, as shown in
Figure 10.7.4. Atoms at adjacent corners of this unit cell contact each other, so the edge length of this cell is equal to two atomic
radii, or one atomic diameter. A cubic unit cell contains only the parts of these atoms that are within it. Since an atom at a corner of
a simple cubic unit cell is contained by a total of eight unit cells, only one-eighth of that atom is within a specific unit cell. And
1
since each simple cubic unit cell has one atom at each of its eight “corners,” there is 8 × =1 atom within one simple cubic unit
8
cell.
Figure 10.7.4 : A simple cubic lattice unit cell contains one-eighth of an atom at each of its eight corners, so it contains one atom
total.
A diagram of two images is shown. In the first image, eight spheres are stacked together to form a cube and dots at the center of
each sphere are connected to form a cube shape. The dots are labeled “Lattice points” while a label under the image reads “Simple
cubic lattice cell.” The second image shows the portion of each sphere that lie inside the cube. The corners of the cube are shown
with small circles labeled “Lattice points” and the phrase “8 corners” is written below the image.
 Example 10.7.1: Calculating Atomic Radius and Density for Metals (Part 1)
The edge length of the unit cell of alpha polonium is 336 pm.
a. Determine the radius of a polonium atom.
b. Determine the density of alpha polonium.
Solution
Alpha polonium crystallizes in a simple cubic unit cell:

(a) Two adjacent Po atoms contact each other, so the edge length of this cell is equal to two Po atomic radii: l = 2r . Therefore,
the radius of Po is
l 336 pm
r = = = 168 pm
2 2
(b) Density is given by

mass
density = .
volume
The density of polonium can be found by determining the density of its unit cell (the mass contained within a unit cell divided
by the volume of the unit cell). Since a Po unit cell contains one-eighth of a Po atom at each of its eight corners, a unit cell
contains one Po atom.
The mass of a Po unit cell can be found by:
1 Po atom 1 mol Po 208.998 g
−22
1 Po unit cell × × × = 3.47 × 10 g
23
1 Po unit cell 6.022 × 10 Po atoms 1 mol Po
The volume of a Po unit cell can be found by:

3 −10 3 −23 3
V =l = (336 × 10 cm) = 3.79 × 10 cm
(Note that the edge length was converted from pm to cm to get the usual volume units for density.)
Therefore, the density of
−22
3.471 × 10 g
3
Po = = 9.16 g/cm
−23
3.79 × 10 cm3
 Exercise 10.7.1
The edge length of the unit cell for nickel is 0.3524 nm. The density of Ni is 8.90 g/cm3. Does nickel crystallize in a simple
cubic structure? Explain.
Answer
No. If Ni were simple cubic, its density would be given by:
1 mol Ni 58.693 g
−23
1 Ni atom × × = 9.746 × 10 g
23
6.022 × 10 Ni atoms 1 mol Ni
3 −8 3 −23 3
V =l = (3.524 × 10 cm) = 4.376 × 10 cm
Then the density of Ni would be

−23
9.746 × 10 g
3
(= = 2.23 g/cm
−23 3
4.376 × 10 cm

Since the actual density of Ni is not close to this, Ni does not form a simple cubic structure.
Most metal crystals are one of the four major types of unit cells. For now, we will focus on the three cubic unit cells: simple cubic
(which we have already seen), body-centered cubic unit cell, and face-centered cubic unit cell—all of which are illustrated in
Figure 10.7.5. (Note that there are actually seven different lattice systems, some of which have more than one type of lattice, for a
total of 14 different types of unit cells. We leave the more complicated geometries for later in this module.)
Figure 10.7.5 : Cubic unit cells of metals show (in the upper figures) the locations of lattice points and (in the lower figures) metal
atoms located in the unit cell.
Three pairs of images are shown. The first three images are in a row and are labeled “Lattice point locations” while the second
three images are in a row labeled “Cubic unit cells.” The first image in the top row shows a cube with black dots at each corner
while the first image in the second row is composed of eight spheres that are stacked together to form a cube and dots at the center
of each sphere are connected to form a cube shape. The name under this image reads “Simple cubic.” The second image in the top
row shows a cube with black dots at each corner and a red dot in the center while the second image in the second row is composed
of eight spheres that are stacked together to form a cube with one sphere in the center of the cube and dots at the center of each
corner sphere connected to form a cube shape. The name under this image reads “Body-centered cubic.” The third image in the top
row shows a cube with black dots at each corner and red dots in the center of each face while the third image in the second row is
composed of eight spheres that are stacked together to form a cube with six more spheres located in the center of each face of the
cube. Dots at the center of each corner sphere are connected to form a cube shape. The name under this image reads “Face-centered
cubic.”
Some metals crystallize in an arrangement that has a cubic unit cell with atoms at all of the corners and an atom in the center, as
shown in Figure 10.7.6. This is called a body-centered cubic (BCC) solid. Atoms in the corners of a BCC unit cell do not contact
each other but contact the atom in the center. A BCC unit cell contains two atoms: one-eighth of an atom at each of the eight
1
corners (8 × =1 atom from the corners) plus one atom from the center. Any atom in this structure touches four atoms in the
8
layer above it and four atoms in the layer below it. Thus, an atom in a BCC structure has a coordination number of eight.
Figure 10.7.6 : In a body-centered cubic structure, atoms in a specific layer do not touch each other. Each atom touches four atoms
in the layer above it and four atoms in the layer below it.
Three images are shown. The first image shows a cube with black dots at each corner and a red dot in the center while the second
image is composed of eight spheres that are stacked together to form a cube with one sphere in the center of the cube and dots at
the center of each corner sphere connected to form a cube shape. The name under this image reads “Body-centered cubic
structure.” The third image is the same as the second, but only shows the portions of the spheres that lie inside the cube shape.

Atoms in BCC arrangements are much more efficiently packed than in a simple cubic structure, occupying about 68% of the total
volume. Isomorphous metals with a BCC structure include K, Ba, Cr, Mo, W, and Fe at room temperature. (Elements or
compounds that crystallize with the same structure are said to be isomorphous.)
Many other metals, such as aluminum, copper, and lead, crystallize in an arrangement that has a cubic unit cell with atoms at all of
the corners and at the centers of each face, as illustrated in Figure 10.7.7. This arrangement is called a face-centered cubic (FCC)
1
solid. A FCC unit cell contains four atoms: one-eighth of an atom at each of the eight corners (8 × =1 atom from the corners)
8
1
and one-half of an atom on each of the six faces (6 × =3 atoms from the faces). The atoms at the corners touch the atoms in the
2
centers of the adjacent faces along the face diagonals of the cube. Because the atoms are on identical lattice points, they have
identical environments.
Figure 10.7.7 :A face-centered cubic solid has atoms at the corners and, as the name implies, at the centers of the faces of its unit
cells.
Three images are shown. The first image shows a cube with black dots at each corner and red dots in the center of each face of the
cube while the second image is composed of eight spheres that are stacked together to form a cube with six more spheres, one
located on each face of the structure. Dots at the center of each corner sphere are connected to form a cube shape. The name under
this image reads “Face-centered cubic structure.” The third image is the same as the second, but only shows the portions of the
spheres that lie inside the cube shape.
Atoms in an FCC arrangement are packed as closely together as possible, with atoms occupying 74% of the volume. This structure
is also called cubic closest packing (CCP). In CCP, there are three repeating layers of hexagonally arranged atoms. Each atom
contacts six atoms in its own layer, three in the layer above, and three in the layer below. In this arrangement, each atom touches 12
near neighbors, and therefore has a coordination number of 12. The fact that FCC and CCP arrangements are equivalent may not be
immediately obvious, but why they are actually the same structure is illustrated in Figure 10.7.8.
Figure 10.7.8 : A CCP arrangement consists of three repeating layers (ABCABC…) of hexagonally arranged atoms. Atoms in a
CCP structure have a coordination number of 12 because they contact six atoms in their layer, plus three atoms in the layer above
and three atoms in the layer below. By rotating our perspective, we can see that a CCP structure has a unit cell with a face
containing an atom from layer A at one corner, atoms from layer B across a diagonal (at two corners and in the middle of the face),
and an atom from layer C at the remaining corner. This is the same as a face-centered cubic arrangement.
Three images are shown. In the first image, a side view shows a layer of blue spheres, labeled “C” stacked on top of, and sitting in
between the gaps in a second layer that is composed of green spheres, labeled “B,” which are sitting atop a purple layer of spheres
labeled “A.” A label below this image reads “Side view.” The second image shows a top view of the same layers of spheres, where
the top layer is “C,” the second layer is “B” and the lowest layer is “C.” This image is labeled “Top view” and written under this is
the phrase “Cubic closest packed structure.” The third image shows an upper view of the side of a cube composed of two sets of the
repeating layers shown in the other images. The layers are arranged “C, B, A, C, B, A, C” and the phrase written under this image
reads “Rotated view.”
Because closer packing maximizes the overall attractions between atoms and minimizes the total intermolecular energy, the atoms
in most metals pack in this manner. We find two types of closest packing in simple metallic crystalline structures: CCP, which we

have already encountered, and hexagonal closest packing (HCP) shown in Figure 10.7.9. Both consist of repeating layers of
hexagonally arranged atoms. In both types, a second layer (B) is placed on the first layer (A) so that each atom in the second layer
is in contact with three atoms in the first layer. The third layer is positioned in one of two ways. In HCP, atoms in the third layer are
directly above atoms in the first layer (i.e., the third layer is also type A), and the stacking consists of alternating type A and type B
close-packed layers (i.e., ABABAB⋯). In CCP, atoms in the third layer are not above atoms in either of the first two layers (i.e.,
the third layer is type C), and the stacking consists of alternating type A, type B, and type C close-packed layers (i.e.,
ABCABCABC⋯). About two–thirds of all metals crystallize in closest-packed arrays with coordination numbers of 12. Metals
that crystallize in an HCP structure include Cd, Co, Li, Mg, Na, and Zn, and metals that crystallize in a CCP structure include Ag,
Al, Ca, Cu, Ni, Pb, and Pt.
Figure 10.7.9 : In both types of closest packing, atoms are packed as compactly as possible. Hexagonal closest packing consists of
two alternating layers (ABABAB…). Cubic closest packing consists of three alternating layers (ABCABCABC…).
Two images are shown. The first image, labeled “Hexagonal closest packed,” shows seven green spheres arranged in a circular
sheet lying atop another sheet that is the same except the spheres are purple. The second sheet is offset just a bit so that the spheres
of the top sheet lie in the grooves of the second sheet. Two more alternating green and purple layers of spheres lie below the first
pair. The second image shows seven blue spheres, labeled “Layer C,” arranged in a circular sheet laying atop another sheet, labeled
“Layer B” that is the same except the spheres are green. The second sheet is offset just a bit so that the spheres of the top sheet lie
in the grooves of the second sheet. Two more alternating purple and then blue layers of spheres lie below the first pair. The purple
layer is labeled “Layer A” and the phrase written below this image reads “Cubic closest packed.”
 Example 10.7.2: Calculating Atomic Radius and Density for Metals (Part 2)
Calcium crystallizes in a face-centered cubic structure. The edge length of its unit cell is 558.8 pm.
a. What is the atomic radius of Ca in this structure?
b. Calculate the density of Ca.
Solution
(a) In an FCC structure, Ca atoms contact each other across the diagonal of the face, so the length of the diagonal is equal to
four Ca atomic radii (d = 4r).
Two adjacent edges and the diagonal of the face form a right triangle, with the length of each side equal to 558.8 pm and the
length of the hypotenuse equal to four Ca atomic radii:
2 2 2
a +a =d
2 2 2
(558.8 pm) + (558.5 pm) = (4r)

Solving this gives
−−−−−−−−−−−−−−−−−−−−−
2 2
(558.8 pm) + (558.5 pm)
r =√ = 197.6 pmg for a Ca radius.
16
mass
(b) Density is given by density = . The density of calcium can be found by determining the density of its unit cell:
volume
for example, the mass contained within a unit cell divided by the volume of the unit cell. A face-centered Ca unit cell has one-
1 1
eighth of an atom at each of the eight corners (8 × =1 atom) and one-half of an atom on each of the six faces 6× =3
8 2
atoms), for a total of four atoms in the unit cell.
The mass of the unit cell can be found by:
4 Ca atoms 1 mol Ca 40.078 g
−22
1 Ca unit cell × × × = 2.662 × 10 g
23
1 Ca unit cell 6.022 × 10 Ca atoms 1 mol Ca
The volume of a Ca unit cell can be found by:

3 −10 3 −22 3
V =a = (558.8 × 10 cm) = 1.745 × 10 cm
(Note that the edge length was converted from pm to cm to get the usual volume units for density.)
Then, the density of polonium:
−22
2.662 × 10 g 3
Po = = 1.53 g/cm
−22 3
1.745 × 10 cm
 Exercise 10.7.2
Silver crystallizes in an FCC structure. The edge length of its unit cell is 409 pm.
a. What is the atomic radius of Ag in this structure?
b. Calculate the density of Ag.
Answer a
144 pm
Answer b
10.5 g/cm3
In general, a unit cell is defined by the lengths of three axes (a, b, and c) and the angles (α, β, and γ) between them, as illustrated in
Figure 10.7.10. The axes are defined as being the lengths between points in the space lattice. Consequently, unit cell axes join
points with identical environments.
Figure 10.7.10: A unit cell is defined by the lengths of its three axes (a, b, and c) and the angles (α, β, and γ) between the axes.
A cube is shown where each corner has a black dot drawn on it. A circle in the bottom of the cube is composed of three double-
ended arrows. The left top of this circle is labeled “alpha,” the top right is labeled “beta” and the bottom is labeled “gamma.” The
bottom left corner of the cube is labeled “a” while the bottom of the back face is labeled “b” and the top, back, left corner is labeled
“c.”

There are seven different lattice systems, some of which have more than one type of lattice, for a total of fourteen different unit
cells, which have the shapes shown in Figure 10.7.11.
Figure 10.7.11:There are seven different lattice systems and 14 different unit cells.
A table is composed of two columns and eight rows. The header row reads “System / Axes / Angles” and “Unit Cells .” The first
column reads “Cubic, a equals b equals c, alpha equals beta equals gamma equals 90 degrees,” “Tetragonal, a equals b does not
equal c, alpha equals beta equals gamma equals 90 degrees,” “Orthorhombic, a does not equal b does not equal c, alpha equals beta
equals gamma equals 90 degrees,” “Monoclinic, a does not equal b does not equal c, alpha equals gamma equals 90 degrees, beta
does not equal 90 degrees,” “Triclinic, a does not equal b does not equal c, alpha does not equal beta does not equal gamma does
not equal 90 degrees,” “Hexagonal, a equals b does not equal c, alpha equals beta equals 90 degrees, gamma equals 120 degrees,”
“Rhombohedral, a equals b equals c, alpha equals beta equals gamma does not equal 90 degrees.” The second column is composed
of diagrams. The first set of diagrams in the first cell show a cube with spheres at each corner labeled “Simple,” a cube with
spheres in each corner and on each face labeled “Face-centered” and a cube with spheres in each corner and one in the center
labeled “Body-centered.” The second set of diagrams in the second cell show a vertical rectangle with spheres at each corner
labeled “Simple” and a vertical rectangle with spheres in each corner and one in the center labeled “Body-centered.” The third set
of diagrams in the third cell show a vertical rectangle with spheres at each corner labeled “Simple,” a vertical rectangle with
spheres in each corner and one in the center labeled “Body-centered,” a vertical rectangle with spheres in each corner and one on
the top and bottom faces labeled “Base-centered,” and a vertical rectangle with spheres in each corner and one on each face labeled
“Face-centered.” The fourth set of diagrams in the fourth cell show a vertical rectangle with spheres at each corner that is slanted to
one side labeled “Simple” and a vertical rectangle with spheres in each corner that is slanted to one side and has two spheres in the
center is labeled “Body-centered.” The fifth diagrams in the fifth cell show a cube that is slanted with spheres at each corner while
the sixth diagram in the sixth cell shows a pair of hexagonal rings that are connected together to form a six-sided shape with
spheres at each corner. The seventh diagram in the seventh cell shows a rectangle that is slanted with spheres at each corner.

The Structures of Ionic Crystals
Ionic crystals consist of two or more different kinds of ions that usually have different sizes. The packing of these ions into a
crystal structure is more complex than the packing of metal atoms that are the same size. Most monatomic ions behave as charged
spheres, and their attraction for ions of opposite charge is the same in every direction. Consequently, stable structures for ionic
compounds result (1) when ions of one charge are surrounded by as many ions as possible of the opposite charge and (2) when the
cations and anions are in contact with each other. Structures are determined by two principal factors: the relative sizes of the ions
and the ratio of the numbers of positive and negative ions in the compound.
In simple ionic structures, we usually find the anions, which are normally larger than the cations, arranged in a closest-packed
array. (As seen previously, additional electrons attracted to the same nucleus make anions larger and fewer electrons attracted to the
same nucleus make cations smaller when compared to the atoms from which they are formed.) The smaller cations commonly
occupy one of two types of holes (or interstices) remaining between the anions. The smaller of the holes is found between three
anions in one plane and one anion in an adjacent plane. The four anions surrounding this hole are arranged at the corners of a
tetrahedron, so the hole is called a tetrahedral hole. The larger type of hole is found at the center of six anions (three in one layer
and three in an adjacent layer) located at the corners of an octahedron; this is called an octahedral hole. Figure 10.7.12 illustrates
both of these types of holes.
Figure 10.7.12: Cations may occupy two types of holes between anions: octahedral holes or tetrahedral holes.
An image shows a top-view of a layer of blue spheres arranged in a sheet lying atop another sheet that is the same except the
spheres are green. The second sheet is offset just a bit so that the spheres of the top sheet lie in the grooves of the second sheet. A
third sheet composed of purple spheres lies at the bottom. The spaces created between the spheres in each layer are labeled
“Octahedral holes” and “Tetrahedral holes.”
Depending on the relative sizes of the cations and anions, the cations of an ionic compound may occupy tetrahedral or octahedral
holes, as illustrated in Figure 10.7.13. Relatively small cations occupy tetrahedral holes, and larger cations occupy octahedral
holes. If the cations are too large to fit into the octahedral holes, the anions may adopt a more open structure, such as a simple cubic
array. The larger cations can then occupy the larger cubic holes made possible by the more open spacing.
Figure 10.7.13:A cation’s size and the shape of the hole occupied by the compound are directly related.
A diagram of three images is shown. In the first image, eight stacked cubes, with purple spheres at each corner, that make up one
large cube are shown. The bottom left cube is different. It has green spheres at each corner and has four orange and six light purple
spheres located on the faces of the cube. Labels below this structure read “Tetrahedral hole” and “Cation radius is about 22.5 to
41.4 percent of the anion radius. In the second image, eight stacked cubes, with alternating orange and green spheres at each corner,
make up one large cube that is shown. The bottom left cube has darker lines that connect the spheres together. Labels below this
structure read “Octahedral hole” and “Cation radius is about 41.4 to 73.2 percent of the anion radius. In the third image, eight
stacked cubes, with purple spheres at each corner and light purple spheres on their interior faces, make up one large cube that is
shown. Labels below this structure read “Cubic hole” and “Cation radius is about 73.2 to 100 percent of the anion radius.”

There are two tetrahedral holes for each anion in either an HCP or CCP array of anions. A compound that crystallizes in a closest-
packed array of anions with cations in the tetrahedral holes can have a maximum cation:anion ratio of 2:1; all of the tetrahedral
holes are filled at this ratio. Examples include Li2O, Na2O, Li2S, and Na2S. Compounds with a ratio of less than 2:1 may also
crystallize in a closest-packed array of anions with cations in the tetrahedral holes, if the ionic sizes fit. In these compounds,
however, some of the tetrahedral holes remain vacant.
 Example 10.7.3: Occupancy of Tetrahedral Holes
Zinc sulfide is an important industrial source of zinc and is also used as a white pigment in paint. Zinc sulfide crystallizes with
zinc ions occupying one-half of the tetrahedral holes in a closest-packed array of sulfide ions. What is the formula of zinc
sulfide?
Solution
Because there are two tetrahedral holes per anion (sulfide ion) and one-half of these holes are occupied by zinc ions, there must
1
be ×2 , or 1, zinc ion per sulfide ion. Thus, the formula is ZnS.
2
 Exercise 10.7.3: Lithium selenide

Lithium selenide can be described as a closest-packed array of selenide ions with lithium ions in all of the tetrahedral holes.
What it the formula of lithium selenide?
Answer
Li Se
2
The ratio of octahedral holes to anions in either an HCP or CCP structure is 1:1. Thus, compounds with cations in octahedral holes
in a closest-packed array of anions can have a maximum cation:anion ratio of 1:1. In NiO, MnS, NaCl, and KH, for example, all of
the octahedral holes are filled. Ratios of less than 1:1 are observed when some of the octahedral holes remain empty.
 Example 10.7.4: Stoichiometry of Ionic Compounds Sapphire
Aluminum oxide crystallizes with aluminum ions in two-thirds of the octahedral holes in a closest-packed array of oxide ions.
What is the formula of aluminum oxide?
Solution
Because there is one octahedral hole per anion (oxide ion) and only two-thirds of these holes are occupied, the ratio of
2
aluminum to oxygen must be :1, which would give Al 2/3 O . The simplest whole number ratio is 2:3, so the formula is Al2O3.
3
 Exercise 10.7.4
The white pigment titanium oxide crystallizes with titanium ions in one-half of the octahedral holes in a closest-packed array
of oxide ions. What is the formula of titanium oxide?
Answer
TiO
2
In a simple cubic array of anions, there is one cubic hole that can be occupied by a cation for each anion in the array. In CsCl, and
in other compounds with the same structure, all of the cubic holes are occupied. Half of the cubic holes are occupied in SrH2, UO2,
SrCl2, and CaF2.

Different types of ionic compounds often crystallize in the same structure when the relative sizes of their ions and their
stoichiometries (the two principal features that determine structure) are similar.
Unit Cells of Ionic Compounds

Many ionic compounds crystallize with cubic unit cells, and we will use these compounds to describe the general features of ionic
structures. When an ionic compound is composed of cations and anions of similar size in a 1:1 ratio, it typically forms a simple
cubic structure. Cesium chloride, CsCl, (Figure 10.7.14) is an example of this, with Cs+ and Cl− having radii of 174 pm and 181
pm, respectively. We can think of this as chloride ions forming a simple cubic unit cell, with a cesium ion in the center; or as
cesium ions forming a unit cell with a chloride ion in the center; or as simple cubic unit cells formed by Cs+ ions overlapping unit
cells formed by Cl− ions. Cesium ions and chloride ions touch along the body diagonals of the unit cells. One cesium ion and one
chloride ion are present per unit cell, giving the l:l stoichiometry required by the formula for cesium chloride. Note that there is no
lattice point in the center of the cell, and CsCl is not a BCC structure because a cesium ion is not identical to a chloride ion.
Figure 10.7.14: Ionic compounds with similar-sized cations and anions, such as CsCl, usually form a simple cubic structure. They
can be described by unit cells with either cations at the corners or anions at the corners.
Three images are shown. The first image shows a cube with black dots at each corner and a red dot in the center. This cube is
stacked with seven others that are not colored to form a larger cube. The second image is composed of eight spheres that are
grouped together to form a cube with one smaller sphere in the center. The name under this image reads “Body-centered simple
cubic structure.” The third image shows five horizontal layers of purple spheres with layers of smaller green spheres in between.
We have said that the location of lattice points is arbitrary. This is illustrated by an alternate description of the CsCl structure in
which the lattice points are located in the centers of the cesium ions. In this description, the cesium ions are located on the lattice
points at the corners of the cell, and the chloride ion is located at the center of the cell. The two unit cells are different, but they
describe identical structures.
When an ionic compound is composed of a 1:1 ratio of cations and anions that differ significantly in size, it typically crystallizes
with an FCC unit cell, like that shown in Figure 10.7.15. Sodium chloride, NaCl, is an example of this, with Na+ and Cl− having
radii of 102 pm and 181 pm, respectively. We can think of this as chloride ions forming an FCC cell, with sodium ions located in
the octahedral holes in the middle of the cell edges and in the center of the cell. The sodium and chloride ions touch each other
along the cell edges. The unit cell contains four sodium ions and four chloride ions, giving the 1:1 stoichiometry required by the
formula, NaCl.
Figure 10.7.15: Ionic compounds with anions that are much larger than cations, such as NaCl, usually form an FCC structure. They
can be described by FCC unit cells with cations in the octahedral holes.
Three images are shown. The first image shows a cube with black dots at each corner and a red dot in the center. This cube is
stacked with seven others that are not colored to form a larger cube. The second image is composed of eight spheres that are
grouped together to form a cube with one much larger sphere in the center. The name under this image reads “Body-centered
simple cubic structure.” The third image shows seven horizontal layers of alternating purple and green spheres that are slightly
offset with one another and form a large cube.
The cubic form of zinc sulfide, zinc blende, also crystallizes in an FCC unit cell, as illustrated in Figure 10.7.16. This structure
contains sulfide ions on the lattice points of an FCC lattice. (The arrangement of sulfide ions is identical to the arrangement of
chloride ions in sodium chloride.) The radius of a zinc ion is only about 40% of the radius of a sulfide ion, so these small Zn2+ ions
are located in alternating tetrahedral holes, that is, in one half of the tetrahedral holes. There are four zinc ions and four sulfide ions
in the unit cell, giving the empirical formula ZnS.

Figure 10.7.16: ZnS, zinc sulfide (or zinc blende) forms an FCC unit cell with sulfide ions at the lattice points and much smaller
zinc ions occupying half of the tetrahedral holes in the structure.
Two images are shown. The first image shows a cube with black dots at each corner and a red dot in the center of each face of the
cube. This cube is stacked with seven others that are not colored to form a larger cube. The second image is composed of eight
spheres that form the corners of a cube with six other spheres located in the face of the cube. The spheres are connected to one
another by lines. The name under this image reads “Z n S, face-centered unit cell.”
A calcium fluoride unit cell, like that shown in Figure 10.7.17, is also an FCC unit cell, but in this case, the cations are located on
the lattice points; equivalent calcium ions are located on the lattice points of an FCC lattice. All of the tetrahedral sites in the FCC
array of calcium ions are occupied by fluoride ions. There are four calcium ions and eight fluoride ions in a unit cell, giving a
calcium:fluorine ratio of 1:2, as required by the chemical formula, CaF2. Close examination of Figure 10.7.17 will reveal a simple
cubic array of fluoride ions with calcium ions in one half of the cubic holes. The structure cannot be described in terms of a space
lattice of points on the fluoride ions because the fluoride ions do not all have identical environments. The orientation of the four
calcium ions about the fluoride ions differs.
Figure 10.7.17: Calcium fluoride, CaF2, forms an FCC unit cell with calcium ions (green) at the lattice points and fluoride ions
(red) occupying all of the tetrahedral sites between them.
Two images are shown. The first image shows a cube with black dots at each corner and a red dot in the center of each face of the
cube. This cube is stacked with seven others that are not colored to form a larger cube. The second image is composed of eight
small green spheres that form the corners of a cube with six other small green spheres located in the faces of the cube. Eight larger
green spheres are spaced inside the cube and all of the spheres are connect to one another by lines. The name under this image
reads “C a F, subscript 2, face-centered unit cell.”
Calculation of Ionic Radii

If we know the edge length of a unit cell of an ionic compound and the position of the ions in the cell, we can calculate ionic radii
for the ions in the compound if we make assumptions about individual ionic shapes and contacts.
 Example 10.7.5: Calculation of Ionic Radii
The edge length of the unit cell of LiCl (NaCl-like structure, FCC) is 0.514 nm or 5.14 Å. Assuming that the lithium ion is
small enough so that the chloride ions are in contact, calculate the ionic radius for the chloride ion. Note: The length unit
angstrom, Å, is often used to represent atomic-scale dimensions and is equivalent to 10−10 m.
Solution
On the face of a LiCl unit cell, chloride ions contact each other across the diagonal of the face:

Drawing a right triangle on the face of the unit cell, we see that the length of the diagonal is equal to four chloride radii (one
radius from each corner chloride and one diameter—which equals two radii—from the chloride ion in the center of the face),
so d = 4r . From the Pythagorean theorem, we have:
2 2 2
a +a =d
which yields:
2 2 2 2
(0.514 nm) + (0.514 nm) = (4r) = 16 r
Solving this gives:

−−−−−−−−−−−−−−−−−−−−−
2 2
(0.514 nm) + (0.514 nm)
r =√ = 0.182 nm (1.82 Å) f or a −
Cl radius.
16
 Exercise 10.7.6
The edge length of the unit cell of KCl (NaCl-like structure, FCC) is 6.28 Å. Assuming anion-cation contact along the cell
edge, calculate the radius of the potassium ion. The radius of the chloride ion is 1.82 Å.
Answer
The radius of the potassium ion is 1.33 Å.
It is important to realize that values for ionic radii calculated from the edge lengths of unit cells depend on numerous assumptions,
such as a perfect spherical shape for ions, which are approximations at best. Hence, such calculated values are themselves
approximate and comparisons cannot be pushed too far. Nevertheless, this method has proved useful for calculating ionic radii from
experimental measurements such as X-ray crystallographic determinations.
X-Ray Crystallography
The size of the unit cell and the arrangement of atoms in a crystal may be determined from measurements of the diffraction of X-
rays by the crystal, termed X-ray crystallography. Diffraction is the change in the direction of travel experienced by an
electromagnetic wave when it encounters a physical barrier whose dimensions are comparable to those of the wavelength of the
light. X-rays are electromagnetic radiation with wavelengths about as long as the distance between neighboring atoms in crystals
(on the order of a few Å).
When a beam of monochromatic X-rays strikes a crystal, its rays are scattered in all directions by the atoms within the crystal.
When scattered waves traveling in the same direction encounter one another, they undergo interference, a process by which the
waves combine to yield either an increase or a decrease in amplitude (intensity) depending upon the extent to which the combining
waves’ maxima are separated (Figure 10.7.18).

Figure 10.7.18: Light waves occupying the same space experience interference, combining to yield waves of greater (a) or lesser
(b) intensity, depending upon the separation of their maxima and minima.
A pair of images is shown that has four sections. In the first section, two sinusoidal waves are shown, one drawn above the other,
and a section from the top of one curve to the top of the next curve is labeled “lambda.” The curves align with one another. The
phrase below this reads “Constructive interference.” A right facing arrow leads from the first section to the second, which shows
one larger sinusoidal curve that has higher and lower peaks and troughs. A section from the top of one curve to the top of the next
curve is labeled “lambda” and the phrase below this reads “Maxima and minima reinforce.” In the second section, two sinusoidal
waves are shown, one drawn above the other, and a section from the top of one curve to the top of the next curve is labeled
“lambda.” The curves do not align with one another. The phrase below this reads “Destructive interference.” A right facing arrow
leads from the first section to the second, which shows one flat line. The phrase below this reads “Maxima and minima cancel.”
When X-rays of a certain wavelength, λ, are scattered by atoms in adjacent crystal planes separated by a distance, d, they may
undergo constructive interference when the difference between the distances traveled by the two waves prior to their combination is
an integer factor, n, of the wavelength. This condition is satisfied when the angle of the diffracted beam, θ, is related to the
wavelength and interatomic distance by the equation:
nλ = 2d sin θ (10.7.1)
This relation is known as the Bragg equation in honor of W. H. Bragg, the English physicist who first explained this phenomenon.
Figure 10.7.18 illustrates two examples of diffracted waves from the same two crystal planes. The figure on the left depicts waves
diffracted at the Bragg angle, resulting in constructive interference, while that on the right shows diffraction and a different angle
that does not satisfy the Bragg condition, resulting in destructive interference.
Figure 10.7.19: The diffraction of X-rays scattered by the atoms within a crystal permits the determination of the distance between
the atoms. The top image depicts constructive interference between two scattered waves and a resultant diffracted wave of high
intensity. The bottom image depicts destructive interference and a low intensity diffracted wave.
Two similar figures are shown. The first figure, labeled “Constructive Interference,” shows two horizontal rows of seven black dots
with a line passing through them. The fourth dots of each row have a vertical line connecting them. The distance between these
rows is labeled “d.” A beam labeled “Incident beam” descends at an angle labeled “theta” until it hits the line connecting the fourth
dots, after which a diffracted beam ascends at the same angle “theta.” A dotted line is drawn across the diffracted beam. The second
figure, labeled “Destructive interference,” is very similar, except that the angles “theta” are far more acute, making the slopes of the
beams more shallow.

An X-ray diffractometer, such as the one illustrated in Figure 10.7.20, may be used to measure the angles at which X-rays are
diffracted when interacting with a crystal as described earlier. From such measurements, the Bragg equation may be used to
compute distances between atoms as demonstrated in the following example exercise.
Figure 10.7.20: (a) In a diffractometer, a beam of X-rays strikes a crystalline material, producing (b) an X-ray diffraction pattern
that can be analyzed to determine the crystal structure.
A diagram, labeled “a” shows a cube on the left with a channel bored into its right side labeled “X dash ray source.” A beam is
leaving from this channel and traveling in a horizontal line toward an oval-shaped, short tube, labeled “Collimator to focus beam”
and “X dash ray diffraction,” where it passes through a cube labeled “Crystalline material” and scatters onto a vertical sheet labeled
“Imaging surface.” A second diagram, labeled “b,” shows a square sheet with a large dot in the center labeled “X dash ray beam,”
that is surrounded by smaller dots arranged in rings and labeled “Diffracted X dash rays.”
 Example 10.7.6: Using the Bragg Equation
In a diffractometer, X-rays with a wavelength of 0.1315 nm were used to produce a diffraction pattern for copper. The first
order diffraction (n = 1) occurred at an angle θ = 25.25°. Determine the spacing between the diffracting planes in copper.
Solution
The distance between the planes is found by solving the Bragg equation (Equation 10.7.1) for d.
This gives
nλ 1(0.1315 nm)
d = = = 0.154 nm
2 sin θ 2 sin(25.25°)
 Exercise 10.7.6
A crystal with spacing between planes equal to 0.394 nm diffracts X-rays with a wavelength of 0.147 nm. What is the angle for
the first order diffraction?
Answer
21.9°
 X-ray Crystallographer Rosalind Franklin
The discovery of the structure of DNA in 1953 by Francis Crick and James Watson is one of the great achievements in the
history of science. They were awarded the 1962 Nobel Prize in Physiology or Medicine, along with Maurice Wilkins, who
provided experimental proof of DNA’s structure. British chemist Rosalind Franklin made invaluable contributions to this
monumental achievement through her work in measuring X-ray diffraction images of DNA. Early in her career, Franklin’s
research on the structure of coals proved helpful to the British war effort. After shifting her focus to biological systems in the
early 1950s, Franklin and doctoral student Raymond Gosling discovered that DNA consists of two forms: a long, thin fiber
formed when wet (type “B”) and a short, wide fiber formed when dried (type “A”). Her X-ray diffraction images of DNA
provided the crucial information that allowed Watson and Crick to confirm that DNA forms a double helix, and to determine

details of its size and structure. Franklin also conducted pioneering research on viruses and the RNA that contains their genetic
information, uncovering new information that radically changed the body of knowledge in the field. After developing ovarian
cancer, Franklin continued to work until her death in 1958 at age 37. Among many posthumous recognitions of her work, the
Chicago Medical School of Finch University of Health Sciences changed its name to the Rosalind Franklin University of
Medicine and Science in 2004, and adopted an image of her famous X-ray diffraction image of DNA as its official university
logo.
Figure 10.7.7 .This illustration shows an X-ray diffraction image similar to the one Franklin found in her research. (credit:
National Institutes of Health)

The structures of crystalline metals and simple ionic compounds can be described in terms of packing of spheres. Metal atoms can
pack in hexagonal closest-packed structures, cubic closest-packed structures, body-centered structures, and simple cubic structures.
The anions in simple ionic structures commonly adopt one of these structures, and the cations occupy the spaces remaining
between the anions. Small cations usually occupy tetrahedral holes in a closest-packed array of anions. Larger cations usually
occupy octahedral holes. Still larger cations can occupy cubic holes in a simple cubic array of anions. The structure of a solid can
be described by indicating the size and shape of a unit cell and the contents of the cell. The type of structure and dimensions of the
unit cell can be determined by X-ray diffraction measurements.
Glossary
body-centered cubic (BCC) solid
crystalline structure that has a cubic unit cell with lattice points at the corners and in the center of the cell
body-centered cubic unit cell

simplest repeating unit of a body-centered cubic crystal; it is a cube containing lattice points at each corner and in the center of
the cube
Bragg equation
equation that relates the angles at which X-rays are diffracted by the atoms within a crystal
coordination number
number of atoms closest to any given atom in a crystal or to the central metal atom in a complex
cubic closest packing (CCP)

crystalline structure in which planes of closely packed atoms or ions are stacked as a series of three alternating layers of
different relative orientations (ABC)
diffraction
redirection of electromagnetic radiation that occurs when it encounters a physical barrier of appropriate dimensions

face-centered cubic (FCC) solid
crystalline structure consisting of a cubic unit cell with lattice points on the corners and in the center of each face
face-centered cubic unit cell

simplest repeating unit of a face-centered cubic crystal; it is a cube containing lattice points at each corner and in the center of
each face
hexagonal closest packing (HCP)

crystalline structure in which close packed layers of atoms or ions are stacked as a series of two alternating layers of different
relative orientations (AB)
hole
(also, interstice) space between atoms within a crystal
isomorphous
possessing the same crystalline structure
octahedral hole
open space in a crystal at the center of six particles located at the corners of an octahedron
simple cubic unit cell

(also, primitive cubic unit cell) unit cell in the simple cubic structure
simple cubic structure

crystalline structure with a cubic unit cell with lattice points only at the corners
space lattice
all points within a crystal that have identical environments
tetrahedral hole
tetrahedral space formed by four atoms or ions in a crystal
unit cell
smallest portion of a space lattice that is repeated in three dimensions to form the entire lattice
X-ray crystallography
experimental technique for determining distances between atoms in a crystal by measuring the angles at which X-rays are
diffracted when passing through the crystal
Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley (Stephen
F. Austin State University) with contributing authors. Textbook content produced by OpenStax College is licensed under a Creative
Commons Attribution License 4.0 license. Download for free at http://cnx.org/contents/[email protected]).
This page titled 10.7: Lattice Structures in Crystalline Solids is shared under a CC BY license and was authored, remixed, and/or curated by
OpenStax.
10.6: Lattice Structures in Crystalline Solids is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

Q10.1.1
In terms of their bulk properties, how do liquids and solids differ? How are they similar?
S10.1.1
Liquids and solids are similar in that they are matter composed of atoms, ions, or molecules. They are incompressible and have
similar densities that are both much larger than those of gases. They are different in that liquids have no fixed shape, and solids are
rigid.
Q10.1.2
In terms of the kinetic molecular theory, in what ways are liquids similar to solids? In what ways are liquids different from solids?
Q10.1.3
In terms of the kinetic molecular theory, in what ways are liquids similar to gases? In what ways are liquids different from gases?
S10.1.3
They are similar in that the atoms or molecules are free to move from one position to another. They differ in that the particles of a
liquid are confined to the shape of the vessel in which they are placed. In contrast, a gas will expand without limit to fill the space
into which it is placed.
Q10.1.4
Explain why liquids assume the shape of any container into which they are poured, whereas solids are rigid and retain their shape.
Q10.1.5
What is the evidence that all neutral atoms and molecules exert attractive forces on each other?
S10.1.5
All atoms and molecules will condense into a liquid or solid in which the attractive forces exceed the kinetic energy of the
molecules, at sufficiently low temperature.
Q10.1.6
Open the PhET States of Matter Simulation to answer the following questions:
a. Select the Solid, Liquid, Gas tab. Explore by selecting different substances, heating and cooling the systems, and changing the
state. What similarities do you notice between the four substances for each phase (solid, liquid, gas)? What differences do you
notice?
b. For each substance, select each of the states and record the given temperatures. How do the given temperatures for each state
correlate with the strengths of their intermolecular attractions? Explain.
c. Select the Interaction Potential tab, and use the default neon atoms. Move the Ne atom on the right and observe how the
potential energy changes. Select the Total Force button, and move the Ne atom as before. When is the total force on each atom
attractive and large enough to matter? Then select the Component Forces button, and move the Ne atom. When do the attractive
(van der Waals) and repulsive (electron overlap) forces balance? How does this relate to the potential energy versus the distance
between atoms graph? Explain.
Q10.1.7
Define the following and give an example of each:
a. dispersion force
b. dipole-dipole attraction
c. hydrogen bond

S10.1.7
a. Dispersion forces occur as an atom develops a temporary dipole moment when its electrons are distributed asymmetrically
about the nucleus. This structure is more prevalent in large atoms such as argon or radon. A second atom can then be distorted
by the appearance of the dipole in the first atom. The electrons of the second atom are attracted toward the positive end of the
first atom, which sets up a dipole in the second atom. The net result is rapidly fluctuating, temporary dipoles that attract one
another (example: Ar).
b. A dipole-dipole attraction is a force that results from an electrostatic attraction of the positive end of one polar molecule for the
negative end of another polar molecule (example: ICI molecules attract one another by dipole-dipole interaction).
c. Hydrogen bonds form whenever a hydrogen atom is bonded to one of the more electronegative atoms, such as a fluorine,
oxygen, nitrogen, or chlorine atom. The electrostatic attraction between the partially positive hydrogen atom in one molecule
and the partially negative atom in another molecule gives rise to a strong dipole-dipole interaction called a hydrogen bond
(example: HF ⋯ HF).
Q10.1.8
The types of intermolecular forces in a substance are identical whether it is a solid, a liquid, or a gas. Why then does a substance
change phase from a gas to a liquid or to a solid?
Q10.1.9
Why do the boiling points of the noble gases increase in the order He < Ne < Ar < Kr < Xe?
S10.1.9
The London forces typically increase as the number of electrons increase.
Q10.1.10
Neon and HF have approximately the same molecular masses.
a. Explain why the boiling points of Neon and HF differ.
b. Compare the change in the boiling points of Ne, Ar, Kr, and Xe with the change of the boiling points of HF, HCl, HBr, and HI,
and explain the difference between the changes with increasing atomic or molecular mass.
Q10.1.11
Arrange each of the following sets of compounds in order of increasing boiling point temperature:
a. HCl, H2O, SiH4
b. F2, Cl2, Br2
c. CH4, C2H6, C3H8
d. O2, NO, N2
S10.1.11
(a) SiH4 < HCl < H2O; (b) F2 < Cl2 < Br2; (c) CH4 < C2H6 < C3H8; (d) N2 < O2 < NO
Q10.1.12
The molecular mass of butanol, C4H9OH, is 74.14; that of ethylene glycol, CH2(OH)CH2OH, is 62.08, yet their boiling points are
117.2 °C and 174 °C, respectively. Explain the reason for the difference.
Q10.1.13
On the basis of intermolecular attractions, explain the differences in the boiling points of n–butane (−1 °C) and chloroethane (12
°C), which have similar molar masses.
S10.1.13
Only rather small dipole-dipole interactions from C-H bonds are available to hold n-butane in the liquid state. Chloroethane,
however, has rather large dipole interactions because of the Cl-C bond; the interaction is therefore stronger, leading to a higher
boiling point.

Q10.1.14
On the basis of dipole moments and/or hydrogen bonding, explain in a qualitative way the differences in the boiling points of
acetone (56.2 °C) and 1-propanol (97.4 °C), which have similar molar masses.
Q10.1.15
The melting point of H2O(s) is 0 °C. Would you expect the melting point of H2S(s) to be −85 °C, 0 °C, or 185 °C? Explain your
answer.
S10.1.15
−85 °C. Water has stronger hydrogen bonds so it melts at a higher temperature.
Q10.1.16
Silane (SiH4), phosphine (PH3), and hydrogen sulfide (H2S) melt at −185 °C, −133 °C, and −85 °C, respectively. What does this
suggest about the polar character and intermolecular attractions of the three compounds?
Q10.1.17
Explain why a hydrogen bond between two water molecules is weaker than a hydrogen bond between two hydrogen fluoride
molecules.
S10.1.17
The hydrogen bond between two hydrogen fluoride molecules is stronger than that between two water molecules because the
electronegativity of F is greater than that of O. Consequently, the partial negative charge on F is greater than that on O. The
hydrogen bond between the partially positive H and the larger partially negative F will be stronger than that formed between H and
O.
Q10.1.18
Under certain conditions, molecules of acetic acid, CH3COOH, form “dimers,” pairs of acetic acid molecules held together by
strong intermolecular attractions:
Draw a dimer of acetic acid, showing how two CH3COOH molecules are held together, and stating the type of IMF that is
responsible.
Q10.1.19
Proteins are chains of amino acids that can form in a variety of arrangements, one of which is a helix. What kind of IMF is
responsible for holding the protein strand in this shape? On the protein image, show the locations of the IMFs that hold the protein
together:
S10.1.19
H-bonding is the principle IMF holding the DNA strands together. The H-bonding is between the N − H and C = O .
Q10.1.20
The density of liquid NH3 is 0.64 g/mL; the density of gaseous NH3 at STP is 0.0007 g/mL. Explain the difference between the
densities of these two phases.

Q10.1.21
Identify the intermolecular forces present in the following solids:
a. CH3CH2OH
b. CH3CH2CH3
c. CH3CH2Cl
S10.1.21
(a) hydrogen bonding and dispersion forces; (b) dispersion forces; (c) dipole-dipole attraction and dispersion forces

Q10.2.1
The test tubes shown here contain equal amounts of the specified motor oils. Identical metal spheres were dropped at the same time
into each of the tubes, and a brief moment later, the spheres had fallen to the heights indicated in the illustration. Rank the motor
oils in order of increasing viscosity, and explain your reasoning:
Q10.2.2
Although steel is denser than water, a steel needle or paper clip placed carefully lengthwise on the surface of still water can be
made to float. Explain at a molecular level how this is possible:
(credit: Cory Zanker)
S10.2.2
The water molecules have strong intermolecular forces of hydrogen bonding. The water molecules are thus attracted strongly to
one another and exhibit a relatively large surface tension, forming a type of “skin” at its surface. This skin can support a bug or
paper clip if gently placed on the water.
Q10.2.3
The surface tension and viscosity values for diethyl ether, acetone, ethanol, and ethylene glycol are shown here.

a. Explain their differences in viscosity in terms of the size and shape of their molecules and their IMFs.
b. Explain their differences in surface tension in terms of the size and shape of their molecules and their IMFs:
Q10.2.4
You may have heard someone use the figure of speech “slower than molasses in winter” to describe a process that occurs slowly.
Explain why this is an apt idiom, using concepts of molecular size and shape, molecular interactions, and the effect of changing
temperature.
S10.2.4
Temperature has an effect on intermolecular forces: the higher the temperature, the greater the kinetic energies of the molecules and
the greater the extent to which their intermolecular forces are overcome, and so the more fluid (less viscous) the liquid; the lower
the temperature, the lesser the intermolecular forces are overcome, and so the less viscous the liquid.
Q10.2.5
It is often recommended that you let your car engine run idle to warm up before driving, especially on cold winter days. While the
benefit of prolonged idling is dubious, it is certainly true that a warm engine is more fuel efficient than a cold one. Explain the
reason for this.
Q10.2.6
The surface tension and viscosity of water at several different temperatures are given in this table.
Water Surface Tension (mN/m) Viscosity (mPa s)
0 °C 75.6 1.79
20 °C 72.8 1.00
60 °C 66.2 0.47
100 °C 58.9 0.28
a. As temperature increases, what happens to the surface tension of water? Explain why this occurs, in terms of molecular
interactions and the effect of changing temperature.
b. As temperature increases, what happens to the viscosity of water? Explain why this occurs, in terms of molecular interactions
and the effect of changing temperature.
S10.2.6
(a) As the water reaches higher temperatures, the increased kinetic energies of its molecules are more effective in overcoming
hydrogen bonding, and so its surface tension decreases. Surface tension and intermolecular forces are directly related. (b) The same
trend in viscosity is seen as in surface tension, and for the same reason.
Q10.2.7
At 25 °C, how high will water rise in a glass capillary tube with an inner diameter of 0.63 mm? Refer to Example for the required
information.

Q10.2.8
Water rises in a glass capillary tube to a height of 17 cm. What is the diameter of the capillary tube?
S10.2.8
9.5 × 10−5 m

Q10.3.1
Heat is added to boiling water. Explain why the temperature of the boiling water does not change. What does change?
Q10.3.2
Heat is added to ice at 0 °C. Explain why the temperature of the ice does not change. What does change?
S10.3.2
The heat is absorbed by the ice, providing the energy required to partially overcome intermolecular attractive forces in the solid and
causing a phase transition to liquid water. The solution remains at 0 °C until all the ice is melted. Only the amount of water existing
as ice changes until the ice disappears. Then the temperature of the water can rise.
Q10.3.3
What feature characterizes the dynamic equilibrium between a liquid and its vapor in a closed container?
Q10.3.4
Identify two common observations indicating some liquids have sufficient vapor pressures to noticeably evaporate?
S10.3.4
We can see the amount of liquid in an open container decrease and we can smell the vapor of some liquids.
Q10.3.5
Identify two common observations indicating some solids, such as dry ice and mothballs, have vapor pressures sufficient to
sublime?
Q10.3.6
What is the relationship between the intermolecular forces in a liquid and its vapor pressure?
S10.3.7
The vapor pressure of a liquid decreases as the strength of its intermolecular forces increases.
Q10.3.7
What is the relationship between the intermolecular forces in a solid and its melting temperature?
Q10.3.8
Why does spilled gasoline evaporate more rapidly on a hot day than on a cold day?
S10.3.8
As the temperature increases, the average kinetic energy of the molecules of gasoline increases and so a greater fraction of
molecules have sufficient energy to escape from the liquid than at lower temperatures.
Q10.3.9
Carbon tetrachloride, CCl4, was once used as a dry cleaning solvent, but is no longer used because it is carcinogenic. At 57.8 °C,
the vapor pressure of CCl4 is 54.0 kPa, and its enthalpy of vaporization is 33.05 kJ/mol. Use this information to estimate the normal
boiling point for CCl4.

Q10.3.10
When is the boiling point of a liquid equal to its normal boiling point?
S10.3.10
When the pressure of gas above the liquid is exactly 1 atm
Q10.3.11
How does the boiling of a liquid differ from its evaporation?
Q10.3.12
Use the information in Figure to estimate the boiling point of water in Denver when the atmospheric pressure is 83.3 kPa.
S10.3.12
approximately 95 °C
Q10.3.13
A syringe at a temperature of 20 °C is filled with liquid ether in such a way that there is no space for any vapor. If the temperature
is kept constant and the plunger is withdrawn to create a volume that can be occupied by vapor, what would be the approximate
pressure of the vapor produced?
Q10.3.14
Explain the following observations:
a. It takes longer to cook an egg in Ft. Davis, Texas (altitude, 5000 feet above sea level) than it does in Boston (at sea level).
b. Perspiring is a mechanism for cooling the body.
S10.3.14
(a) At 5000 feet, the atmospheric pressure is lower than at sea level, and water will therefore boil at a lower temperature. This
lower temperature will cause the physical and chemical changes involved in cooking the egg to proceed more slowly, and a longer
time is required to fully cook the egg. (b) As long as the air surrounding the body contains less water vapor than the maximum that
air can hold at that temperature, perspiration will evaporate, thereby cooling the body by removing the heat of vaporization
required to vaporize the water.
Q10.3.15
The enthalpy of vaporization of water is larger than its enthalpy of fusion. Explain why.
Q10.3.16
Explain why the molar enthalpies of vaporization of the following substances increase in the order CH4 < C2H6 < C3H8, even
though all three substances experience the same dispersion forces when in the liquid state.
S10.3.16
Dispersion forces increase with molecular mass or size. As the number of atoms composing the molecules in this homologous
series increases, so does the extent of intermolecular attraction via dispersion forces and, consequently, the energy required to
overcome these forces and vaporize the liquids.
Q10.3.17
Explain why the enthalpies of vaporization of the following substances increase in the order CH4 < NH3 < H2O, even though all
three substances have approximately the same molar mass.
Q10.3.18
The enthalpy of vaporization of CO2(l) is 9.8 kJ/mol. Would you expect the enthalpy of vaporization of CS2(l) to be 28 kJ/mol, 9.8
kJ/mol, or −8.4 kJ/mol? Discuss the plausibility of each of these answers.

S10.3.18
The boiling point of CS2 is higher than that of CO2 partially because of the higher molecular weight of CS2; consequently, the
attractive forces are stronger in CS2. It would be expected, therefore, that the heat of vaporization would be greater than that of 9.8
kJ/mol for CO2. A value of 28 kJ/mol would seem reasonable. A value of −8.4 kJ/mol would indicate a release of energy upon
vaporization, which is clearly implausible.
Q10.3.19
The hydrogen fluoride molecule, HF, is more polar than a water molecule, H2O (for example, has a greater dipole moment), yet the
molar enthalpy of vaporization for liquid hydrogen fluoride is lesser than that for water. Explain.
Q10.3.20
Ethyl chloride (boiling point, 13 °C) is used as a local anesthetic. When the liquid is sprayed on the skin, it cools the skin enough to
freeze and numb it. Explain the cooling effect of liquid ethyl chloride.
S10.3.20
The thermal energy (heat) needed to evaporate the liquid is removed from the skin.
Q10.3.21
Which contains the compounds listed correctly in order of increasing boiling points?
a. N2 < CS2 < H2O < KCl
b. H2O < N2 < CS2 < KCl
c. N2 < KCl < CS2 < H2O
d. CS2 < N2 < KCl < H2O
e. KCl < H2O < CS2 < N2
Q10.3.22
How much heat is required to convert 422 g of liquid H2O at 23.5 °C into steam at 150 °C?
S10.3.22
1130 kJ
Q10.3.22
Evaporation of sweat requires energy and thus take excess heat away from the body. Some of the water that you drink may
eventually be converted into sweat and evaporate. If you drink a 20-ounce bottle of water that had been in the refrigerator at 3.8 °C,
how much heat is needed to convert all of that water into sweat and then to vapor?? (Note: Your body temperature is 36.6 °C. For
the purpose of solving this problem, assume that the thermal properties of sweat are the same as for water.)
Q10.3.24
Titanium tetrachloride, TiCl4, has a melting point of −23.2 °C and has a ΔH fusion = 9.37 kJ/mol.
a. How much energy is required to melt 263.1 g TiCl4?
b. For TiCl4, which will likely have the larger magnitude: ΔH fusion or ΔH vaporization? Explain your reasoning.
S10.3.24
(a) 13.0 kJ; (b) It is likely that the heat of vaporization will have a larger magnitude since in the case of vaporization the
intermolecular interactions have to be completely overcome, while melting weakens or destroys only some of them.

Q10.4.1
From the phase diagram for water, determine the state of water at:
a. 35 °C and 85 kPa
b. −15 °C and 40 kPa

c. −15 °C and 0.1 kPa
d. 75 °C and 3 kPa
e. 40 °C and 0.1 kPa
f. 60 °C and 50 kPa
Q10.4.2
What phase changes will take place when water is subjected to varying pressure at a constant temperature of 0.005 °C? At 40 °C?
At −40 °C?
S10.4.2
At low pressures and 0.005 °C, the water is a gas. As the pressure increases to 4.6 torr, the water becomes a solid; as the pressure
increases still more, it becomes a liquid. At 40 °C, water at low pressure is a vapor; at pressures higher than about 75 torr, it
converts into a liquid. At −40 °C, water goes from a gas to a solid as the pressure increases above very low values.
Q10.4.3
Pressure cookers allow food to cook faster because the higher pressure inside the pressure cooker increases the boiling temperature
of water. A particular pressure cooker has a safety valve that is set to vent steam if the pressure exceeds 3.4 atm. What is the
approximate maximum temperature that can be reached inside this pressure cooker? Explain your reasoning.
Q10.4.4
From the phase diagram for carbon dioxide, determine the state of CO2 at:
a. 20 °C and 1000 kPa
b. 10 °C and 2000 kPa
c. 10 °C and 100 kPa
d. −40 °C and 500 kPa
e. −80 °C and 1500 kPa
f. −80 °C and 10 kPa
The pressure and temperature axes on this phase diagram of carbon dioxide are not drawn to constant scale in order to illustrate
several important properties.

S10.4.4
(a) liquid; (b) solid; (c) gas; (d) gas; (e) gas; (f) gas
Q10.4.5
Determine the phase changes that carbon dioxide undergoes as the pressure changes if the temperature is held at −50 °C? If the
temperature is held at −40 °C? At 20 °C?
The pressure and temperature axes on this phase diagram of carbon dioxide are not drawn to constant scale in order to illustrate
several important properties.
Q10.4.6
Consider a cylinder containing a mixture of liquid carbon dioxide in equilibrium with gaseous carbon dioxide at an initial pressure
of 65 atm and a temperature of 20 °C. Sketch a plot depicting the change in the cylinder pressure with time as gaseous carbon
dioxide is released at constant temperature.
S10.4.6
Q10.4.7
Dry ice, CO2(s), does not melt at atmospheric pressure. It sublimes at a temperature of −78 °C. What is the lowest pressure at
which CO2(s) will melt to give CO2(l)? At approximately what temperature will this occur? (See Figure for the phase diagram.)

S10.4.7
Dry ice, CO2(s), will melt to give CO2(l) at 5.11 atm at −56.6 °C, the triple point of carbon dioxide.
Q10.4.8
If a severe storm results in the loss of electricity, it may be necessary to use a clothesline to dry laundry. In many parts of the
country in the dead of winter, the clothes will quickly freeze when they are hung on the line. If it does not snow, will they dry
anyway? Explain your answer.
S10.4.8
Yes, ice will sublime, although it may take it several days. Ice has a small vapor pressure, and some ice molecules form gas and
escape from the ice crystals. As time passes, more and more solid converts to gas until eventually the clothes are dry.
Q10.4.9
Is it possible to liquefy nitrogen at room temperature (about 25 °C)? Is it possible to liquefy sulfur dioxide at room temperature?
Explain your answers.
Q10.4.10
Elemental carbon has one gas phase, one liquid phase, and three different solid phases, as shown in the phase diagram:
a. On the phase diagram, label the gas and liquid regions.

b. Graphite is the most stable phase of carbon at normal conditions. On the phase diagram, label the graphite phase.
c. If graphite at normal conditions is heated to 2500 K while the pressure is increased to 1010 Pa, it is converted into diamond.
Label the diamond phase.
d. Circle each triple point on the phase diagram.
e. In what phase does carbon exist at 5000 K and 108 Pa?
f. If the temperature of a sample of carbon increases from 3000 K to 5000 K at a constant pressure of 106 Pa, which phase
transition occurs, if any?

Q10.5.1
What types of liquids typically form amorphous solids?
S10.5.1
Amorphous solids lack an ordered internal structure. Liquid materials that contain large, cumbersome molecules that cannot move
readily into ordered positions generally form such solids.

Q10.5.2
At very low temperatures oxygen, O2, freezes and forms a crystalline solid. Which best describes these crystals?
a. ionic
b. covalent network
c. metallic
d. amorphous
e. molecular crystals
S10.5.3
(e) molecular crystals
Q10.5.4
As it cools, olive oil slowly solidifies and forms a solid over a range of temperatures. Which best describes the solid?
a. ionic
b. covalent network
c. metallic
d. amorphous
e. molecular crystals
S10.5.4
(d) amorphous
Q10.5.5
Explain why ice, which is a crystalline solid, has a melting temperature of 0 °C, whereas butter, which is an amorphous solid,
softens over a range of temperatures.
S10.5.6
Ice has a crystalline structure stabilized by hydrogen bonding. These intermolecular forces are of comparable strength and thus
require the same amount of energy to overcome. As a result, ice melts at a single temperature and not over a range of temperatures.
The various, very large molecules that compose butter experience varied van der Waals attractions of various strengths that are
overcome at various temperatures, and so the melting process occurs over a wide temperature range.
Q10.5.7
Identify the type of crystalline solid (metallic, network covalent, ionic, or molecular) formed by each of the following substances:
a. SiO2
b. KCl
c. Cu
d. CO2
e. C (diamond)
f. BaSO4
g. NH3
h. NH4F
i. C2H5OH
S10.5.7
(a) SiO2, covalent network; (b) KCl, ionic; (c) Cu, metallic; (d) CO, molecular; (e) C (diamond), covalent network; (f) BaSO4,
ionic; (g) NH3, molecular; (h) NH4F, ionic; (i) C2H5OH, molecular
Q10.5.8
Identify the type of crystalline solid (metallic, network covalent, ionic, or molecular) formed by each of the following substances:
a. CaCl2
b. SiC

c. N2
d. Fe
e. C (graphite)
f. CH3CH2CH2CH3
g. HCl
h. NH4NO3
i. K3PO4
S10.5.8
(a) CaCl2, ionic; (b) SiC, covalent network; (c) N2, molecular; (d) Fe, metallic; (e) C (graphite), covalent network; (f)
CH3CH2CH2CH3, molecular; (g) HCl, molecular; (h) NH4NO3, ionic; (i) K3PO4, ionic
Q10.5.9
Classify each substance in the table as either a metallic, ionic, molecular, or covalent network solid:
Substance Appearance Melting Point Electrical Conductivity Solubility in Water
X lustrous, malleable 1500 °C high insoluble
Y soft, yellow 113 °C none insoluble
Z hard, white 800 °C only if melted/dissolved soluble
S10.5.9
X = metallic; Y = covalent network; Z = ionic
Q10.5.10
Classify each substance in the table as either a metallic, ionic, molecular, or covalent network solid:
Substance Appearance Melting Point Electrical Conductivity Solubility in Water
X brittle, white 800 °C only if melted/dissolved soluble
Y shiny, malleable 1100 °C high insoluble
Z hard, colorless 3550 °C none insoluble
S10.5.10
X = ionic; Y = metallic; Z = covalent network
Q10.5.11
Identify the following substances as ionic, metallic, covalent network, or molecular solids:
Substance A is malleable, ductile, conducts electricity well, and has a melting point of 1135 °C. Substance B is brittle, does not
conduct electricity as a solid but does when molten, and has a melting point of 2072 °C. Substance C is very hard, does not conduct
electricity, and has a melting point of 3440 °C. Substance D is soft, does not conduct electricity, and has a melting point of 185 °C.
S10.5.11
A = metallic; B = ionic; C = covalent network; D = molecular
Q10.5.12
Substance A is shiny, conducts electricity well, and melts at 975 °C. Substance A is likely a(n):
a. ionic solid
b. metallic solid
c. molecular solid
d. covalent network solid

S10.5.12
(b) metallic solid
Q10.5.13
Substance B is hard, does not conduct electricity, and melts at 1200 °C. Substance B is likely a(n):
a. ionic solid
b. metallic solid
c. molecular solid
d. covalent network solid
S10.5.13
(d) covalent network solid
10.6: Lattice Structures

Q10.6.1
Describe the crystal structure of iron, which crystallizes with two equivalent metal atoms in a cubic unit cell.
S10.6.1
The structure of this low-temperature form of iron (below 910 °C) is body-centered cubic. There is one-eighth atom at each of the
eight corners of the cube and one atom in the center of the cube.
Q10.6.2
Describe the crystal structure of Pt, which crystallizes with four equivalent metal atoms in a cubic unit cell.
Q10.6.3
What is the coordination number of a chromium atom in the body-centered cubic structure of chromium?
S10.6.3
eight
Q10.6.4
What is the coordination number of an aluminum atom in the face-centered cubic structure of aluminum?
Q10.6.5
Cobalt metal crystallizes in a hexagonal closest packed structure. What is the coordination number of a cobalt atom?
S10.6.5
12
Q10.6.6
Nickel metal crystallizes in a cubic closest packed structure. What is the coordination number of a nickel atom?
Q10.6.7
Tungsten crystallizes in a body-centered cubic unit cell with an edge length of 3.165 Å.
a. What is the atomic radius of tungsten in this structure?
b. Calculate the density of tungsten.
S10.6.7
(a) 1.370 Å; (b) 19.26 g/cm

Q10.6.8
Platinum (atomic radius = 1.38 Å) crystallizes in a cubic closely packed structure. Calculate the edge length of the face-centered
cubic unit cell and the density of platinum.
Q10.6.9
Barium crystallizes in a body-centered cubic unit cell with an edge length of 5.025 Å
a. What is the atomic radius of barium in this structure?
b. Calculate the density of barium.
S10.6.9
(a) 2.176 Å; (b) 3.595 g/cm3
Q10.6.10
Aluminum (atomic radius = 1.43 Å) crystallizes in a cubic closely packed structure. Calculate the edge length of the face-centered
cubic unit cell and the density of aluminum.
Q10.6.11
The density of aluminum is 2.7 g/cm3; that of silicon is 2.3 g/cm3. Explain why Si has the lower density even though it has heavier
atoms.
S10.6.11
The crystal structure of Si shows that it is less tightly packed (coordination number 4) in the solid than Al (coordination number
12).
Q10.6.12
The free space in a metal may be found by subtracting the volume of the atoms in a unit cell from the volume of the cell. Calculate
the percentage of free space in each of the three cubic lattices if all atoms in each are of equal size and touch their nearest
neighbors. Which of these structures represents the most efficient packing? That is, which packs with the least amount of unused
space?
Q10.6.13
Cadmium sulfide, sometimes used as a yellow pigment by artists, crystallizes with cadmium, occupying one-half of the tetrahedral
holes in a closest packed array of sulfide ions. What is the formula of cadmium sulfide? Explain your answer.
S10.6.13
In a closest-packed array, two tetrahedral holes exist for each anion. If only half the tetrahedral holes are occupied, the numbers of
anions and cations are equal. The formula for cadmium sulfide is CdS.
Q10.6.14
A compound of cadmium, tin, and phosphorus is used in the fabrication of some semiconductors. It crystallizes with cadmium
occupying one-fourth of the tetrahedral holes and tin occupying one-fourth of the tetrahedral holes in a closest packed array of
phosphide ions. What is the formula of the compound? Explain your answer.
Q10.6.15
What is the formula of the magnetic oxide of cobalt, used in recording tapes, that crystallizes with cobalt atoms occupying one-
eighth of the tetrahedral holes and one-half of the octahedral holes in a closely packed array of oxide ions?
S10.6.15
Co3O4
Q10.6.16
A compound containing zinc, aluminum, and sulfur crystallizes with a closest-packed array of sulfide ions. Zinc ions are found in
one-eighth of the tetrahedral holes and aluminum ions in one-half of the octahedral holes. What is the empirical formula of the

compound?
Q10.6.17
A compound of thallium and iodine crystallizes in a simple cubic array of iodide ions with thallium ions in all of the cubic holes.
What is the formula of this iodide? Explain your answer.
S10.6.17
In a simple cubic array, only one cubic hole can be occupied be a cation for each anion in the array. The ratio of thallium to iodide
must be 1:1; therefore, the formula for thallium is TlI.
Q10.6.18
Which of the following elements reacts with sulfur to form a solid in which the sulfur atoms form a closest-packed array with all of
the octahedral holes occupied: Li, Na, Be, Ca, or Al?
Q10.6.19
What is the percent by mass of titanium in rutile, a mineral that contains titanium and oxygen, if structure can be described as a
closest packed array of oxide ions with titanium ions in one-half of the octahedral holes? What is the oxidation number of titanium?
S10.6.19
59.95%; The oxidation number of titanium is +4.
Q10.6.20
Explain why the chemically similar alkali metal chlorides NaCl and CsCl have different structures, whereas the chemically
different NaCl and MnS have the same structure.
Q10.6.21
As minerals were formed from the molten magma, different ions occupied the same cites in the crystals. Lithium often occurs along
with magnesium in minerals despite the difference in the charge on their ions. Suggest an explanation.
S10.6.21
Both ions are close in size: Mg, 0.65; Li, 0.60. This similarity allows the two to interchange rather easily. The difference in charge
is generally compensated by the switch of Si4+ for Al3+.
Q10.6.22
Rubidium iodide crystallizes with a cubic unit cell that contains iodide ions at the corners and a rubidium ion in the center. What is
the formula of the compound?
Q10.6.23
One of the various manganese oxides crystallizes with a cubic unit cell that contains manganese ions at the corners and in the
center. Oxide ions are located at the center of each edge of the unit cell. What is the formula of the compound?
S10.6.23
Mn2O3
Q10.6.24
NaH crystallizes with the same crystal structure as NaCl. The edge length of the cubic unit cell of NaH is 4.880 Å.
a. Calculate the ionic radius of H−. (The ionic radius of Li+ is 0.0.95 Å.)
b. Calculate the density of NaH.
Q10.6.25
Thallium(I) iodide crystallizes with the same structure as CsCl. The edge length of the unit cell of TlI is 4.20 Å. Calculate the ionic
radius of TI+. (The ionic radius of I− is 2.16 Å.)

S10.6.25
1.48 Å
Q10.6.26
A cubic unit cell contains manganese ions at the corners and fluoride ions at the center of each edge.
a. What is the empirical formula of this compound? Explain your answer.
b. What is the coordination number of the Mn3+ ion?
c. Calculate the edge length of the unit cell if the radius of a Mn3+ ion is 0.65 A.
d. Calculate the density of the compound.
Q10.6.27
What is the spacing between crystal planes that diffract X-rays with a wavelength of 1.541 nm at an angle θ of 15.55° (first order
reflection)?
S10.6.27
2.874 Å
Q10.6.28
A diffractometer using X-rays with a wavelength of 0.2287 nm produced first-order diffraction peak for a crystal angle θ = 16.21°.
Determine the spacing between the diffracting planes in this crystal.
Q10.6.29
A metal with spacing between planes equal to 0.4164 nm diffracts X-rays with a wavelength of 0.2879 nm. What is the diffraction
angle for the first order diffraction peak?
S10.6.29
20.2°
Q10.6.30
Gold crystallizes in a face-centered cubic unit cell. The second-order reflection (n = 2) of X-rays for the planes that make up the
tops and bottoms of the unit cells is at θ = 22.20°. The wavelength of the X-rays is 1.54 Å. What is the density of metallic gold?
Q10.6.31
When an electron in an excited molybdenum atom falls from the L to the K shell, an X-ray is emitted. These X-rays are diffracted
at an angle of 7.75° by planes with a separation of 2.64 Å. What is the difference in energy between the K shell and the L shell in
molybdenum assuming a first-order diffraction?
S10.6.31
1.74 × 104 eV
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CHAPTER OVERVIEW
11: Solutions and Colloids

General Chemistry
In this chapter, we will consider the nature of solutions, and examine factors that determine whether a solution will form and what
properties it may have. In addition, we will discuss colloids—systems that resemble solutions but consist of dispersions of particles
somewhat larger than ordinary molecules or ions.
11.3: Electrolytes
11.4: Solubility
11.6: Colloids
Thumbnail: Nile red solution. Image use with permission (CC BY-SA 3.0; Armin Kübelbeck).
Contributors
[email protected]).
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1
Coral reefs are home to about 25% of all marine species. They are being threatened by climate change, oceanic acidification, and
water pollution, all of which change the composition of the solution we know as seawater. Dissolved oxygen in seawater is critical
for sea creatures, but as the oceans warm, oxygen becomes less soluble. As the concentration of carbon dioxide in the atmosphere
increases, the concentration of carbon dioxide in the oceans increases, contributing to oceanic acidification. Coral reefs are
particularly sensitive to the acidification of the ocean, since the exoskeletons of the coral polyps are soluble in acidic solutions.
Humans contribute to the changing of seawater composition by allowing agricultural runoff and other forms of pollution to affect
our oceans.
Figure 11.1.1 : Coral reefs, such as this one at the Palmyra Atoll National Wildlife Refuge, are vital to the ecosystem of earth’s
oceans but are threatened by climate change and dissolved pollution. Marine life depends on the specific chemical composition of
the complex mixture we know as seawater. (credit: modification of work by “USFWS – Pacific Region”/Wikimedia Commons)
Solutions are crucial to the processes that sustain life and to many other processes involving chemical reactions. In this chapter, we
will consider the nature of solutions, and examine factors that determine whether a solution will form and what properties it may
have. In addition, we will discuss colloids—systems that resemble solutions but consist of dispersions of particles somewhat larger
than ordinary molecules or ions.
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Describe the basic properties of solutions and how they form.
Predict whether a given mixture will yield a solution based on molecular properties of its components.
Explain why some solutions either produce or absorb heat when they form.
An earlier chapter of this text introduced solutions, defined as homogeneous mixtures of two or more substances. Often, one
component of a solution is present at a significantly greater concentration, in which case it is called the solvent. The other
components of the solution present in relatively lesser concentrations are called solutes. Sugar is a covalent solid composed of
sucrose molecules, C H O . When this compound dissolves in water, its molecules become uniformly distributed among the
12 22 11
molecules of water:
C H O (s) ⟶ C H O (aq) (11.2.1)
12 22 11 12 22 11
The subscript “aq” in the equation signifies that the sucrose molecules are solutes and are therefore individually dispersed
throughout the aqueous solution (water is the solvent). Although sucrose molecules are heavier than water molecules, they remain
dispersed throughout the solution; gravity does not cause them to “settle out” over time.
Potassium dichromate, K Cr O , is an ionic compound composed of colorless potassium ions, K , and orange dichromate ions,
2 2 7
+
Cr O
2 7
. When a small amount of solid potassium dichromate is added to water, the compound dissolves and dissociates to yield
2 −
potassium ions and dichromate ions uniformly distributed throughout the mixture (Figure 11.2.1), as indicated in this equation:
+ 2 −
K Cr O (s) ⟶ 2 K (aq) + Cr O7 (aq) (11.2.2)
2 2 7 2
As with the mixture of sugar and water, this mixture is also an aqueous solution. Its solutes, potassium and dichromate ions, remain
individually dispersed among the solvent (water) molecules.
Figure 11.2.1 : When potassium dichromate (K Cr O ) is mixed with water, it forms a homogeneous orange solution. (credit:
2 2 7
modification of work by Mark Ott).

The first photo shows a small mound of an orange crystalline solid. There is a right-facing arrow. The second photo shows a
translucent, colorless liquid in a clear container. There is a right-facing arrow. The third photo shows a translucent orange liquid in
a clear, covered container.
Water is used so often as a solvent that the word solution has come to imply an aqueous solution to many people. However, almost
any gas, liquid, or solid can act as a solvent. Many alloys are solid solutions of one metal dissolved in another; for example, US
five-cent coins contain nickel dissolved in copper. Air is a gaseous solution, a homogeneous mixture of nitrogen, oxygen, and
several other gases. Oxygen (a gas), alcohol (a liquid), and sugar (a solid) all dissolve in water (a liquid) to form liquid solutions.
Table 11.2.1 gives examples of several different solutions and the phases of the solutes and solvents.
Table 11.2.1 : Different Types of Solutions
Solution Solute Solvent
air O2(g) N2(g)
soft drinks CO2(g) H2O(l)
hydrogen in palladium H2(g) Pd(s)
rubbing alcohol H2O(l) C3H8O(l) (2-propanol)
saltwater NaCl(s) H2O(l)

Solution Solute Solvent
brass Zn(s) Cu(s)
Solutions exhibit these defining traits:

They are homogeneous; that is, after a solution is mixed, it has the same composition at all points throughout (its composition is
uniform).
The physical state of a solution—solid, liquid, or gas—is typically the same as that of the solvent, as demonstrated by the
examples in Table 11.2.1.
The components of a solution are dispersed on a molecular scale; that is, they consist of a mixture of separated molecules,
atoms, and/or ions.
The dissolved solute in a solution will not settle out or separate from the solvent.
The composition of a solution, or the concentrations of its components, can be varied continuously, within limits.
The Formation of Solutions

The formation of a solution is an example of a spontaneous process, a process that occurs under specified conditions without the
requirement of energy from some external source. Sometimes we stir a mixture to speed up the dissolution process, but this is not
necessary; a homogeneous solution would form if we waited long enough. The topic of spontaneity is critically important to the
study of chemical thermodynamics and is treated more thoroughly in a later chapter of this text. For purposes of this chapter’s
discussion, it will suffice to consider two criteria that favor, but do not guarantee, the spontaneous formation of a solution:
1. a decrease in the internal energy of the system (an exothermic change, as discussed in the previous chapter on thermochemistry)
2. an increase in the disorder in the system (which indicates an increase in the entropy of the system, as you will learn about in the
later chapter on thermodynamics)
In the process of dissolution, an internal energy change often, but not always, occurs as heat is absorbed or evolved. An increase in
disorder always results when a solution forms.
When the strengths of the intermolecular forces of attraction between solute and solvent species in a solution are no different than
those present in the separated components, the solution is formed with no accompanying energy change. Such a solution is called
an ideal solution. A mixture of ideal gases (or gases such as helium and argon, which closely approach ideal behavior) is an
example of an ideal solution, since the entities comprising these gases experience no significant intermolecular attractions.
When containers of helium and argon are connected, the gases spontaneously mix due to diffusion and form a solution (Figure
11.2.2). The formation of this solution clearly involves an increase in disorder, since the helium and argon atoms occupy a volume
twice as large as that which each occupied before mixing.
Figure 11.2.2 : Samples of helium and argon spontaneously mix to give a solution in which the disorder of the atoms of the two
gases is increased.
Two figures are shown. The first contains two spherical containers joined by a closed stopcock. The container to the left is labeled
H e. It holds about thirty evenly dispersed, small, light blue spheres. The container on the right is labeled A r and contains about
thirty slightly larger blue-green spheres. The second, similar figure has an open stopcock between the two spherical containers. The
light blue and green spheres are evenly dispersed and present in both containers.
Ideal solutions may also form when structurally similar liquids are mixed. For example, mixtures of the alcohols methanol
(CH3OH) and ethanol (C2H5OH) form ideal solutions, as do mixtures of the hydrocarbons pentane, C H , and hexane, C H .
5 12 6 14
Placing methanol and ethanol, or pentane and hexane, in the bulbs shown in Figure 11.2.2 will result in the same diffusion and
subsequent mixing of these liquids as is observed for the He and Ar gases (although at a much slower rate), yielding solutions with
no significant change in energy. Unlike a mixture of gases, however, the components of these liquid-liquid solutions do, indeed,

experience intermolecular attractive forces. But since the molecules of the two substances being mixed are structurally very similar,
the intermolecular attractive forces between like and unlike molecules are essentially the same, and the dissolution process,
therefore, does not entail any appreciable increase or decrease in energy. These examples illustrate how diffusion alone can provide
the driving force required to cause the spontaneous formation of a solution. In some cases, however, the relative magnitudes of
intermolecular forces of attraction between solute and solvent species may prevent dissolution.
Figure 11.2.3 : This schematic representation of dissolution shows a stepwise process involving the endothermic separation of
solute and solvent species (Steps 1 and 2) and exothermic solvation (Step 3).
The top, central region of the figure shows solute particles as seven blue spheres and solvent particles as 16 red spheres in separate,
labeled boxes. The particles in these boxes are touching. An arrow labeled “Step 1” points left of the solute box, and shows the blue
spheres no longer touching in another box labeled “expanded solute.” An arrow labeled “Step 2” points right from the solvent box
and shows the red spheres no longer touching in another box labeled “expanded solvent.” Arrows proceed from the bottom of the
expanded solute and expanded solvent boxes and join at the bottom of the figure where a step 3 label is shown. The joined arrows
point to a box just above in which the red and blue spheres are mixed together and touching. The solute and solvent boxes are
joined by another arrow labeled “direct formation of solution” which points downward at the center of the figure. This arrow also
points to the box containing mixed red and blue spheres near the bottom of the figure.
Three types of intermolecular attractive forces are relevant to the dissolution process: solute-solute, solvent-solvent, and solute-
solvent. As illustrated in Figure 11.2.3, the formation of a solution may be viewed as a stepwise process in which energy is
consumed to overcome solute-solute and solvent-solvent attractions (endothermic processes) and released when solute-solvent
attractions are established (an exothermic process referred to as solvation). The relative magnitudes of the energy changes
associated with these stepwise processes determine whether the dissolution process overall will release or absorb energy. In some
cases, solutions do not form because the energy required to separate solute and solvent species is so much greater than the energy
released by solvation.
Figure 11.2.4 : A mixture of nonpolar cooking oil and polar water does not yield a solution. (credit: Gautam Dogra).
For example, cooking oils and water will not mix to any appreciable extent to yield solutions (Figure 11.2.4). Hydrogen bonding is
the dominant intermolecular attractive force present in liquid water; the nonpolar hydrocarbon molecules of cooking oils are not

capable of hydrogen bonding, instead being held together by dispersion forces. Forming an oil-water solution would require
overcoming the very strong hydrogen bonding in water, as well as the significantly strong dispersion forces between the relatively
large oil molecules. And, since the polar water molecules and nonpolar oil molecules would not experience very strong
intermolecular attraction, very little energy would be released by solvation.
On the other hand, a mixture of ethanol and water will mix in any proportions to yield a solution. In this case, both substances are
capable of hydrogen bonding, and so the solvation process is sufficiently exothermic to compensate for the endothermic separations
of solute and solvent molecules.
Figure 11.2.5 : An instant cold pack gets cold when certain salts, such as ammonium nitrate, dissolve in water—an endothermic
process.
This figure shows a single use instant cold pack with labels indicating an inner bag of water surrounded by white particulate
ammonium nitrate.
As noted at the beginning of this module, spontaneous solution formation is favored, but not guaranteed, by exothermic dissolution
processes. While many soluble compounds do, indeed, dissolve with the release of heat, some dissolve endothermically.
Ammonium nitrate (NH4NO3) is one such example and is used to make instant cold packs for treating injuries like the one pictured
in Figure 11.2.5. A thin-walled plastic bag of water is sealed inside a larger bag with solid NH4NO3. When the smaller bag is
broken, a solution of NH4NO3 forms, absorbing heat from the surroundings (the injured area to which the pack is applied) and
providing a cold compress that decreases swelling. Endothermic dissolutions such as this one require a greater energy input to
separate the solute species than is recovered when the solutes are solvated, but they are spontaneous nonetheless due to the increase
in disorder that accompanies formation of the solution.
Comparing Temperature Change from …
Video 11.2.1 : Watch this brief video illustrating endothermic and exothermic dissolution processes.

Summary
A solution forms when two or more substances combine physically to yield a mixture that is homogeneous at the molecular level.
The solvent is the most concentrated component and determines the physical state of the solution. The solutes are the other
components typically present at concentrations less than that of the solvent. Solutions may form endothermically or exothermically,
depending upon the relative magnitudes of solute and solvent intermolecular attractive forces. Ideal solutions form with no
appreciable change in energy.
Footnotes
1. If bubbles of gas are observed within the liquid, the mixture is not homogeneous and, thus, not a solution.
Glossary
alloy
solid mixture of a metallic element and one or more additional elements
ideal solution
solution that forms with no accompanying energy change
solvation
exothermic process in which intermolecular attractive forces between the solute and solvent in a solution are established
spontaneous process
physical or chemical change that occurs without the addition of energy from an external source
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11.3: Electrolytes
Define and give examples of electrolytes
Distinguish between the physical and chemical changes that accompany dissolution of ionic and covalent electrolytes
Relate electrolyte strength to solute-solvent attractive forces
When some substances are dissolved in water, they undergo either a physical or a chemical change that yields ions in solution.
These substances constitute an important class of compounds called electrolytes. Substances that do not yield ions when dissolved
are called nonelectrolytes. If the physical or chemical process that generates the ions is essentially 100% efficient (all of the
dissolved compound yields ions), then the substance is known as a strong electrolyte. If only a relatively small fraction of the
dissolved substance undergoes the ion-producing process, it is called a weak electrolyte.
Substances may be identified as strong, weak, or nonelectrolytes by measuring the electrical conductance of an aqueous solution
containing the substance. To conduct electricity, a substance must contain freely mobile, charged species. Most familiar is the
conduction of electricity through metallic wires, in which case the mobile, charged entities are electrons. Solutions may also
conduct electricity if they contain dissolved ions, with conductivity increasing as ion concentration increases. Applying a voltage to
electrodes immersed in a solution permits assessment of the relative concentration of dissolved ions, either quantitatively, by
measuring the electrical current flow, or qualitatively, by observing the brightness of a light bulb included in the circuit (Figure
11.3.1).
Figure 11.3.1 : Solutions of nonelectrolytes such as ethanol do not contain dissolved ions and cannot conduct electricity. Solutions
of electrolytes contain ions that permit the passage of electricity. The conductivity of an electrolyte solution is related to the
strength of the electrolyte.
This diagram shows three separate beakers. Each has a wire plugged into a wall outlet. In each case, the wire leads from the wall to
the beaker and is split resulting in two ends. One end leads to a light bulb and continues on to a rectangle labeled with a plus sign.
The other end leads to a rectangle labeled with a minus sign. The rectangles are in a solution. In the first beaker, labeled “Ethanol
No Conductivity,” four pairs of linked small green spheres suspended in the solution between the rectangles. In the second beaker,
labeled “K C l Strong Conductivity,” six individual green spheres, three labeled plus and three labeled minus are suspended in the
solution. Each of the six spheres has an arrow extending from it pointing to the rectangle labeled with the opposite sign. In the third
beaker, labeled “Acetic acid solution Weak conductivity,” two pairs of joined green spheres and two individual spheres, one labeled
plus and one labeled minus are shown suspended between the two rectangles. The plus labeled sphere has an arrow pointing to the
rectangle labeled minus and the minus labeled sphere has an arrow pointing to the rectangle labeled plus.
Ionic Electrolytes
Water and other polar molecules are attracted to ions, as shown in Figure 11.3.2. The electrostatic attraction between an ion and a
molecule with a dipole is called an ion-dipole attraction. These attractions play an important role in the dissolution of ionic
compounds in water.

Figure 11.3.2 : As potassium chloride (KCl) dissolves in water, the ions are hydrated. The polar water molecules are attracted by
the charges on the K+ and Cl− ions. Water molecules in front of and behind the ions are not shown.
The diagram shows eight purple spheres labeled K superscript plus and eight green spheres labeled C l superscript minus mixed
and touching near the center of the diagram. Outside of this cluster of spheres are seventeen clusters of three spheres, which include
one red and two white spheres. A red sphere in one of these clusters is labeled O. A white sphere is labeled H. Two of the green C l
superscript minus spheres are surrounded by three of the red and white clusters, with the red spheres closer to the green spheres
than the white spheres. One of the K superscript plus purple spheres is surrounded by four of the red and white clusters. The white
spheres of these clusters are closest to the purple spheres.
When ionic compounds dissolve in water, the ions in the solid separate and disperse uniformly throughout the solution because
water molecules surround and solvate the ions, reducing the strong electrostatic forces between them. This process represents a
physical change known as dissociation. Under most conditions, ionic compounds will dissociate nearly completely when dissolved,
and so they are classified as strong electrolytes.
Let us consider what happens at the microscopic level when we add solid KCl to water. Ion-dipole forces attract the positive
(hydrogen) end of the polar water molecules to the negative chloride ions at the surface of the solid, and they attract the negative
(oxygen) ends to the positive potassium ions. The water molecules penetrate between individual K+ and Cl− ions and surround
them, reducing the strong interionic forces that bind the ions together and letting them move off into solution as solvated ions, as
Figure shows. The reduction of the electrostatic attraction permits the independent motion of each hydrated ion in a dilute solution,
resulting in an increase in the disorder of the system as the ions change from their fixed and ordered positions in the crystal to
mobile and much more disordered states in solution. This increased disorder is responsible for the dissolution of many ionic
compounds, including KCl, which dissolve with absorption of heat.
In other cases, the electrostatic attractions between the ions in a crystal are so large, or the ion-dipole attractive forces between the
ions and water molecules are so weak, that the increase in disorder cannot compensate for the energy required to separate the ions,
and the crystal is insoluble. Such is the case for compounds such as calcium carbonate (limestone), calcium phosphate (the
inorganic component of bone), and iron oxide (rust).
Covalent Electrolytes
Pure water is an extremely poor conductor of electricity because it is only very slightly ionized—only about two out of every 1
billion molecules ionize at 25 °C. Water ionizes when one molecule of water gives up a proton to another molecule of water,
yielding hydronium and hydroxide ions.
+ + −
H O(l) H O(l) ⇌ H O (aq) + OH (aq) (11.3.1)
2 2 3
In some cases, we find that solutions prepared from covalent compounds conduct electricity because the solute molecules react
chemically with the solvent to produce ions. For example, pure hydrogen chloride is a gas consisting of covalent HCl molecules.
This gas contains no ions. However, when we dissolve hydrogen chloride in water, we find that the solution is a very good
conductor. The water molecules play an essential part in forming ions: Solutions of hydrogen chloride in many other solvents, such
as benzene, do not conduct electricity and do not contain ions.
Hydrogen chloride is an acid, and so its molecules react with water, transferring H+ ions to form hydronium ions (H 3O
+
) and
chloride ions (Cl−):

A chemical equation is shown. To the left, two hydrogen atoms are linked, each with a single dash to a central oxygen atom to the
left and below the oxygen symbol, which has two pairs of dots, above and to the right of the atom. A plus sign is shown to the
right, then a hydrogen atom linked to the left side of chlorine atom by a single dash with three pairs of dots, above, to the right, and
below the element symbol. An arrow points to the products which are three hydrogen atoms linked by single dashes to a central
oxygen atom shown in brackets with superscript plus. The oxygen atom has a single pair of dots above the element symbol. This is
followed by a plus and C l superscript minus. This symbol is surrounded by four pairs of dots, above and below and to the left and
right of the element symbol.
This reaction is essentially 100% complete for HCl (i.e., it is a strong acid and, consequently, a strong electrolyte). Likewise, weak
acids and bases that only react partially generate relatively low concentrations of ions when dissolved in water and are classified as
weak electrolytes. The reader may wish to review the discussion of strong and weak acids provided in the earlier chapter of this
text on reaction classes and stoichiometry.
Summary
Substances that dissolve in water to yield ions are called electrolytes. Electrolytes may be covalent compounds that chemically
react with water to produce ions (for example, acids and bases), or they may be ionic compounds that dissociate to yield their
constituent cations and anions, when dissolved. Dissolution of an ionic compound is facilitated by ion-dipole attractions between
the ions of the compound and the polar water molecules. Soluble ionic substances and strong acids ionize completely and are
strong electrolytes, while weak acids and bases ionize to only a small extent and are weak electrolytes. Nonelectrolytes are
substances that do not produce ions when dissolved in water.
Glossary
dissociation
physical process accompanying the dissolution of an ionic compound in which the compound’s constituent ions are solvated
and dispersed throughout the solution
electrolyte
substance that produces ions when dissolved in water
ion-dipole attraction
electrostatic attraction between an ion and a polar molecule
nonelectrolyte
substance that does not produce ions when dissolved in water
strong electrolyte
substance that dissociates or ionizes completely when dissolved in water
weak electrolyte
substance that ionizes only partially when dissolved in water
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11.2: Electrolytes is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

11.4: Solubility
Describe the effects of temperature and pressure on solubility
State Henry’s law and use it in calculations involving the solubility of a gas in a liquid
Explain the degrees of solubility possible for liquid-liquid solutions
Imagine adding a small amount of salt to a glass of water, stirring until all the salt has dissolved, and then adding a bit more. You
can repeat this process until the salt concentration of the solution reaches its natural limit, a limit determined primarily by the
relative strengths of the solute-solute, solute-solvent, and solvent-solvent attractive forces discussed in the previous two modules of
this chapter. You can be certain that you have reached this limit because, no matter how long you stir the solution, undissolved salt
remains. The concentration of salt in the solution at this point is known as its solubility.
The solubility of a solute in a particular solvent is the maximum concentration that may be achieved under given conditions when
the dissolution process is at equilibrium. Referring to the example of salt in water:
+ −
NaCl(s) ⇌ Na (aq) + Cl (aq) (11.4.1)
When a solute’s concentration is equal to its solubility, the solution is said to be saturated with that solute. If the solute’s
concentration is less than its solubility, the solution is said to be unsaturated. A solution that contains a relatively low concentration
of solute is called dilute, and one with a relatively high concentration is called concentrated.
If we add more salt to a saturated solution of salt, we see it fall to the bottom and no more seems to dissolve. In fact, the added salt
does dissolve, as represented by the forward direction of the dissolution equation. Accompanying this process, dissolved salt will
precipitate, as depicted by the reverse direction of the equation. The system is said to be at equilibrium when these two reciprocal
processes are occurring at equal rates, and so the amount of undissolved and dissolved salt remains constant. Support for the
simultaneous occurrence of the dissolution and precipitation processes is provided by noting that the number and sizes of the
undissolved salt crystals will change over time, though their combined mass will remain the same.
crystallization of sodium acetate (v2)
Video 11.4.1 : Watch this impressive video showing the precipitation of sodium acetate from a supersaturated solution.
Solutions may be prepared in which a solute concentration exceeds its solubility. Such solutions are said to be supersaturated, and
they are interesting examples of nonequilibrium states. For example, the carbonated beverage in an open container that has not yet
“gone flat” is supersaturated with carbon dioxide gas; given time, the CO2 concentration will decrease until it reaches its
equilibrium value.
Solutions of Gases in Liquids

In an earlier module of this chapter, the effect of intermolecular attractive forces on solution formation was discussed. The
chemical structures of the solute and solvent dictate the types of forces possible and, consequently, are important factors in
determining solubility. For example, under similar conditions, the water solubility of oxygen is approximately three times greater
than that of helium, but 100 times less than the solubility of chloromethane, CHCl3. Considering the role of the solvent’s chemical

structure, note that the solubility of oxygen in the liquid hydrocarbon hexane, C6H14, is approximately 20 times greater than it is in
water.
Other factors also affect the solubility of a given substance in a given solvent. Temperature is one such factor, with gas solubility
typically decreasing as temperature increases (Figure 11.4.1). This is one of the major impacts resulting from the thermal pollution
of natural bodies of water.
Figure 11.4.1 : The solubilities of these gases in water decrease as the temperature increases. All solubilities were measured with a
constant pressure of 101.3 kPa (1 atm) of gas above the solutions.
When the temperature of a river, lake, or stream is raised abnormally high, usually due to the discharge of hot water from some
industrial process, the solubility of oxygen in the water is decreased. Decreased levels of dissolved oxygen may have serious
consequences for the health of the water’s ecosystems and, in severe cases, can result in large-scale fish kills (Figure 11.4.2).
Figure 11.4.2 : (a) The small bubbles of air in this glass of chilled water formed when the water warmed to room temperature and
the solubility of its dissolved air decreased. (b) The decreased solubility of oxygen in natural waters subjected to thermal pollution
can result in large-scale fish kills. (credit a: modification of work by Liz West; credit b: modification of work by U.S. Fish and
Wildlife Service)
The solubility of a gaseous solute is also affected by the partial pressure of solute in the gas to which the solution is exposed. Gas
solubility increases as the pressure of the gas increases. Carbonated beverages provide a nice illustration of this relationship. The
carbonation process involves exposing the beverage to a relatively high pressure of carbon dioxide gas and then sealing the
beverage container, thus saturating the beverage with CO2 at this pressure. When the beverage container is opened, a familiar hiss
is heard as the carbon dioxide gas pressure is released, and some of the dissolved carbon dioxide is typically seen leaving solution
in the form of small bubbles (Figure 11.4.3). At this point, the beverage is supersaturated with carbon dioxide and, with time, the
dissolved carbon dioxide concentration will decrease to its equilibrium value and the beverage will become “flat.”

Figure 11.4.3 : Opening the bottle of carbonated beverage reduces the pressure of the gaseous carbon dioxide above the beverage.
The solubility of CO2 is thus lowered, and some dissolved carbon dioxide may be seen leaving the solution as small gas bubbles.
(credit: modification of work by Derrick Coetzee)
A dark brown liquid is shown in a clear, colorless container. A thick layer of beige bubbles appear at the surface of the liquid. In
the liquid, thirteen small clusters of single black spheres with two red spheres attached to the left and right are shown. Red spheres
represent oxygen atoms and black represent carbon atoms. Seven white arrows point upward in the container from these clusters to
the bubble layer at the top of the liquid.
For many gaseous solutes, the relation between solubility, C , and partial pressure, P , is a proportional one:
g g
Cg = kPg
where k is a proportionality constant that depends on the identities of the gaseous solute and solvent, and on the solution
temperature. This is a mathematical statement of Henry’s law: The quantity of an ideal gas that dissolves in a definite volume of
liquid is directly proportional to the pressure of the gas.
 Example 11.4.1: Application of Henry’s Law
At 20 °C, the concentration of dissolved oxygen in water exposed to gaseous oxygen at a partial pressure of 101.3 kPa (760
torr) is 1.38 × 10−3 mol L−1. Use Henry’s law to determine the solubility of oxygen when its partial pressure is 20.7 kPa (155
torr), the approximate pressure of oxygen in earth’s atmosphere.
Solution
According to Henry’s law, for an ideal solution the solubility, Cg, of a gas (1.38 × 10−3 mol L−1, in this case) is directly
proportional to the pressure, Pg, of the undissolved gas above the solution (101.3 kPa, or 760 torr, in this case). Because we
know both Cg and Pg, we can rearrange this expression to solve for k.
Cg = kPg
Cg
k =
Pg
−3 −1
1.38 × 10 mol L
=
101.3 kPa
−5 −1 −1
= 1.36 × 10 mol L kPa
−6 −1 −1
(1.82 × 10 mol L torr )
Now we can use k to find the solubility at the lower pressure.
Cg = kPg
−5 −1 −1
1.36 × 10 mol L kPa × 20.7 kPa
−6 −1 −1
(or 1.82 × 10 mol L torr × 155 torr)
−4 −1
= 2.82 × 10 mol L
Note that various units may be used to express the quantities involved in these sorts of computations. Any combination of units
that yield to the constraints of dimensional analysis are acceptable.

 Exercise 11.4.1
Exposing a 100.0 mL sample of water at 0 °C to an atmosphere containing a gaseous solute at 20.26 kPa (152 torr) resulted in
the dissolution of 1.45 × 10−3 g of the solute. Use Henry’s law to determine the solubility of this gaseous solute when its
pressure is 101.3 kPa (760 torr).
Answer
7.25 × 10−3 g in 100.0 mL or 0.0725 g/L
 Case Study: Decompression Sickness (“The Bends”)
Decompression sickness (DCS), or “the bends,” is an effect of the increased pressure of the air inhaled by scuba divers when
swimming underwater at considerable depths. In addition to the pressure exerted by the atmosphere, divers are subjected to
additional pressure due to the water above them, experiencing an increase of approximately 1 atm for each 10 m of depth.
Therefore, the air inhaled by a diver while submerged contains gases at the corresponding higher ambient pressure, and the
concentrations of the gases dissolved in the diver’s blood are proportionally higher per Henry’s law.
Figure 11.4.4 : (a) US Navy divers undergo training in a recompression chamber. (b) Divers receive hyperbaric oxygen therapy.
Two photos are shown. The first shows two people seated in a steel chamber on benches that run length of the chamber on each
side. The chamber has a couple of small circular windows and an open hatch-type door. One of the two people is giving a
thumbs up gesture. The second image provides a view through a small, circular window. Inside the two people can be seen
with masks over their mouths and noses. The people appear to be reading.
As the diver ascends to the surface of the water, the ambient pressure decreases and the dissolved gases becomes less soluble.
If the ascent is too rapid, the gases escaping from the diver’s blood may form bubbles that can cause a variety of symptoms
ranging from rashes and joint pain to paralysis and death. To avoid DCS, divers must ascend from depths at relatively slow
speeds (10 or 20 m/min) or otherwise make several decompression stops, pausing for several minutes at given depths during
the ascent. When these preventive measures are unsuccessful, divers with DCS are often provided hyperbaric oxygen therapy
in pressurized vessels called decompression (or recompression) chambers (Figure 11.4.4).
Deviations from Henry’s law are observed when a chemical reaction takes place between the gaseous solute and the solvent. Thus,
for example, the solubility of ammonia in water does not increase as rapidly with increasing pressure as predicted by the law
because ammonia, being a base, reacts to some extent with water to form ammonium ions and hydroxide ions.
Gases can form supersaturated solutions. If a solution of a gas in a liquid is prepared either at low temperature or under pressure
(or both), then as the solution warms or as the gas pressure is reduced, the solution may become supersaturated. In 1986, more than
1700 people in Cameroon were killed when a cloud of gas, almost certainly carbon dioxide, bubbled from Lake Nyos (Figure
11.4.5), a deep lake in a volcanic crater. The water at the bottom of Lake Nyos is saturated with carbon dioxide by volcanic activity
beneath the lake. It is believed that the lake underwent a turnover due to gradual heating from below the lake, and the warmer, less-

dense water saturated with carbon dioxide reached the surface. Consequently, tremendous quantities of dissolved CO2 were
released, and the colorless gas, which is denser than air, flowed down the valley below the lake and suffocated humans and animals
living in the valley.
Figure 11.4.5 : (a) It is believed that the 1986 disaster that killed more than 1700 people near Lake Nyos in Cameroon resulted
when a large volume of carbon dioxide gas was released from the lake. (b) A CO2 vent has since been installed to help outgas the
lake in a slow, controlled fashion and prevent a similar catastrophe from happening in the future. (credit a: modification of work by
Jack Lockwood; credit b: modification of work by Bill Evans)
Two photos are shown. The first is an aerial view of a lake surrounded by green hills. The second shows a large body of water with
a fountain sending liquid up into the air several yards or meters above the surface of the water.
Solutions of Liquids in Liquids

We know that some liquids mix with each other in all proportions; in other words, they have infinite mutual solubility and are said
to be miscible. Ethanol, sulfuric acid, and ethylene glycol (popular for use as antifreeze, pictured in Figure 11.4.6) are examples of
liquids that are completely miscible with water. Two-cycle motor oil is miscible with gasoline.
Figure 11.4.6 : Water and antifreeze are miscible; mixtures of the two are homogeneous in all proportions. (credit:
“dno1967”/Wikimedia commons)
Liquids that mix with water in all proportions are usually polar substances or substances that form hydrogen bonds. For such
liquids, the dipole-dipole attractions (or hydrogen bonding) of the solute molecules with the solvent molecules are at least as strong
as those between molecules in the pure solute or in the pure solvent. Hence, the two kinds of molecules mix easily. Likewise,
nonpolar liquids are miscible with each other because there is no appreciable difference in the strengths of solute-solute, solvent-
solvent, and solute-solvent intermolecular attractions. The solubility of polar molecules in polar solvents and of nonpolar molecules
in nonpolar solvents is, again, an illustration of the chemical axiom “like dissolves like.”
Two liquids that do not mix to an appreciable extent are called immiscible. Layers are formed when we pour immiscible liquids
into the same container. Gasoline, oil (Figure 11.4.7), benzene, carbon tetrachloride, some paints, and many other nonpolar liquids
are immiscible with water. The attraction between the molecules of such nonpolar liquids and polar water molecules is ineffectively
weak. The only strong attractions in such a mixture are between the water molecules, so they effectively squeeze out the molecules
of the nonpolar liquid. The distinction between immiscibility and miscibility is really one of degrees, so that miscible liquids are of
infinite mutual solubility, while liquids said to be immiscible are of very low (though not zero) mutual solubility.

Figure 11.4.7 : Water and oil are immiscible. Mixtures of these two substances will form two separate layers with the less dense oil
floating on top of the water. (credit: “Yortw”/Flickr)
This is a photo of a clear, colorless martini glass containing a golden colored liquid layer resting on top of a clear, colorless liquid.
Two liquids, such as bromine and water, that are of moderate mutual solubility are said to be partially miscible. Two partially
miscible liquids usually form two layers when mixed. In the case of the bromine and water mixture, the upper layer is water,
saturated with bromine, and the lower layer is bromine saturated with water. Since bromine is nonpolar, and, thus, not very soluble
in water, the water layer is only slightly discolored by the bright orange bromine dissolved in it. Since the solubility of water in
bromine is very low, there is no noticeable effect on the dark color of the bromine layer (Figure 11.4.8).
Figure 11.4.8 : Bromine (the deep orange liquid on the left) and water (the clear liquid in the middle) are partially miscible. The top
layer in the mixture on the right is a saturated solution of bromine in water; the bottom layer is a saturated solution of water in
bromine. (credit: Paul Flowers)
This figure shows three test tubes. The first test tube holds a dark orange-brown substance. The second test tube holds a clear
substance. The amount of substance in both test tubes is the same. The third test tube holds a dark orange-brown substance on the
bottom with a lighter orange substance on top. The amount of substance in the third test tube is almost double of the first two.
Solutions of Solids in Liquids

The dependence of solubility on temperature for a number of inorganic solids in water is shown by the solubility curves in Figure
11.4.9. Reviewing these data indicate a general trend of increasing solubility with temperature, although there are exceptions, as
illustrated by the ionic compound cerium sulfate.

Figure 11.4.9 : This graph shows how the solubility of several solids changes with temperature.
This shows a graph of the solubility of sugar C subscript 12 H subscript 22 O subscript 11, K N O subscript 3, N a N O subscript 3,
N a B r, K B r, N a subscript 2 S O subscript 4, K C l, and C e subscript 2 left parenthesis S O subscript 4 right parenthesis subscript
3 in g solute per 100 g H subscript 2 O at temperatures ranging from 0 degrees Celsius to 100 degrees Celsius. At 0 degrees
Celsius, solubilities are approximately 180 for sugar C subscript 12 H subscript 22 O subscript 11, 115 for K N O subscript 3, 75
for N a N O subscript 3, 115 for N a B r, 55 for K B r, 7 for N a subscript 2 S O subscript 4, 25 for K C l, and 20 for C e subscript 2
left parenthesis S O subscript 4 right parenthesis subscript 3. At 0 degrees Celsius, solubilities are approximately 180 for sugar C
subscript 12 H subscript 22 O subscript 11, 115 for K N O subscript 3, 75 for N a N O subscript 3, 115 for N a B r, 55 for K B r, 7
for N a subscript 2 S O subscript 4, 25 for K C l, and 20 for C e subscript 2 left parenthesis S O subscript 4 right parenthesis
subscript 3. At 100 degrees Celsius, sugar C subscript 12 H subscript 22 O subscript 11 has exceeded the upper limit of solubility
indicated on the graph, 240 for K N O subscript 3, 178 for N a N O subscript 3, 123 for N a B r, 105 for K B r, 52 for N a subscript
2 S O subscript 4, 58 for K C l, and the graph for C e subscript 2 left parenthesis S O subscript 4 right parenthesis subscript 3 stops
at about 92 degrees Celsius where the solubility is nearly zero. The graph for N a subscript 2 S O subscript 4 is shown in red. All
others substances are shown in blue. The solubility of this substance increases until about 30 degrees Celsius and declines beyond
that point with increasing temperature.
The temperature dependence of solubility can be exploited to prepare supersaturated solutions of certain compounds. A solution
may be saturated with the compound at an elevated temperature (where the solute is more soluble) and subsequently cooled to a
lower temperature without precipitating the solute. The resultant solution contains solute at a concentration greater than its
equilibrium solubility at the lower temperature (i.e., it is supersaturated) and is relatively stable. Precipitation of the excess solute
can be initiated by adding a seed crystal (see the video in the Link to Learning earlier in this module) or by mechanically agitating
the solution. Some hand warmers, such as the one pictured in Figure 11.4.10, take advantage of this behavior.
Figure 11.4.10: This hand warmer produces heat when the sodium acetate in a supersaturated solution precipitates. Precipitation of
the solute is initiated by a mechanical shockwave generated when the flexible metal disk within the solution is “clicked.” (credit:
modification of work by “Velela”/Wikimedia Commons)
Three photos of hand warmers are shown side by side with an arrow pointing from the first photo to the second, and another arrow
pointing from the second photo to the third. The first packet contains a clear colorless liquid and a small metal disc can be seen. In
the second packet, the disc can’t be seen and a dispersion of white liquid is beginning. In the third packet, all of the liquid is white.

Crystallization of the "Magic" Gel Hand …
Video 11.4.2: This video shows the crystallization process occurring in a hand warmer.
Summary
The extent to which one substance will dissolve in another is determined by several factors, including the types and relative
strengths of intermolecular attractive forces that may exist between the substances’ atoms, ions, or molecules. This tendency to
dissolve is quantified as substance’s solubility, its maximum concentration in a solution at equilibrium under specified conditions.
A saturated solution contains solute at a concentration equal to its solubility. A supersaturated solution is one in which a solute’s
concentration exceeds its solubility—a nonequilibrium (unstable) condition that will result in solute precipitation when the solution
is appropriately perturbed. Miscible liquids are soluble in all proportions, and immiscible liquids exhibit very low mutual solubility.
Solubilities for gaseous solutes decrease with increasing temperature, while those for most, but not all, solid solutes increase with
temperature. The concentration of a gaseous solute in a solution is proportional to the partial pressure of the gas to which the
solution is exposed, a relation known as Henry’s law.
Key Equations
Cg = kPg
Glossary
Henry’s law
law stating the proportional relationship between the concentration of dissolved gas in a solution and the partial pressure of the
gas in contact with the solution
immiscible
of negligible mutual solubility; typically refers to liquid substances
miscible
mutually soluble in all proportions; typically refers to liquid substances
partially miscible
of moderate mutual solubility; typically refers to liquid substances
saturated
of concentration equal to solubility; containing the maximum concentration of solute possible for a given temperature and
pressure
solubility
extent to which a solute may be dissolved in water, or any solvent
supersaturated
of concentration that exceeds solubility; a nonequilibrium state

unsaturated
of concentration less than solubility
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Express concentrations of solution components using mole fraction and molality
Describe the effect of solute concentration on various solution properties (vapor pressure, boiling point, freezing point, and
osmotic pressure)
Perform calculations using the mathematical equations that describe these various colligative effects
Describe the process of distillation and its practical applications
Explain the process of osmosis and describe how it is applied industrially and in nature
The properties of a solution are different from those of either the pure solute(s) or solvent. Many solution properties are dependent
upon the chemical identity of the solute. Compared to pure water, a solution of hydrogen chloride is more acidic, a solution of
ammonia is more basic, a solution of sodium chloride is more dense, and a solution of sucrose is more viscous. There are a few
solution properties, however, that depend only upon the total concentration of solute species, regardless of their identities. These
colligative properties include vapor pressure lowering, boiling point elevation, freezing point depression, and osmotic pressure.
This small set of properties is of central importance to many natural phenomena and technological applications, as will be
described in this module.
Mole Fraction and Molality

Several units commonly used to express the concentrations of solution components were introduced in an earlier chapter of this
text, each providing certain benefits for use in different applications. For example, molarity (M) is a convenient unit for use in
stoichiometric calculations, since it is defined in terms of the molar amounts of solute species:
mol solute
M = (11.5.1)
L solution
Because solution volumes vary with temperature, molar concentrations will likewise vary. When expressed as molarity, the
concentration of a solution with identical numbers of solute and solvent species will be different at different temperatures, due to
the contraction/expansion of the solution. More appropriate for calculations involving many colligative properties are mole-based
concentration units whose values are not dependent on temperature. Two such units are mole fraction (introduced in the previous
chapter on gases) and molality.
The mole fraction, χ, of a component is the ratio of its molar amount to the total number of moles of all solution components:
mol A
χA = (11.5.2)
total mol of all components
Molality is a concentration unit defined as the ratio of the numbers of moles of solute to the mass of the solvent in kilograms:
mol solute
m = (11.5.3)
kg solvent
Since these units are computed using only masses and molar amounts, they do not vary with temperature and, thus, are better suited
for applications requiring temperature-independent concentrations, including several colligative properties, as will be described in
this chapter module.
 Example 11.5.1: Calculating Mole Fraction and Molality

The antifreeze in most automobile radiators is a mixture of equal volumes of ethylene glycol and water, with minor amounts of
other additives that prevent corrosion. What are the (a) mole fraction and (b) molality of ethylene glycol, C2H4(OH)2, in a
solution prepared from 2.22 × 10 g of ethylene glycol and 2.00 × 10 g of water (approximately 2 L of glycol and 2 L of
3 3
water)?
Solution

(a) The mole fraction of ethylene glycol may be computed by first deriving molar amounts of both solution components and
then substituting these amounts into the unit definition.
1 mol C2 H4 (OH)2
mol C2 H4 (OH)2 = 2220 g × = 35.8 mol C2 H4 (OH)2
62.07 g C2 H4 (OH)2
1 mol H2 O
mol H2 O = 2000 g × = 111 mol H2 O
18.02 g H2 O
35.8 mol C2 H4 (OH)2

χethylene glycol = = 0.245
(35.8 + 111) mol total
Notice that mole fraction is a dimensionless property, being the ratio of properties with identical units (moles).
(b) To find molality, we need to know the moles of the solute and the mass of the solvent (in kg).
First, use the given mass of ethylene glycol and its molar mass to find the moles of solute:
mol C2 H2 (OH)2
2220 g C2 H4 (OH)2 ( ) = 35.8 mol C2 H4 (OH)2
62.07 g
Then, convert the mass of the water from grams to kilograms:

1 kg
2000 g H2 O ( ) = 2 kg H2 O
1000 g
Finally, calculate molarity per its definition:

mol solute
molality =
kg solvent
35.8 mol C2 H4 (OH)2

molality =
2 kg H2 O
molality = 17.9 m
 Exercise 11.5.1
What are the mole fraction and molality of a solution that contains 0.850 g of ammonia, NH3, dissolved in 125 g of water?
Answer
7.14 × 10−3; 0.399 m
 Example 11.5.2: Converting Mole Fraction and Molal Concentrations
Calculate the mole fraction of solute and solvent in a 3.0 m solution of sodium chloride.
Solution
Converting from one concentration unit to another is accomplished by first comparing the two unit definitions. In this case,
both units have the same numerator (moles of solute) but different denominators. The provided molal concentration may be
written as:
3.0 mol NaCl
1.0 kg H2 O
The numerator for this solution’s mole fraction is, therefore, 3.0 mol NaCl. The denominator may be computed by deriving the
molar amount of water corresponding to 1.0 kg
1000 g mol H2 O
1.0 kg H2 O ( )( ) = 55 mol H2 O
1 kg 18.02 g

and then substituting these molar amounts into the definition for mole fraction.
mol H2 O
XH O =
2
mol NaCl + mol H2 O
55 mol H2 O
XH2 O =
3.0 mol NaCl + 55 mol H2 O
XH O = 0.95
2
mol NaCl
XNaCl =
mol NaCl + mol H2 O
3.0 mol NaCl

XNaCl =
3.0 mol NaCl + 55 mol H2 O
XNaCl = 0.052
 Exercise 11.5.2
The mole fraction of iodine, I , dissolved in dichloromethane, CH

2 2
Cl
2
, is 0.115. What is the molal concentration, m, of iodine
in this solution?
Answer
1.50 m
Vapor Pressure Lowering

As described in the chapter on liquids and solids, the equilibrium vapor pressure of a liquid is the pressure exerted by its gaseous
phase when vaporization and condensation are occurring at equal rates:
liquid⇌ gas (11.5.4)
Dissolving a nonvolatile substance in a volatile liquid results in a lowering of the liquid’s vapor pressure. This phenomenon can be
rationalized by considering the effect of added solute molecules on the liquid's vaporization and condensation processes. To
vaporize, solvent molecules must be present at the surface of the solution. The presence of solute decreases the surface area
available to solvent molecules and thereby reduces the rate of solvent vaporization. Since the rate of condensation is unaffected by
the presence of solute, the net result is that the vaporization-condensation equilibrium is achieved with fewer solvent molecules in
the vapor phase (i.e., at a lower vapor pressure) (Figure 11.5.1). While this kinetic interpretation is useful, it does not account for
several important aspects of the colligative nature of vapor pressure lowering. A more rigorous explanation involves the property of
entropy, a topic of discussion in a later text chapter on thermodynamics. For purposes of understanding the lowering of a liquid's
vapor pressure, it is adequate to note that the greater entropy of a solution in comparison to its separate solvent and solute serves to
effectively stabilize the solvent molecules and hinder their vaporization. A lower vapor pressure results, and a correspondingly
higher boiling point as described in the next section of this module.

Figure 11.5.1 : The presence of nonvolatile solutes lowers the vapor pressure of a solution by impeding the evaporation of solvent
molecules.
This figure contains two images. Figure a is labeled “pure water.” It shows a beaker half-filled with liquid. In the liquid, eleven
molecules are evenly dispersed in the liquid each consisting of one central red sphere and two slightly smaller white spheres are
shown. Four molecules near the surface of the liquid have curved arrows drawn from them pointing to the space above the liquid in
the beaker. Above the liquid, twelve molecules are shown, with arrows pointing from three of them into the liquid below. Figure b
is labeled “Aqueous solution.” It is similar to figure a except that eleven blue spheres, slightly larger in size than the molecules, are
dispersed evenly in the liquid. Only four curved arrows appear in this diagram with two from the molecules in the liquid pointing to
the space above and two from molecules in the space above the liquid pointing into the liquid below.
The relationship between the vapor pressures of solution components and the concentrations of those components is described by
Raoult’s law: The partial pressure exerted by any component of an ideal solution is equal to the vapor pressure of the pure
component multiplied by its mole fraction in the solution.
∘
PA = XA P (11.5.5)
A
where PA is the partial pressure exerted by component A in the solution, P is the vapor pressure of pure A, and XA is the mole
∘
A
fraction of A in the solution. (Mole fraction is a concentration unit introduced in the chapter on gases.)
Recalling that the total pressure of a gaseous mixture is equal to the sum of partial pressures for all its components (Dalton’s law of
partial pressures), the total vapor pressure exerted by a solution containing i components is
∘
Psolution = ∑ Pi = ∑ Xi P (11.5.6)
i
i i
A nonvolatile substance is one whose vapor pressure is negligible (P° ≈ 0), and so the vapor pressure above a solution containing
only nonvolatile solutes is due only to the solvent:
∘
Psolution = Xsolvent P (11.5.7)
solvent
 Example 11.5.3: Calculation of a Vapor Pressure
Compute the vapor pressure of an ideal solution containing 92.1 g of glycerin, C3H5(OH)3, and 184.4 g of ethanol, C2H5OH, at
40 °C. The vapor pressure of pure ethanol is 0.178 atm at 40 °C. Glycerin is essentially nonvolatile at this temperature.
Solution
Since the solvent is the only volatile component of this solution, its vapor pressure may be computed per Raoult’s law as:
∘
Psolution = Xsolvent P
solvent
First, calculate the molar amounts of each solution component using the provided mass data.
1 mol C3 H5 (OH)3
92.1 g C3 H5 (OH)3 × = 1.00 mol C3 H5 (OH)3
92.094 g C3 H5 (OH)3
1 mol C2 H5 OH
184.4 g C2 H5 OH × = 4.000 mol C2 H5 OH
46.069 g C2 H5 OH
Next, calculate the mole fraction of the solvent (ethanol) and use Raoult’s law to compute the solution’s vapor pressure.

4.000 mol
XC2 H5 OH = = 0.800
(1.00 mol + 4.000 mol)
∘
Psolv = XsolvP = 0.800 × 0.178 atm = 0.142 atm
solv
 Exercise 11.5.3
A solution contains 5.00 g of urea, CO(NH2)2 (a nonvolatile solute) and 0.100 kg of water. If the vapor pressure of pure water
at 25 °C is 23.7 torr, what is the vapor pressure of the solution?
Answer
23.4 torr
Elevation of the Boiling Point of a Solvent

As described in the chapter on liquids and solids, the boiling point of a liquid is the temperature at which its vapor pressure is equal
to ambient atmospheric pressure. Since the vapor pressure of a solution is lowered due to the presence of nonvolatile solutes, it
stands to reason that the solution’s boiling point will subsequently be increased. Compared to pure solvent, a solution, therefore,
will require a higher temperature to achieve any given vapor pressure, including one equivalent to that of the surrounding
atmosphere. The increase in boiling point observed when nonvolatile solute is dissolved in a solvent, ΔT , is called boiling point
b
elevation and is directly proportional to the molal concentration of solute species:
ΔTb = Kb m (11.5.8)
where
Kb is the boiling point elevation constant, or the ebullioscopic constant and
m is the molal concentration (molality) of all solute species.
Boiling point elevation constants are characteristic properties that depend on the identity of the solvent. Values of Kb for several
solvents are listed in Table 11.5.1.
Table 11.5.1 : Boiling Point Elevation and Freezing Point Depression Constants for Several Solvents
Freezing Point (°C at 1
Solvent Boiling Point (°C at 1 atm) Kb (Cm−1) Kf (Cm−1)
atm)
water 100.0 0.512 0.0 1.86
hydrogen acetate 118.1 3.07 16.6 3.9
benzene 80.1 2.53 5.5 5.12
chloroform 61.26 3.63 −63.5 4.68
nitrobenzene 210.9 5.24 5.67 8.1
The extent to which the vapor pressure of a solvent is lowered and the boiling point is elevated depends on the total number of
solute particles present in a given amount of solvent, not on the mass or size or chemical identities of the particles. A 1 m aqueous
solution of sucrose (342 g/mol) and a 1 m aqueous solution of ethylene glycol (62 g/mol) will exhibit the same boiling point
because each solution has one mole of solute particles (molecules) per kilogram of solvent.
 Example 11.5.4: Calculating the Boiling Point of a Solution
What is the boiling point of a 0.33 m solution of a nonvolatile solute in benzene?
Solution
Use the equation relating boiling point elevation to solute molality to solve this problem in two steps.

1. Calculate the change in boiling point.
−1
ΔTb = Kb m = 2.53 °C m × 0.33 m = 0.83 °C
Add the boiling point elevation to the pure solvent’s boiling point.
Boiling temperature = 80.1 °C + 0.83 °C = 80.9 °C
 Exercise 11.5.4
What is the boiling point of the antifreeze described in Example 11.5.4?
Answer
109.2 °C
 Example 11.5.5: The Boiling Point of an Iodine Solution
Find the boiling point of a solution of 92.1 g of iodine, I

2
, in 800.0 g of chloroform, CHCl
3
, assuming that the iodine is
nonvolatile and that the solution is ideal.
Solution
We can solve this problem using four steps.
1. Convert from grams to moles of I using the molar mass of I in the unit conversion factor.
2 2
Result: 0.363 mol

Determine the molality of the solution from the number of moles of solute and the mass of solvent, in kilograms.
Result: 0.454 m
Use the direct proportionality between the change in boiling point and molal concentration to determine how much the boiling
point changes.
Result: 1.65 °C
Determine the new boiling point from the boiling point of the pure solvent and the change.
Result: 62.91 °C
Check each result as a self-assessment.
 Exercise 11.5.5: glycerin:Water Solution

What is the boiling point of a solution of 1.0 g of glycerin, C 3
H (OH)
5 3
, in 47.8 g of water? Assume an ideal solution.
Answer

100.12 °C
Distillation of Solutions
Distillation is a technique for separating the components of mixtures that is widely applied in both in the laboratory and in
industrial settings. It is used to refine petroleum, to isolate fermentation products, and to purify water. This separation technique
involves the controlled heating of a sample mixture to selectively vaporize, condense, and collect one or more components of
interest. A typical apparatus for laboratory-scale distillations is shown in Figure 11.5.2.
Figure 11.5.2 : A typical laboratory distillation unit is shown in (a) a photograph and (b) a schematic diagram of the components.
(credit a: modification of work by “Rifleman82”/Wikimedia commons; credit b: modification of work by “Slashme”/Wikimedia
Commons)
Figure a contains a photograph of a common laboratory distillation unit. Figure b provides a diagram labeling typical components
of a laboratory distillation unit, including a stirrer/heat plate with heat and stirrer speed control, a heating bath of oil or sand,
stirring means such as boiling chips, a still pot, a still head, a thermometer for boiling point temperature reading, a condenser with a
cool water inlet and outlet, a still receiver with a vacuum or gas inlet, a receiving flask for holding distillate, and a cooling bath.
Oil refineries use large-scale fractional distillation to separate the components of crude oil. The crude oil is heated to high
temperatures at the base of a tall fractionating column, vaporizing many of the components that rise within the column. As
vaporized components reach adequately cool zones during their ascent, they condense and are collected. The collected liquids are
simpler mixtures of hydrocarbons and other petroleum compounds that are of appropriate composition for various applications
(e.g., diesel fuel, kerosene, gasoline), as depicted in Figure 11.5.3.

Figure 11.5.3 : Crude oil is a complex mixture that is separated by large-scale fractional distillation to isolate various simpler
mixtures.
This figure contains a photo of a refinery, showing large columnar structures. A diagram of a fractional distillation column used in
separating crude oil is also shown. Near the bottom of the column, an arrow pointing into the column shows a point of entry for
heated crude oil. The column contains several layers at which different components are removed. At the very bottom, residue
materials are removed as indicated by an arrow out of the column. At each successive level, different materials are removed
proceeding from the bottom to the top of the column. The materials are fuel oil, followed by diesel oil, kerosene, naptha, gasoline,
and refinery gas at the very top. To the right of the column diagram, a double sided arrow is shown that is blue at the top and
gradually changes color to red moving downward. The blue top of the arrow is labeled, “small molecules: low boiling point, very
volatile, flows easily, ignites easily.” The red bottom of the arrow is labeled, “large molecules: high boiling point, not very volatile,
does not flow easily, does not ignite easily.”
Depression of the Freezing Point of a Solvent

Solutions freeze at lower temperatures than pure liquids. This phenomenon is exploited in “de-icing” schemes that use salt (Figure
11.5.4), calcium chloride, or urea to melt ice on roads and sidewalks, and in the use of ethylene glycol as an “antifreeze” in
automobile radiators. Seawater freezes at a lower temperature than fresh water, and so the Arctic and Antarctic oceans remain
unfrozen even at temperatures below 0 °C (as do the body fluids of fish and other cold-blooded sea animals that live in these
oceans).
Figure 11.5.4 : Rock salt (NaCl), calcium chloride (CaCl2), or a mixture of the two are used to melt ice. (credit: modification of
work by Eddie Welker)
The decrease in freezing point of a dilute solution compared to that of the pure solvent, ΔTf, is called the freezing point depression
and is directly proportional to the molal concentration of the solute
ΔTf = Kf m (11.5.9)
where
m is the molal concentration of the solute in the solvent and
Kf is called the freezing point depression constant (or cryoscopic constant).
Just as for boiling point elevation constants, these are characteristic properties whose values depend on the chemical identity of the
solvent. Values of Kf for several solvents are listed in Table 11.5.1.

 Example 11.5.5: Calculation of the Freezing Point of a Solution
What is the freezing point of the 0.33 m solution of a nonvolatile nonelectrolyte solute in benzene described in Example
11.5.4?
Solution
Use the equation relating freezing point depression to solute molality to solve this problem in two steps.
1. Calculate the change in freezing point.

−1
ΔTf = Kf m = 5.12 °C m × 0.33 m = 1.7 °C
2. Subtract the freezing point change observed from the pure solvent’s freezing point.
Freezing Temperature = 5.5 °C − 1.7 °C = 3.8 °C
 Exercise 11.5.6
What is the freezing point of a 1.85 m solution of a nonvolatile nonelectrolyte solute in nitrobenzene?
Answer
−9.3 °C
 Colligative Properties and De-Icing
Sodium chloride and its group 2 analogs calcium and magnesium chloride are often used to de-ice roadways and sidewalks,
due to the fact that a solution of any one of these salts will have a freezing point lower than 0 °C, the freezing point of pure
water. The group 2 metal salts are frequently mixed with the cheaper and more readily available sodium chloride (“rock salt”)
for use on roads, since they tend to be somewhat less corrosive than the NaCl, and they provide a larger depression of the
freezing point, since they dissociate to yield three particles per formula unit, rather than two particles like the sodium chloride.
Because these ionic compounds tend to hasten the corrosion of metal, they would not be a wise choice to use in antifreeze for
the radiator in your car or to de-ice a plane prior to takeoff. For these applications, covalent compounds, such as ethylene or
propylene glycol, are often used. The glycols used in radiator fluid not only lower the freezing point of the liquid, but they
elevate the boiling point, making the fluid useful in both winter and summer. Heated glycols are often sprayed onto the surface
of airplanes prior to takeoff in inclement weather in the winter to remove ice that has already formed and prevent the formation
of more ice, which would be particularly dangerous if formed on the control surfaces of the aircraft (Video 11.5.1).

Aircraft De-Icing - Close Up, Details [HD]
Video 11.5.1 : Freezing point depression is exploited to remove ice from the control surfaces of aircraft.
Phase Diagram for an Aqueous Solution of a Nonelectrolyte

The colligative effects on vapor pressure, boiling point, and freezing point described in the previous section are conveniently
summarized by comparing the phase diagrams for a pure liquid and a solution derived from that liquid. Phase diagrams for water
and an aqueous solution are shown in Figure 11.5.5.
Figure 11.5.5 : These phase diagrams show water (solid curves) and an aqueous solution of nonelectrolyte (dashed curves).
This phase diagram indicates the pressure in atmospheres of water and a solution at various temperatures. The graph shows the
freezing point of water and the freezing point of the solution, with the difference between these two values identified as delta T
subscript f. The graph shows the boiling point of water and the boiling point of the solution, with the difference between these two
values identified as delta T subscript b. Similarly, the difference in the pressure of water and the solution at the boiling point of
water is shown and identified as delta P. This difference in pressure is labeled vapor pressure lowering. The lower level of the vapor
pressure curve for the solution as opposed to that of pure water shows vapor pressure lowering in the solution. Background colors
on the diagram indicate the presence of water and the solution in the solid state to the left, liquid state in the central upper region,
and gas to the right.
The liquid-vapor curve for the solution is located beneath the corresponding curve for the solvent, depicting the vapor pressure
lowering, ΔP, that results from the dissolution of nonvolatile solute. Consequently, at any given pressure, the solution’s boiling
point is observed at a higher temperature than that for the pure solvent, reflecting the boiling point elevation, ΔTb, associated with
the presence of nonvolatile solute. The solid-liquid curve for the solution is displaced left of that for the pure solvent, representing
the freezing point depression, ΔTf, that accompanies solution formation. Finally, notice that the solid-gas curves for the solvent and
its solution are identical. This is the case for many solutions comprising liquid solvents and nonvolatile solutes. Just as for
vaporization, when a solution of this sort is frozen, it is actually just the solvent molecules that undergo the liquid-to-solid
transition, forming pure solid solvent that excludes solute species. The solid and gaseous phases, therefore, are composed solvent
only, and so transitions between these phases are not subject to colligative effects.

Osmosis and Osmotic Pressure of Solutions
A number of natural and synthetic materials exhibit selective permeation, meaning that only molecules or ions of a certain size,
shape, polarity, charge, and so forth, are capable of passing through (permeating) the material. Biological cell membranes provide
elegant examples of selective permeation in nature, while dialysis tubing used to remove metabolic wastes from blood is a more
simplistic technological example. Regardless of how they may be fabricated, these materials are generally referred to as
semipermeable membranes.
Consider the apparatus illustrated in Figure 11.5.6, in which samples of pure solvent and a solution are separated by a membrane
that only solvent molecules may permeate. Solvent molecules will diffuse across the membrane in both directions. Since the
concentration of solvent is greater in the pure solvent than the solution, these molecules will diffuse from the solvent side of the
membrane to the solution side at a faster rate than they will in the reverse direction. The result is a net transfer of solvent molecules
from the pure solvent to the solution. Diffusion-driven transfer of solvent molecules through a semipermeable membrane is a
process known as osmosis.
Figure 11.5.6 : Osmosis results in the transfer of solvent molecules from a sample of low (or zero) solute concentration to a sample
of higher solute concentration.
The figure shows two U shaped tubes with a semi permeable membrane placed at the base of the U. In figure a, pure solvent is
present and indicated by small yellow spheres to the left of the membrane. To the right, a solution exists with larger blue spheres
intermingled with some small yellow spheres. At the membrane, arrows pointing from three small yellow spheres on both sides of
the membrane cross over the membrane. An arrow drawn from one of the large blue spheres does not cross the membrane, but
rather is reflected back from the surface of the membrane. The levels of liquid in both sides of the U shaped tube are equal. In
figure b, arrows again point from small yellow spheres across the semipermeable membrane from both sides. This diagram shows
the level of liquid in the left, pure solvent, side to be significantly lower than the liquid level on the right. Dashed lines are drawn
from these two liquid levels into the middle of the U-shaped tube and between them is the term osmotic pressure.
When osmosis is carried out in an apparatus like that shown in Figure 11.5.6, the volume of the solution increases as it becomes
diluted by accumulation of solvent. This causes the level of the solution to rise, increasing its hydrostatic pressure (due to the
weight of the column of solution in the tube) and resulting in a faster transfer of solvent molecules back to the pure solvent side.
When the pressure reaches a value that yields a reverse solvent transfer rate equal to the osmosis rate, bulk transfer of solvent
ceases. This pressure is called the osmotic pressure (Π ) of the solution. The osmotic pressure of a dilute solution is related to its
solute molarity, M, and absolute temperature, T, according to the equation
Π = M RT (11.5.10)
where R is the universal gas constant.
 Example 11.5.7: Calculation of Osmotic Pressure
What is the osmotic pressure (atm) of a 0.30 M solution of glucose in water that is used for intravenous infusion at body
temperature, 37 °C?

Solution
We can find the osmotic pressure, $Π$, using Equation 11.5.10, where T is on the Kelvin scale (310 K) and the value of R is
expressed in appropriate units (0.08206 L atm/mol K).
Π = M RT
= 0.03 mol/L × 0.08206 L atm/mol K × 310 K
= 7.6 atm
 Exercise 11.5.7
What is the osmotic pressure (atm) a solution with a volume of 0.750 L that contains 5.0 g of methanol, CH3OH, in water at 37
°C?
Answer
5.3 atm
If a solution is placed in an apparatus like the one shown in Figure 11.5.7, applying pressure greater than the osmotic pressure of
the solution reverses the osmosis and pushes solvent molecules from the solution into the pure solvent. This technique of reverse
osmosis is used for large-scale desalination of seawater and on smaller scales to produce high-purity tap water for drinking.
Figure 11.5.7 : Applying a pressure greater than the osmotic pressure of a solution will reverse osmosis. Solvent molecules from the
solution are pushed into the pure solvent.
The figure shows a U shaped tube with a semi permeable membrane placed at the base of the U. Pure solvent is present and
indicated by small yellow spheres to the left of the membrane. To the right, a solution exists with larger blue spheres intermingled
with some small yellow spheres. At the membrane, arrows point from four small yellow spheres to the left of the membrane. On
the right side of the U, there is a disk that is the same width of the tube and appears to block it. The disk is at the same level as the
solution. An arrow points down from the top of the tube to the disk and is labeled, “Pressure greater than Π subscript solution.”
Examples of osmosis are evident in many biological systems because cells are surrounded by semipermeable membranes. Carrots
and celery that have become limp because they have lost water can be made crisp again by placing them in water. Water moves into
the carrot or celery cells by osmosis. A cucumber placed in a concentrated salt solution loses water by osmosis and absorbs some
salt to become a pickle. Osmosis can also affect animal cells. Solute concentrations are particularly important when solutions are
injected into the body. Solutes in body cell fluids and blood serum give these solutions an osmotic pressure of approximately 7.7
atm. Solutions injected into the body must have the same osmotic pressure as blood serum; that is, they should be isotonic with
blood serum. If a less concentrated solution, a hypotonic solution, is injected in sufficient quantity to dilute the blood serum, water
from the diluted serum passes into the blood cells by osmosis, causing the cells to expand and rupture. This process is called

hemolysis. When a more concentrated solution, a hypertonic solution, is injected, the cells lose water to the more concentrated
solution, shrivel, and possibly die in a process called crenation (Figure 11.5.8).
Figure 11.5.8 : Red blood cell membranes are water permeable and will (a) swell and possibly rupture in a hypotonic solution; (b)
maintain normal volume and shape in an isotonic solution; and (c) shrivel and possibly die in a hypertonic solution. (credit a/b/c:
modifications of work by “LadyofHats”/Wikimedia commons)
This figure shows three scenarios relating to red blood cell membranes. In a, H subscript 2 O has two arrows drawn from it
pointing into a red disk. Beneath it in a circle are eleven similar disks with a bulging appearance, one of which appears to have
burst with blue liquid erupting from it. In b, the image is similar except that rather than having two arrows pointing into the red
disk, one points in and a second points out toward the H subscript 2 O. In the circle beneath, twelve of the red disks are present. In
c, both arrows are drawn from a red shriveled disk toward the H subscript 2 O. In the circle below, twelve shriveled disks are
shown.
Determination of Molar Masses

Osmotic pressure and changes in freezing point, boiling point, and vapor pressure are directly proportional to the concentration of
solute present. Consequently, we can use a measurement of one of these properties to determine the molar mass of the solute from
the measurements.
 Example 11.5.8: Determining Molar Mass from Freezing Point Depression
A solution of 4.00 g of a nonelectrolyte dissolved in 55.0 g of benzene is found to freeze at 2.32 °C. What is the molar mass of
this compound?
Solution
We can solve this problem using the following steps.
1. Determine the change in freezing point from the observed freezing point and the freezing point of pure benzene (Table
11.5.1).

ΔTf = 5.5 °C − 2.32 °C = 3.2 °C
1. Determine the molal concentration from Kf, the freezing point depression constant for benzene (Table 11.5.1), and ΔTf.
$ΔT_\ce{f}=K_\ce{f}m$
ΔTf 3.2 °C
m = = = 0.63 m
−1
Kf 5.12 °Cm
1. Determine the number of moles of compound in the solution from the molal concentration and the mass of solvent used to make
the solution.
0.62 mol solute
Moles of solute = × 0.0550 kg solvent = 0.035 mol
1.00 kg solvent
2. Determine the molar mass from the mass of the solute and the number of moles in that mass.
$\mathrm{Molar\: mass=\dfrac{4.00\:g}{0.034\:mol}=1.2×10^2\:g/mol}$
 Exercise 11.5.8
A solution of 35.7 g of a nonelectrolyte in 220.0 g of chloroform has a boiling point of 64.5 °C. What is the molar mass of this
compound?
Answer
1.8 × 102 g/mol
 Example 11.5.9: Determination of a Molar Mass from Osmotic Pressure
A 0.500 L sample of an aqueous solution containing 10.0 g of hemoglobin has an osmotic pressure of 5.9 torr at 22 °C. What is
the molar mass of hemoglobin?
Solution
Here is one set of steps that can be used to solve the problem:
5.9 torr × 1 atm

1. Π = = 7.8 × 10
−3
atm
760 torr
Π = M RT
−3
Π 7.8 × 10 atm
−4
M = = = 3.2 × 10 M
RT (0.08206 L atm/mol K)(295 K)
−4
3.2 × 10 mol
1. moles of hemoglobin = × 0.500 L solution = 1.6 × 10
−4
mol
1 L solution
2. Determine the molar mass from the mass of hemoglobin and the number of moles in that mass.
10.0 g
4
molar mass = = 6.2 × 10 g/mol
−4
1.6 × 10 mol

 Exercise 11.5.9
What is the molar mass of a protein if a solution of 0.02 g of the protein in 25.0 mL of solution has an osmotic pressure of 0.56
torr at 25 °C?
Answer
2.7 × 104 g/mol
Colligative Properties of Electrolytes

As noted previously in this module, the colligative properties of a solution depend only on the number, not on the kind, of solute
species dissolved. For example, 1 mole of any nonelectrolyte dissolved in 1 kilogram of solvent produces the same lowering of the
freezing point as does 1 mole of any other nonelectrolyte. However, 1 mole of sodium chloride (an electrolyte) forms 2 moles of
ions when dissolved in solution. Each individual ion produces the same effect on the freezing point as a single molecule does.
 Example 11.5.10: The Freezing Point of a Solution of an Electrolyte
The concentration of ions in seawater is approximately the same as that in a solution containing 4.2 g of NaCl dissolved in 125
g of water. Assume that each of the ions in the NaCl solution has the same effect on the freezing point of water as a
nonelectrolyte molecule, and determine the freezing temperature the solution (which is approximately equal to the freezing
temperature of seawater).
Solution
We can solve this problem using the following series of steps.
Convert from grams to moles of NaCl using the molar mass of NaCl in the unit conversion factor. Result: 0.072 mol NaCl
Determine the number of moles of ions present in the solution using the number of moles of ions in 1 mole of NaCl as the
conversion factor (2 mol ions/1 mol NaCl). Result: 0.14 mol ions
Determine the molality of the ions in the solution from the number of moles of ions and the mass of solvent, in kilograms.
Result: 1.1 m
Use the direct proportionality between the change in freezing point and molal concentration to determine how much the
freezing point changes. Result: 2.0 °C
Determine the new freezing point from the freezing point of the pure solvent and the change. Result: −2.0 °C
Check each result as a self-assessment.
 Exercise 11.5.10
Assume that each of the ions in calcium chloride, CaCl2, has the same effect on the freezing point of water as a nonelectrolyte
molecule. Calculate the freezing point of a solution of 0.724 g of CaCl2 in 175 g of water.
Answer
−0.208 °C
Assuming complete dissociation, a 1.0 m aqueous solution of NaCl contains 2.0 mole of ions (1.0 mol Na+ and 1.0 mol Cl−) per
each kilogram of water, and its freezing point depression is expected to be
ΔTf = 2.0 mol ions/kg water × 1.86 °C kg water/mol ion = 3.7 °C. (11.5.11)
When this solution is actually prepared and its freezing point depression measured, however, a value of 3.4 °C is obtained. Similar
discrepancies are observed for other ionic compounds, and the differences between the measured and expected colligative property

values typically become more significant as solute concentrations increase. These observations suggest that the ions of sodium
chloride (and other strong electrolytes) are not completely dissociated in solution.
To account for this and avoid the errors accompanying the assumption of total dissociation, an experimentally measured parameter
named in honor of Nobel Prize-winning German chemist Jacobus Henricus van’t Hoff is used. The van’t Hoff factor (i) is defined
as the ratio of solute particles in solution to the number of formula units dissolved:
moles of particles in solution
i = (11.5.12)
moles of formula units dissolved
Values for measured van’t Hoff factors for several solutes, along with predicted values assuming complete dissociation, are shown
in Table 11.5.2.
Table 11.5.2 : Expected and Observed van’t Hoff Factors for Several 0.050 m Aqueous Electrolyte Solutions
Electrolyte Particles in Solution i (Predicted) i (Measured)
HCl H+, Cl− 2 1.9
NaCl Na+, Cl− 2 1.9
MgSO4 Mg2+, SO
2−
4
2 1.3
MgCl2 Mg2+, 2Cl− 3 2.7
FeCl3 Fe3+, 3Cl− 4 3.4
glucose (a non-electrolyte) C12H22O11 1 1.0
In 1923, the chemists Peter Debye and Erich Hückel proposed a theory to explain the apparent incomplete ionization of strong
electrolytes. They suggested that although interionic attraction in an aqueous solution is very greatly reduced by solvation of the
ions and the insulating action of the polar solvent, it is not completely nullified. The residual attractions prevent the ions from
behaving as totally independent particles (Figure 11.5.9). In some cases, a positive and negative ion may actually touch, giving a
solvated unit called an ion pair. Thus, the activity, or the effective concentration, of any particular kind of ion is less than that
indicated by the actual concentration. Ions become more and more widely separated the more dilute the solution, and the residual
interionic attractions become less and less. Thus, in extremely dilute solutions, the effective concentrations of the ions (their
activities) are essentially equal to the actual concentrations. Note that the van’t Hoff factors for the electrolytes in Table 11.5.2 are
for 0.05 m solutions, at which concentration the value of i for NaCl is 1.9, as opposed to an ideal value of 2.
Figure 11.5.9 : Ions become more and more widely separated the more dilute the solution, and the residual interionic attractions
become less.
The diagram shows four purple spheres labeled K superscript plus and four green spheres labeled C l superscript minus dispersed in
H subscript 2 O as shown by clusters of single red spheres with two white spheres attached. Red spheres represent oxygen and
white represent hydrogen. In two locations, the purple and green spheres are touching. In these two locations, the diagram is
labeled ion pair. All red and green spheres are surrounded by the white and red H subscript 2 O clusters. The white spheres are
attracted to the purple spheres and the red spheres are attracted to the green spheres.

Summary
Properties of a solution that depend only on the concentration of solute particles are called colligative properties. They include
changes in the vapor pressure, boiling point, and freezing point of the solvent in the solution. The magnitudes of these properties
depend only on the total concentration of solute particles in solution, not on the type of particles. The total concentration of solute
particles in a solution also determines its osmotic pressure. This is the pressure that must be applied to the solution to prevent
diffusion of molecules of pure solvent through a semipermeable membrane into the solution. Ionic compounds may not completely
dissociate in solution due to activity effects, in which case observed colligative effects may be less than predicted.
Key Equations
∘
(PA = XA P )
A
∘
Psolution = ∑i Pi = ∑i Xi P
i
∘
Psolution = Xsolvent P
solvent
ΔTb = Kbm
ΔTf = Kfm
Π = MRT
Footnotes
1. A nonelectrolyte shown for comparison.
Glossary
boiling point elevation
elevation of the boiling point of a liquid by addition of a solute
boiling point elevation constant

the proportionality constant in the equation relating boiling point elevation to solute molality; also known as the ebullioscopic
constant
colligative property
property of a solution that depends only on the concentration of a solute species
crenation
process whereby biological cells become shriveled due to loss of water by osmosis
freezing point depression

lowering of the freezing point of a liquid by addition of a solute
freezing point depression constant

(also, cryoscopic constant) proportionality constant in the equation relating freezing point depression to solute molality
hemolysis
rupture of red blood cells due to the accumulation of excess water by osmosis
hypertonic
of greater osmotic pressure
hypotonic
of less osmotic pressure
ion pair
solvated anion/cation pair held together by moderate electrostatic attraction
isotonic
of equal osmotic pressure

molality (m)
a concentration unit defined as the ratio of the numbers of moles of solute to the mass of the solvent in kilograms
osmosis
diffusion of solvent molecules through a semipermeable membrane
osmotic pressure (Π)

opposing pressure required to prevent bulk transfer of solvent molecules through a semipermeable membrane
Raoult’s law
the partial pressure exerted by a solution component is equal to the product of the component’s mole fraction in the solution and
its equilibrium vapor pressure in the pure state
semipermeable membrane
a membrane that selectively permits passage of certain ions or molecules
van’t Hoff factor (i)

the ratio of the number of moles of particles in a solution to the number of moles of formula units dissolved in the solution
This page titled 11.5: Colligative Properties is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
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11.6: Colloids
Describe the composition and properties of colloidal dispersions
List and explain several technological applications of colloids
As a child, you may have made suspensions such as mixtures of mud and water, flour and water, or a suspension of solid pigments
in water, known as tempera paint. These suspensions are heterogeneous mixtures composed of relatively large particles that are
visible (or that can be seen with a magnifying glass). They are cloudy, and the suspended particles settle out after mixing. On the
other hand, when we make a solution, we prepare a homogeneous mixture in which no settling occurs and in which the dissolved
species are molecules or ions. Solutions exhibit completely different behavior from suspensions. A solution may be colored, but it
is transparent, the molecules or ions are invisible, and they do not settle out on standing. A group of mixtures called colloids (or
colloidal dispersions) exhibit properties intermediate between those of suspensions and solutions (Figure 11.6.1). The particles in a
colloid are larger than most simple molecules; however, colloidal particles are small enough that they do not settle out upon
standing.
Figure 11.6.1 : (a) A solution is a homogeneous mixture that appears clear, such as the saltwater in this aquarium. (b) In a colloid,
such as milk, the particles are much larger but remain dispersed and do not settle. (c) A suspension, such as mud, is a
heterogeneous mixture of suspended particles that appears cloudy and in which the particles can settle. (credit a photo:
modification of work by Adam Wimsatt; credit b photo: modification of work by Melissa Wiese; credit c photo: modification of
work by Peter Burgess)
This figure contains three photos and correponding particle diagrams. In a, a photo of an aquarium containing fish is shown. The
particle diagram beneath it shows 90 tiny red spheres. In b, a photo is shown of milk being poured into a cup. The corresponding
particle diagram shows about 25 medium sized red spheres.In c, a photo is shown of two pairs of sandal clad feet in mud. The
particle diagram below shows 10 fairly large red spheres.
The particles in a colloid are large enough to scatter light, a phenomenon called the Tyndall effect. This can make colloidal
mixtures appear cloudy or opaque, such as the searchlight beams shown in Figure 11.6.2. Clouds are colloidal mixtures. They are
composed of water droplets that are much larger than molecules, but that are small enough that they do not settle out.

Figure 11.6.2 : The paths of searchlight beams are made visible when light is scattered by colloidal-size particles in the air (fog,
smoke, etc.). (credit: “Bahman”/Wikimedia Commons)
The term “colloid”—from the Greek words kolla, meaning “glue,” and eidos, meaning “like”—was first used in 1861 by Thomas
Graham to classify mixtures such as starch in water and gelatin. Many colloidal particles are aggregates of hundreds or thousands
of molecules, but others (such as proteins and polymer molecules) consist of a single extremely large molecule. The protein and
synthetic polymer molecules that form colloids may have molecular masses ranging from a few thousand to many million atomic
mass units.
Analogous to the identification of solution components as “solute” and “solvent,” the components of a colloid are likewise
classified according to their relative amounts. The particulate component typically present in a relatively minor amount is called the
dispersed phase and the substance or solution throughout which the particulate is dispersed is called the dispersion medium.
Colloids may involve virtually any combination of physical states (gas in liquid, liquid in solid, solid in gas, etc.), as illustrated by
the examples of colloidal systems given in Table 11.6.1.
Table 11.6.2 : Examples of Colloidal Systems
Dispersed Phase Dispersion Medium Common Examples Name
solid gas smoke, dust —
starch in water, some inks, paints,

solid liquid sol
milk of magnesia
solid solid some colored gems, some alloys —
liquid gas clouds, fogs, mists, sprays aerosol
liquid liquid milk, mayonnaise, butter emulsion
jellies, gels, pearl, opal (H2O in

liquid solid gel
SiO2)
foams, whipped cream, beaten egg

gas liquid foam
whites
gas solid pumice, floating soaps —
Preparation of Colloidal Systems

We can prepare a colloidal system by producing particles of colloidal dimensions and distributing these particles throughout a
dispersion medium. Particles of colloidal size are formed by two methods:
1. Dispersion methods: that is, by breaking down larger particles. For example, paint pigments are produced by dispersing large
particles by grinding in special mills.
2. Condensation methods: that is, growth from smaller units, such as molecules or ions. For example, clouds form when water
molecules condense and form very small droplets.

A few solid substances, when brought into contact with water, disperse spontaneously and form colloidal systems. Gelatin, glue,
starch, and dehydrated milk powder behave in this manner. The particles are already of colloidal size; the water simply disperses
them. Powdered milk particles of colloidal size are produced by dehydrating milk spray. Some atomizers produce colloidal
dispersions of a liquid in air.
We can prepare an emulsion by shaking together or blending two immiscible liquids. This breaks one liquid into droplets of
colloidal size, which then disperse throughout the other liquid. Oil spills in the ocean may be difficult to clean up, partly because
wave action can cause the oil and water to form an emulsion. In many emulsions, however, the dispersed phase tends to coalesce,
form large drops, and separate. Therefore, emulsions are usually stabilized by an emulsifying agent, a substance that inhibits the
coalescence of the dispersed liquid. For example, a little soap will stabilize an emulsion of kerosene in water. Milk is an emulsion
of butterfat in water, with the protein casein as the emulsifying agent. Mayonnaise is an emulsion of oil in vinegar, with egg yolk
components as the emulsifying agents.
Condensation methods form colloidal particles by aggregation of molecules or ions. If the particles grow beyond the colloidal size
range, drops or precipitates form, and no colloidal system results. Clouds form when water molecules aggregate and form colloid-
sized particles. If these water particles coalesce to form adequately large water drops of liquid water or crystals of solid water, they
settle from the sky as rain, sleet, or snow. Many condensation methods involve chemical reactions. We can prepare a red colloidal
suspension of iron(III) hydroxide by mixing a concentrated solution of iron(III) chloride with hot water:
3+ − + −
Fe (aq)
+ 3Cl (aq)
+ 6 H2 O(l) ⟶ Fe(OH) + H3 O (aq)
+ 3Cl (aq)
(11.6.1)
3(s)
A colloidal gold sol results from the reduction of a very dilute solution of gold(III) chloride by a reducing agent such as
formaldehyde, tin(II) chloride, or iron(II) sulfate:
3+ −
Au +3 e → Au (11.6.2)
Some gold sols prepared in 1857 are still intact (the particles have not coalesced and settled), illustrating the long-term stability of
many colloids.
Soaps and Detergents

Pioneers made soap by boiling fats with a strongly basic solution made by leaching potassium carbonate, K CO , from wood 2 3
ashes with hot water. Animal fats contain polyesters of fatty acids (long-chain carboxylic acids). When animal fats are treated with
a base like potassium carbonate or sodium hydroxide, glycerol and salts of fatty acids such as palmitic, oleic, and stearic acid are
formed. The salts of fatty acids are called soaps. The sodium salt of stearic acid, sodium stearate, has the formula C H CO Na 17 35 2
and contains an uncharged nonpolar hydrocarbon chain, the C H − unit, and an ionic carboxylate group, the −CO unit
17 35
−
(Figure 11.6.3).
Figure 11.6.3 : Soaps contain a nonpolar hydrocarbon end (blue) and an ionic end (red). The ionic end is a carboxylate group. The
length of the hydrocarbon end can vary from soap to soap.
This figure shows a structural formula for soap known as sodium stearate. A hydrocarbon chain composed of 18 carbon atoms and
35 hydrogen atoms is shown with an ionic end with 2 oxygen atoms and a negative charge. A positively charged N a superscript
plus is also shown at the ionic end.
Detergents (soap substitutes) also contain nonpolar hydrocarbon chains, such as C H —, and an ionic group, such as a sulfate
12 25
— OSO , or a sulfonate — SO (Figure 11.6.4). Soaps form insoluble calcium and magnesium compounds in hard water;
− −
3 3
detergents form water-soluble products—a definite advantage for detergents.
Figure 11.6.4 : Detergents contain a nonpolar hydrocarbon end (blue) and an ionic end (red). The ionic end can be either a sulfate or
a sulfonate. The length of the hydrocarbon end can vary from detergent to detergent.
This figure shows a structural formula for a detergent known as sodium lauryl sulfate. A hydrocarbon chain composed of 12 carbon
atoms and 25 hydrogen atoms is shown with an ionic end involving a negatively charged sulfur and four oxygen atoms at the ionic
end of the chain. A positively charged N a superscript plus is also shown at the ionic end.

The cleaning action of soaps and detergents can be explained in terms of the structures of the molecules involved. The hydrocarbon
(nonpolar) end of a soap or detergent molecule dissolves in, or is attracted to, nonpolar substances such as oil, grease, or dirt
particles. The ionic end is attracted by water (polar), illustrated in Figure 11.6.5. As a result, the soap or detergent molecules
become oriented at the interface between the dirt particles and the water so they act as a kind of bridge between two different kinds
of matter, nonpolar and polar. Molecules such as this are termed amphiphilic since they have both a hydrophobic (“water-fearing”)
part and a hydrophilic (“water-loving”) part. As a consequence, dirt particles become suspended as colloidal particles and are
readily washed away.
Figure 11.6.5 : This diagrammatic cross section of an emulsified drop of oil in water shows how soap or detergent acts as an
emulsifier.
This figure shows a drop of oil in which approximately thirty hydrocarbon tails are oriented toward the center of the drop with
ionic ends indicated as tiny red spheres on the surface of the oil drop. Solvated cations are indicated as purple spheres surrounded
by clusters of H subscript 2 subscript O molecules shown as tiny clusters of red central oxygen spheres with two white hydrogen
spheres attached.
 Deepwater Horizon Oil Spill
The blowout of the Deepwater Horizon oil drilling rig on April 20, 2010, in the Gulf of Mexico near Mississippi began the
largest marine oil spill in the history of the petroleum. In the 87 days following the blowout, an estimated 4.9 million barrels
(210 million gallons) of oil flowed from the ruptured well 5000 feet below the water’s surface. The well was finally declared
sealed on September 19, 2010.
Crude oil is immiscible with and less dense than water, so the spilled oil rose to the surface of the water. Floating booms,
skimmer ships, and controlled burns were used to remove oil from the water’s surface in an attempt to protect beaches and
wetlands along the Gulf coast. In addition to removal of the oil, attempts were also made to lessen its environmental impact by
rendering it “soluble” (in the loose sense of the term) and thus allowing it to be diluted to hopefully less harmful levels by the
vast volume of ocean water. This approach used 1.84 million gallons of the oil dispersant Corexit 9527, most of which was
injected underwater at the site of the leak, with small amounts being sprayed on top of the spill. Corexit 9527 contains 2-
butoxyethanol (C6H14O2), an amphiphilic molecule whose polar and nonpolar ends are useful for emulsifying oil into small
droplets, increasing the surface area of the oil and making it more available to marine bacteria for digestion (Figure 11.6.6).
While this approach avoids many of the immediate hazards that bulk oil poses to marine and coastal ecosystems, it introduces
the possibility of long-term effects resulting from the introduction of the complex and potential toxic components of petroleum
into the ocean’s food chain. A number of organizations are involved in monitoring the extended impact of this oil spill,
including the National Oceanic and Atmospheric Administration.

Figure 11.6.6 : (a) This NASA satellite image shows the oil slick from the Deepwater Horizon spill. (b) A US Air Force plane
sprays Corexit, a dispersant. (c) The molecular structure of 2-butoxyethanol is shown. (credit a: modification of work by
“NASA, FT2, demis.nl”/Wikimedia Commons; credit b: modification of work by “NASA/MODIS Rapid Response
Team”/Wikimedia Commons)
Electrical Properties of Colloidal Particles

Dispersed colloidal particles are often electrically charged. A colloidal particle of iron(III) hydroxide, for example, does not contain
enough hydroxide ions to compensate exactly for the positive charges on the iron(III) ions. Thus, each individual colloidal particle
bears a positive charge, and the colloidal dispersion consists of charged colloidal particles and some free hydroxide ions, which
keep the dispersion electrically neutral. Most metal hydroxide colloids have positive charges, whereas most metals and metal
sulfides form negatively charged dispersions. All colloidal particles in any one system have charges of the same sign. This helps
keep them dispersed because particles containing like charges repel each other.
We can take advantage of the charge on colloidal particles to remove them from a variety of mixtures. If we place a colloidal
dispersion in a container with charged electrodes, positively charged particles, such as iron(III) hydroxide particles, would move to
the negative electrode. There, the colloidal particles lose their charge and coagulate as a precipitate.
Figure 11.6.7 : In a Cottrell precipitator, positively and negatively charged particles are attracted to highly charged electrodes,
where they are neutralized and deposited as dust.
This figure shows a diagram of a Cottrell precipitator. An arrow pointing into a cylindrical chamber shows the path of soot laden
smoke. In the presence of high DC voltage and both point and plate electrodes, soot particles are removed at the bottom of the
chamber and soot free air exits the top. A photo shows the honeycomb electrodes of a modern electrostatic precipitator.
The carbon and dust particles in smoke are often colloidally dispersed and electrically charged. The charged particles are attracted
to highly charged electrodes, where they are neutralized and deposited as dust (Figure 11.6.7. This is one of the important methods
used to clean up the smoke from a variety of industrial processes. The process is also important in the recovery of valuable
products from the smoke and flue dust of smelters, furnaces, and kilns. There are also ionic air filters designed for home use to
improve indoor air quality.

Gels
When we make gelatin, such as Jell-O, we are making a type of colloid (Figure 11.6.8). Gelatin sets on cooling because the hot
aqueous mixture of gelatin coagulates as it cools and the whole mass, including the liquid, sets to an extremely viscous body
known as a gel, a colloid in which the dispersing medium is a solid and the dispersed phase is a liquid. It appears that the fibers of
the dispersing medium form a complex three-dimensional network, the interstices being filled with the liquid medium or a dilute
solution of the dispersing medium. Because the formation of a gel is accompanied by the taking up of water or some other solvent,
the gel is said to be hydrated or solvated.
Figure 11.6.8 : Gelatin desserts are colloids in which an aqueous solution of sweeteners and flavors is dispersed throughout a
medium of solid proteins. (credit photo: modification of work by Steven Depolo).
In this figure, a large molecular model of gelatin is shown with black carbon atoms, red oxygen atoms, white hydrogen atoms, and
blue nitrogen atoms. A photo is shown of gelatin dessert cut into colorful rectangles.
Pectin, a carbohydrate from fruit juices, is a gel-forming substance important in jelly making. Silica gel, a colloidal dispersion of
hydrated silicon dioxide, is formed when dilute hydrochloric acid is added to a dilute solution of sodium silicate. Canned Heat is a
gel made by mixing alcohol and a saturated aqueous solution of calcium acetate.
Summary
Colloids are mixtures in which one or more substances are dispersed as relatively large solid particles or liquid droplets throughout
a solid, liquid, or gaseous medium. The particles of a colloid remain dispersed and do not settle due to gravity, and they are often
electrically charged. Colloids are widespread in nature and are involved in many technological applications.
Glossary
amphiphilic
molecules possessing both hydrophobic (nonpolar) and a hydrophilic (polar) parts
colloid
(also, colloidal dispersion) mixture in which relatively large solid or liquid particles are dispersed uniformly throughout a gas,
liquid, or solid
dispersion medium
solid, liquid, or gas in which colloidal particles are dispersed
dispersed phase
substance present as relatively large solid or liquid particles in a colloid
emulsifying agent

amphiphilic substance used to stabilize the particles of some emulsions
emulsion
colloid formed from immiscible liquids
gel
colloidal dispersion of a liquid in a solid
Tyndall effect
scattering of visible light by a colloidal dispersion
This page titled 11.6: Colloids is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
11.5: Colloids is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

Q11.2.1
How do solutions differ from compounds? From other mixtures?
S11.2.1
A solution can vary in composition, while a compound cannot vary in composition. Solutions are homogeneous at the molecular
level, while other mixtures are heterogeneous.
Q11.2.2
Which of the principal characteristics of solutions can we see in the solutions of K 2
Cr O
2 7
shown in
Figure: When potassium dichromate (K 2

Cr O
2
) is mixed with water, it forms a homogeneous orange solution. (credit:
7
modification of work by Mark Ott)
S11.2.2
The solutions are the same throughout (the color is constant throughout), and the composition of a solution of K2Cr2O7 in water
can vary.
Q11.2.3
When KNO3 is dissolved in water, the resulting solution is significantly colder than the water was originally.
a. Is the dissolution of KNO3 an endothermic or an exothermic process?
b. What conclusions can you draw about the intermolecular attractions involved in the process?
c. Is the resulting solution an ideal solution?
S11.2.3
(a) The process is endothermic as the solution is consuming heat. (b) Attraction between the K+ and NO ions is stronger than
−
between the ions and water molecules (the ion-ion interactions have a lower, more negative energy). Therefore, the dissolution
process increases the energy of the molecular interactions, and it consumes the thermal energy of the solution to make up for the
difference. (c) No, an ideal solution is formed with no appreciable heat release or consumption.
Q11.2.4
Give an example of each of the following types of solutions:
a. a gas in a liquid
b. a gas in a gas
c. a solid in a solid
S11.2.4
(a) CO2 in water; (b) O2 in N2 (air); (c) bronze (solution of tin or other metals in copper)
Q11.2.5
Indicate the most important types of intermolecular attractions in each of the following solutions:
a. The solution in Figure.

b. NO(l) in CO(l)
c. Cl2(g) in Br2(l)
d. HCl(aq) in benzene C6H6(l)
e. Methanol CH3OH(l) in H2O(l)
S11.2.5
(a) ion-dipole forces; (b) dipole-dipole forces; (c) dispersion forces; (d) dispersion forces; (e) hydrogen bonding
Q11.2.5
Predict whether each of the following substances would be more soluble in water (polar solvent) or in a hydrocarbon such as
heptane (C7H16, nonpolar solvent):
a. vegetable oil (nonpolar)
b. isopropyl alcohol (polar)
c. potassium bromide (ionic)
S11.2.5
(a) heptane; (b) water; (c) water
Q11.2.6
Heat is released when some solutions form; heat is absorbed when other solutions form. Provide a molecular explanation for the
difference between these two types of spontaneous processes.
S11.2.6
Heat is released when the total intermolecular forces (IMFs) between the solute and solvent molecules are stronger than the total
IMFs in the pure solute and in the pure solvent: Breaking weaker IMFs and forming stronger IMFs releases heat. Heat is absorbed
when the total IMFs in the solution are weaker than the total of those in the pure solute and in the pure solvent: Breaking stronger
IMFs and forming weaker IMFs absorbs heat.
Q11.2.7
Solutions of hydrogen in palladium may be formed by exposing Pd metal to H2 gas. The concentration of hydrogen in the
palladium depends on the pressure of H2 gas applied, but in a more complex fashion than can be described by Henry’s law. Under
certain conditions, 0.94 g of hydrogen gas is dissolved in 215 g of palladium metal.
a. Determine the molarity of this solution (solution density = 1.8 g/cm3).
b. Determine the molality of this solution (solution density = 1.8 g/cm3).
c. Determine the percent by mass of hydrogen atoms in this solution (solution density = 1.8 g/cm3).
S11.2.7
http://cnx.org/contents/mH6aqegx@2/The-Dissolution-Process
11.3: Electrolytes
Q11.3.1
Explain why the ions Na+ and Cl− are strongly solvated in water but not in hexane, a solvent composed of nonpolar molecules.
S11.3.2
Crystals of NaCl dissolve in water, a polar liquid with a very large dipole moment, and the individual ions become strongly
solvated. Hexane is a nonpolar liquid with a dipole moment of zero and, therefore, does not significantly interact with the ions of
the NaCl crystals.
Q11.3.2
Explain why solutions of HBr in benzene (a nonpolar solvent) are nonconductive, while solutions in water (a polar solvent) are
conductive.

S11.3.2
HBr is an acid and so its molecules react with water molecules to form H3O+ and Br− ions that provide conductivity to the solution.
Though HBr is soluble in benzene, it does not react chemically but remains dissolved as neutral HBr molecules. With no ions
present in the benzene solution, it is electrically nonconductive.
Q11.3.3
Consider the solutions presented:
(a) Which of the following sketches best represents the ions in a solution of Fe(NO3)3(aq)?
(b) Write a balanced chemical equation showing the products of the dissolution of Fe(NO3)3.
S11.3.3
(a) Fe(NO3)3 is a strong electrolyte, thus it should completely dissociate into Fe3+ and (NO −
3
) ions. Therefore, (z) best represents
the solution. (b) Fe(NO ) (s) ⟶ Fe (aq) + 3 NO (aq)
3 3
3+ −
Q11.3.4
Compare the processes that occur when methanol (CH3OH), hydrogen chloride (HCl), and sodium hydroxide (NaOH) dissolve in
water. Write equations and prepare sketches showing the form in which each of these compounds is present in its respective
solution.
S11.3.3
Methanol, C H 3 OH , dissolves in water in all proportions, interacting via hydrogen bonding.
Methanol:
C H3 OH(l) + H2 O(l) ⟶ C H3 OH(aq) (11.E.1)
Hydrogen chloride, HCl, dissolves in and reacts with water to yield hydronium cations and chloride anions that are solvated by
strong ion-dipole interactions.
Hydrogen chloride:
+ −
H C l(g) + H2 O(l) → H3 O + Cl (11.E.2)
(aq) (aq)
Sodium hydroxide, NaOH, dissolves in water and dissociates to yield sodium cations and hydroxide anions that are strongly
solvated by ion-dipole interactions and hydrogen bonding, respectively.
Sodium hydroxide:
+ −
N aOH(s) → N a + OH (11.E.3)
(aq) (aq)

Q11.3.5
What is the expected electrical conductivity of the following solutions?
a. NaOH(aq)
b. HCl(aq)
c. C6H12O6(aq) (glucose)
d. NH3(l)
S11.3.5
(a) high conductivity (solute is an ionic compound that will dissociate when dissolved); (b) high conductivity (solute is a strong
acid and will ionize completely when dissolved); (c) nonconductive (solute is a covalent compound, neither acid nor base,
unreactive towards water); (d) low conductivity (solute is a weak base and will partially ionize when dissolved)
Q11.3.6
Why are most solid ionic compounds electrically nonconductive, whereas aqueous solutions of ionic compounds are good
conductors? Would you expect a liquid (molten) ionic compound to be electrically conductive or nonconductive? Explain.
S11.3.6
A medium must contain freely mobile, charged entities to be electrically conductive. The ions present in a typical ionic solid are
immobilized in a crystalline lattice and so the solid is not able to support an electrical current. When the ions are mobilized, either
by melting the solid or dissolving it in water to dissociate the ions, current may flow and these forms of the ionic compound are
conductive.
Q11.3.7
Indicate the most important type of intermolecular attraction responsible for solvation in each of the following solutions:
a. the solutions in Figure
b. methanol, CH3OH, dissolved in ethanol, C2H5OH
c. methane, CH4, dissolved in benzene, C6H6
d. the polar halocarbon CF2Cl2 dissolved in the polar halocarbon CF2ClCFCl2
e. O2(l) in N2(l)
S11.3.7
(a) ion-dipole; (b) hydrogen bonds; (c) dispersion forces; (d) dipole-dipole attractions; (e) dispersion forces
11.4: Solubility
Q11.4.1
Suppose you are presented with a clear solution of sodium thiosulfate, Na2S2O3. How could you determine whether the solution is
unsaturated, saturated, or supersaturated?
S11.4.1
Add a small crystal of N a S O . It will dissolve in an unsaturated solution, remain apparently unchanged in a saturated solution,
2 2 3
or initiate precipitation in a supersaturated solution.
Q11.4.2
Supersaturated solutions of most solids in water are prepared by cooling saturated solutions. Supersaturated solutions of most gases
in water are prepared by heating saturated solutions. Explain the reasons for the difference in the two procedures.
S11.4.2
The solubility of solids usually decreases upon cooling a solution, while the solubility of gases usually decreases upon heating.
Q11.4.3
Suggest an explanation for the observations that ethanol, C2H5OH, is completely miscible with water and that ethanethiol,
C2H5SH, is soluble only to the extent of 1.5 g per 100 mL of water.

S11.4.3
The hydrogen bonds between water and C2H5OH are much stronger than the intermolecular attractions between water and
C2H5SH.
Q11.4.4
Calculate the percent by mass of KBr in a saturated solution of KBr in water at 10 °C using the following figure for useful data,
and report the computed percentage to one significant digit.
This graph shows how the solubility of several solids changes with temperature.
S11.4.4
At 10 °C, the solubility of KBr in water is approximately 60 g per 100 g of water.
60 g KBr
% KBr = = 40% (11.E.4)
(60 + 100) g solution
Q11.4.5
Which of the following gases is expected to be most soluble in water? Explain your reasoning.
a. CH4
b. CCl4
c. CHCl3
S11.4.5
(c) CHCl3 is expected to be most soluble in water. Of the three gases, only this one is polar and thus capable of experiencing
relatively strong dipole-dipole attraction to water molecules.
Q11.4.6
At 0 °C and 1.00 atm, as much as 0.70 g of O2 can dissolve in 1 L of water. At 0 °C and 4.00 atm, how many grams of O2 dissolve
in 1 L of water?
S11.4.6
This problem requires the application of Henry’s law. The governing equation is C g = kPg .
Cg 0.70 g
−1
k = = = 0.70 g atm (11.E.5)
Pg 1.00 atm
Under the new conditions, C g = 0.70 g atm

−1
× 4.00 atm = 2.80 g .

Q11.4.7
Refer to following figure for the following three questions:
a. How did the concentration of dissolved CO2 in the beverage change when the bottle was opened?
b. What caused this change?
c. Is the beverage unsaturated, saturated, or supersaturated with CO2?
S11.4.7
(a) It decreased as some of the CO2 gas left the solution (evidenced by effervescence). (b) Opening the bottle released the high-
pressure CO2 gas above the beverage. The reduced CO2 gas pressure, per Henry’s law, lowers the solubility for CO2. (c) The
dissolved CO2 concentration will continue to slowly decrease until equilibrium is reestablished between the beverage and the very
low CO2 gas pressure in the opened bottle. Immediately after opening, the beverage, therefore, contains dissolved CO2 at a
concentration greater than its solubility, a nonequilibrium condition, and is said to be supersaturated.
Q11.4.8
The Henry’s law constant for CO2 is 3.4 × 10 M /atm at 25 °C. What pressure of carbon dioxide is needed to maintain a CO2
−2
concentration of 0.10 M in a can of lemon-lime soda?
S11.4.8
Cg 0.10 M
Pg = = = 2.9 atm (11.E.6)
−2
k 3.4 × 10 M /atm
Q11.4.9
The Henry’s law constant for O2 is 1.3 × 10 M /atm at 25 °C. What mass of oxygen would be dissolved in a 40-L aquarium at
−3
25 °C, assuming an atmospheric pressure of 1.00 atm, and that the partial pressure of O2 is 0.21 atm?
S11.4.9
Start with Henry's law
Cg = kPg (11.E.7)
and apply it to O 2
−3 −4
C (O2 ) = (1.3 × 10 M /atm)(0.21 atm) = 2.7 × 10 mol/L (11.E.8)
The total amount is \((2.7 \times 10^{−4}\; mol/L)(40\;L=1.08 \times 10^{−2} \;mol\]

The mass of oxygen is (1.08 × 10 −2
mol)(32.0 g/mol) = 0.346 g
or, using two significant figures, 0.35 g.
Q11.4.10
How many liters of HCl gas, measured at 30.0 °C and 745 torr, are required to prepare 1.25 L of a 3.20-M solution of hydrochloric
acid?
S11.4.10
First, calculate the moles of HCl needed. Then use the ideal gas law to find the volume required.
M = mol L−1
3.20M=xmol1.25L
x = 4.00 mol HCl
Before using the ideal gas law, change pressure to atmospheres and convert temperature from °C to kelvin.
\[1\;atmx=760torr745torr
x = 0.9803 atm
V=nRTP=(4.000molHCl)(0.08206LatmK−1mol−1)(303.15K)0.9803atm=102 L HCl
102 L HCl
more http://cnx.org/contents/2488fW6W@2/Solubility

Q11.5.1
Which is/are part of the macroscopic domain of solutions and which is/are part of the microscopic domain: boiling point elevation,
Henry’s law, hydrogen bond, ion-dipole attraction, molarity, nonelectrolyte, nonstoichiometric compound, osmosis, solvated ion?
Q11.5.2
What is the microscopic explanation for the macroscopic behavior illustrated in [link]?
S11.5.2
The strength of the bonds between like molecules is stronger than the strength between unlike molecules. Therefore, some regions
will exist in which the water molecules will exclude oil molecules and other regions will exist in which oil molecules will exclude
water molecules, forming a heterogeneous region.
Q11.5.3
Sketch a qualitative graph of the pressure versus time for water vapor above a sample of pure water and a sugar solution, as the
liquids evaporate to half their original volume.
Q11.5.4
A solution of potassium nitrate, an electrolyte, and a solution of glycerin (C3H5(OH)3), a nonelectrolyte, both boil at 100.3 °C.
What other physical properties of the two solutions are identical?
S11.5.4
Both form homogeneous solutions; their boiling point elevations are the same, as are their lowering of vapor pressures. Osmotic
pressure and the lowering of the freezing point are also the same for both solutions.
Q11.5.5
What are the mole fractions of H3PO4 and water in a solution of 14.5 g of H3PO4 in 125 g of water?

Q11.5.6
What are the mole fractions of HNO3 and water in a concentrated solution of nitric acid (68.0% HNO3 by mass)?
S11.5.6
a. Find number of moles of HNO3 and H2O in 100 g of the solution. Find the mole fractions for the components.
b. The mole fraction of HNO3 is 0.378. The mole fraction of H2O is 0.622.
Q11.5.7
Calculate the mole fraction of each solute and solvent:
a. 583 g of H2SO4 in 1.50 kg of water—the acid solution used in an automobile battery
b. 0.86 g of NaCl in 1.00 × 102 g of water—a solution of sodium chloride for intravenous injection
c. 46.85 g of codeine, C18H21NO3, in 125.5 g of ethanol, C2H5OH
d. 25 g of I2 in 125 g of ethanol, C2H5OH
S11.5.7
1 mole H SO
a. 583 g H SO
2 4
×
2 4
= 5.94 mole H SO
2 4
98.08 g H SO
2 4
1000 g 1 mole H O
2
1.50 kg H O × × = 83.2 moles H O
2 2
1 kg 18.02 g H O
2
Q11.5.8
Calculate the mole fraction of each solute and solvent:
a. 0.710 kg of sodium carbonate (washing soda), Na2CO3, in 10.0 kg of water—a saturated solution at 0 °C
b. 125 g of NH4NO3 in 275 g of water—a mixture used to make an instant ice pack
c. 25 g of Cl2 in 125 g of dichloromethane, CH2Cl2
d. 0.372 g of histamine, C5H9N, in 125 g of chloroform, CHCl3
S11.5.8
a. X = 0.0119; X
Na2 C O3 H2 O = 0.988 ;
b. X = 0.9927; X
NH4 NO3 H2 O = 0.907 ;
c. X = 0.192; X
Cl2 C H2 C I2 = 0.808 ;
d. X = 0.00426; X
C5 H9 N CHCl3 = 0.997
Q11.5.9
Calculate the mole fractions of methanol, CH3OH; ethanol, C2H5OH; and water in a solution that is 40% methanol, 40% ethanol,
and 20% water by mass. (Assume the data are good to two significant figures.)
Q11.5.10
What is the difference between a 1 M solution and a 1 m solution?
S11.5.10
In a 1 M solution, the mole is contained in exactly 1 L of solution. In a 1 m solution, the mole is contained in exactly 1 kg of
solvent.
Q11.5.11
What is the molality of phosphoric acid, H3PO4, in a solution of 14.5 g of H3PO4 in 125 g of water?
Q11.5.12
What is the molality of nitric acid in a concentrated solution of nitric acid (68.0% HNO3 by mass)?
S11.5.12
(a) Determine the molar mass of HNO3. Determine the number of moles of acid in the solution. From the number of moles and the
mass of solvent, determine the molality. (b) 33.7 m

Q11.5.13
Calculate the molality of each of the following solutions:
a. 583 g of H2SO4 in 1.50 kg of water—the acid solution used in an automobile battery
b. 0.86 g of NaCl in 1.00 × 102 g of water—a solution of sodium chloride for intravenous injection
c. 46.85 g of codeine, C18H21NO3, in 125.5 g of ethanol, C2H5OH
d. 25 g of I2 in 125 g of ethanol, C2H5OH
Q11.5.14
Calculate the molality of each of the following solutions:
a. 0.710 kg of sodium carbonate (washing soda), Na2CO3, in 10.0 kg of water—a saturated solution at 0°C
b. 125 g of NH4NO3 in 275 g of water—a mixture used to make an instant ice pack
c. 25 g of Cl2 in 125 g of dichloromethane, CH2Cl2
d. 0.372 g of histamine, C5H9N, in 125 g of chloroform, CHCl3
S11.5.14
(a) 6.70 × 10−1 m; (b) 5.67 m; (c) 2.8 m; (d) 0.0358 m
Q11.5.15
75 mg
The concentration of glucose, C6H12O6, in normal spinal fluid is . What is the molality of the solution?
100 g
Q11.5.16
A 13.0% solution of K2CO3 by mass has a density of 1.09 g/cm3. Calculate the molality of the solution.
S11.5.16
1.08 m
Q11.5.17
a. Why does 1 mol of sodium chloride depress the freezing point of 1 kg of water almost twice as much as 1 mol of glycerin?
b. What is the boiling point of a solution of 115.0 g of sucrose, C12H22O11, in 350.0 g of water?
S11.5.17
a. Determine the molar mass of sucrose; determine the number of moles of sucrose in the solution; convert the mass of solvent to
units of kilograms; from the number of moles and the mass of solvent, determine the molality; determine the difference between
the boiling point of water and the boiling point of the solution; determine the new boiling point.
b. 100.5 °C
Q11.5.18
What is the boiling point of a solution of 9.04 g of I2 in 75.5 g of benzene, assuming the I2 is nonvolatile?
Q11.5.19
What is the freezing temperature of a solution of 115.0 g of sucrose, C12H22O11, in 350.0 g of water, which freezes at 0.0 °C when
pure?
S11.5.19
(a) Determine the molar mass of sucrose; determine the number of moles of sucrose in the solution; convert the mass of solvent to
units of kilograms; from the number of moles and the mass of solvent, determine the molality; determine the difference between
the freezing temperature of water and the freezing temperature of the solution; determine the new freezing temperature. (b) −1.8 °C
Q11.5.20
What is the freezing point of a solution of 9.04 g of I2 in 75.5 g of benzene?

Q11.5.21
What is the osmotic pressure of an aqueous solution of 1.64 g of Ca(NO3)2 in water at 25 °C? The volume of the solution is 275
mL.
S11.5.21
(a) Determine the molar mass of Ca(NO3)2; determine the number of moles of Ca(NO3)2 in the solution; determine the number of
moles of ions in the solution; determine the molarity of ions, then the osmotic pressure. (b) 2.67 atm
Q11.5.22
What is osmotic pressure of a solution of bovine insulin (molar mass, 5700 g mol−1) at 18 °C if 100.0 mL of the solution contains
0.103 g of the insulin?
Q11.5.23
What is the molar mass of a solution of 5.00 g of a compound in 25.00 g of carbon tetrachloride (bp 76.8 °C; Kb = 5.02 °C/m) that
boils at 81.5 °C at 1 atm?
S11.5.24
(a) Determine the molal concentration from the change in boiling point and Kb; determine the moles of solute in the solution from
the molal concentration and mass of solvent; determine the molar mass from the number of moles and the mass of solute. (b) 2.1 ×
102 g mol−1
Q11.5.25
A sample of an organic compound (a nonelectrolyte) weighing 1.35 g lowered the freezing point of 10.0 g of benzene by 3.66 °C.
Calculate the molar mass of the compound.
Q11.5.26
A 1.0 m solution of HCl in benzene has a freezing point of 0.4 °C. Is HCl an electrolyte in benzene? Explain.
S11.5.26
No. Pure benzene freezes at 5.5 °C, and so the observed freezing point of this solution is depressed by ΔTf = 5.5 − 0.4 = 5.1 °C.
The value computed, assuming no ionization of HCl, is ΔTf = (1.0 m)(5.14 °C/m) = 5.1 °C. Agreement of these values supports the
assumption that HCl is not ionized.
Q11.5.27
A solution contains 5.00 g of urea, CO(NH2)2, a nonvolatile compound, dissolved in 0.100 kg of water. If the vapor pressure of
pure water at 25 °C is 23.7 torr, what is the vapor pressure of the solution?
Q11.5.28
A 12.0-g sample of a nonelectrolyte is dissolved in 80.0 g of water. The solution freezes at −1.94 °C. Calculate the molar mass of
the substance.
S11.5.28
144 g mol−1
Q11.5.29
Arrange the following solutions in order by their decreasing freezing points: 0.1 m Na3PO4, 0.1 m C2H5OH, 0.01 m CO2, 0.15 m
NaCl, and 0.2 m CaCl2.
Q11.5.30
Calculate the boiling point elevation of 0.100 kg of water containing 0.010 mol of NaCl, 0.020 mol of Na2SO4, and 0.030 mol of
MgCl2, assuming complete dissociation of these electrolytes.

S11.5.30
0.870 °C
Q11.5.31
How could you prepare a 3.08 m aqueous solution of glycerin, C3H8O3? What is the freezing point of this solution?
Q11.5.32
A sample of sulfur weighing 0.210 g was dissolved in 17.8 g of carbon disulfide, CS2 (Kb = 2.43 °C/m). If the boiling point
elevation was 0.107 °C, what is the formula of a sulfur molecule in carbon disulfide?
S11.5.32
S8
Q11.5.33
In a significant experiment performed many years ago, 5.6977 g of cadmium iodide in 44.69 g of water raised the boiling point
0.181 °C. What does this suggest about the nature of a solution of CdI2?
Q11.5.34
Lysozyme is an enzyme that cleaves cell walls. A 0.100-L sample of a solution of lysozyme that contains 0.0750 g of the enzyme
exhibits an osmotic pressure of 1.32 × 10−3 atm at 25 °C. What is the molar mass of lysozyme?
S11.5.34
1.39 × 104 g mol−1
Q11.5.35
The osmotic pressure of a solution containing 7.0 g of insulin per liter is 23 torr at 25 °C. What is the molar mass of insulin?
Q11.5.36
The osmotic pressure of human blood is 7.6 atm at 37 °C. What mass of glucose, C6H12O6, is required to make 1.00 L of aqueous
solution for intravenous feeding if the solution must have the same osmotic pressure as blood at body temperature, 37 °C?
S11.5.36
54 g
Q11.5.37
What is the freezing point of a solution of dibromobenzene, C6H4Br2, in 0.250 kg of benzene, if the solution boils at 83.5 °C?
Q11.5.38
What is the boiling point of a solution of NaCl in water if the solution freezes at −0.93 °C?
S11.5.38
100.26 °C
Q11.5.39
The sugar fructose contains 40.0% C, 6.7% H, and 53.3% O by mass. A solution of 11.7 g of fructose in 325 g of ethanol has a
boiling point of 78.59 °C. The boiling point of ethanol is 78.35 °C, and Kb for ethanol is 1.20 °C/m. What is the molecular formula
of fructose?
Q11.5.40
The vapor pressure of methanol, CH3OH, is 94 torr at 20 °C. The vapor pressure of ethanol, C2H5OH, is 44 torr at the same
temperature.
a. Calculate the mole fraction of methanol and of ethanol in a solution of 50.0 g of methanol and 50.0 g of ethanol.
b. Ethanol and methanol form a solution that behaves like an ideal solution. Calculate the vapor pressure of methanol and of
ethanol above the solution at 20 °C.

c. Calculate the mole fraction of methanol and of ethanol in the vapor above the solution.
S11.5.40
(a) XC H3 OH ;
= 0.590 XC2 H5 OH = 0.410 ; (b) Vapor pressures are: CH3OH: 55 torr; C2H5OH: 18 torr; (c) CH3OH: 0.75; C2H5OH:
0.25
Q11.5.41
The triple point of air-free water is defined as 273.15 K. Why is it important that the water be free of air?
Q11.5.42
Meat can be classified as fresh (not frozen) even though it is stored at −1 °C. Why wouldn’t meat freeze at this temperature?
S11.5.42
The ions and compounds present in the water in the beef lower the freezing point of the beef below −1 °C.
Q11.5.43
An organic compound has a composition of 93.46% C and 6.54% H by mass. A solution of 0.090 g of this compound in 1.10 g of
camphor melts at 158.4 °C. The melting point of pure camphor is 178.4 °C. Kf for camphor is 37.7 °C/m. What is the molecular
formula of the solute? Show your calculations.
Q11.5.44
A sample of HgCl2 weighing 9.41 g is dissolved in 32.75 g of ethanol, C2H5OH (Kb = 1.20 °C/m). The boiling point elevation of
the solution is 1.27 °C. Is HgCl2 an electrolyte in ethanol? Show your calculations.
S11.5.44
1 mol HgCl2
⎛ 9.41 g × ⎞
⎜ 271.496 g ⎟
Δbp = Kb m = (1.20 °C/m)⎜ ⎟ = 1.27 °C
⎜ 0.03275 kg ⎟
⎝ ⎠
The observed change equals the theoretical change; therefore, no dissociation occurs.
Q11.5.45
A salt is known to be an alkali metal fluoride. A quick approximate determination of freezing point indicates that 4 g of the salt
dissolved in 100 g of water produces a solution that freezes at about −1.4 °C. What is the formula of the salt? Show your
calculations.
11.6: Colloids
Q11.6.1
Identify the dispersed phase and the dispersion medium in each of the following colloidal systems: starch dispersion, smoke, fog,
pearl, whipped cream, floating soap, jelly, milk, and ruby.
S11.6.1
Colloidal System Dispersed Phase Dispersion Medium
starch dispersion starch water
smoke solid particles air
fog water air
pearl water calcium carbonate (CaCO3)
whipped cream air cream
floating soap air soap
jelly fruit juice pectin gel

Colloidal System Dispersed Phase Dispersion Medium
milk butterfat water
ruby chromium(III) oxide (Cr2O3) aluminum oxide (Al2O3)
Q11.6.2
Distinguish between dispersion methods and condensation methods for preparing colloidal systems.
S11.6.2
Dispersion methods use a grinding device or some other means to bring about the subdivision of larger particles. Condensation
methods bring smaller units together to form a larger unit. For example, water molecules in the vapor state come together to form
very small droplets that we see as clouds.
Q11.6.3
How do colloids differ from solutions with regard to dispersed particle size and homogeneity?
S11.6.3
Colloidal dispersions consist of particles that are much bigger than the solutes of typical solutions. Colloidal particles are either
very large molecules or aggregates of smaller species that usually are big enough to scatter light. Colloids are homogeneous on a
macroscopic (visual) scale, while solutions are homogeneous on a microscopic (molecular) scale.
Q11.6.4
Explain the cleansing action of soap.
S11.6.4
Soap molecules have both a hydrophobic and a hydrophilic end. The charged (hydrophilic) end, which is usually associated with an
alkali metal ion, ensures water solubility The hydrophobic end permits attraction to oil, grease, and other similar nonpolar
substances that normally do not dissolve in water but are pulled into the solution by the soap molecules.
Q11.6.5
How can it be demonstrated that colloidal particles are electrically charged?
S11.6.5
If they are placed in an electrolytic cell, dispersed particles will move toward the electrode that carries a charge opposite to their
own charge. At this electrode, the charged particles will be neutralized and will coagulate as a precipitate.
Contributors and Attributions

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OpenStax.

CHAPTER OVERVIEW
12: Appendices

General Chemistry
Contributors
[email protected]).
This page titled 12: Appendices is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.
1
Composition of Commercial Acids and Bases
Composition of Commercial Acids and Bases
Acid or Base1 Density (g/mL)2 Percentage by Mass Molarity
acetic acid, glacial 1.05 99.5% 17.4
aqueous ammonia3 0.90 28% 14.8
hydrochloric acid 1.18 36% 11.6
nitric acid 1.42 71% 16.0
perchloric acid 1.67 70% 11.65
phosphoric acid 1.70 85% 14.7
sodium hydroxide 1.53 50% 19.1
sulfuric acid 1.84 96% 18.0
Footnotes
1. 1 Acids and bases are commercially available as aqueous solutions. This table lists properties (densities and concentrations) of
common acid and base solutions. Nominal values are provided in cases where the manufacturer cites a range of concentrations
and densities.
2. 2 This column contains specific gravity data. In the case of this table, specific gravity is the ratio of density of a substance to the
density of pure water at the same conditions. Specific gravity is often cited on commercial labels.
3. 3 This solution is sometimes called “ammonium hydroxide,” although this term is not chemically accurate.
This page titled 12.1: Composition of Commercial Acids and Bases is shared under a CC BY license and was authored, remixed, and/or curated
by OpenStax.
Composition of Commercial Acids and Bases is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

Exponential Arithmetic
Exponential notation is used to express very large and very small numbers as a product of two numbers. The first number of the
product, the digit term, is usually a number not less than 1 and not greater than 10. The second number of the product, the
exponential term, is written as 10 with an exponent. Some examples of exponential notation are:
3
1000 = 1 × 10
2
100 = 1 × 10
1
10 = 1 × 10
0
1 = 1 × 10
−1
0.1 = 1 × 10
−3
0.001 = 1 × 10
3
2386 = 2.386 × 1000 = 2.386 × 10
−1
0.123 = 1.23 × 0.1 = 1.23 × 10
The power (exponent) of 10 is equal to the number of places the decimal is shifted to give the digit number. The exponential
method is particularly useful notation for every large and very small numbers. For example, 1,230,000,000 = 1.23 × 109, and
0.00000000036 = 3.6 × 10−10.
Addition of Exponentials
Convert all numbers to the same power of 10, add the digit terms of the numbers, and if appropriate, convert the digit term back to
a number between 1 and 10 by adjusting the exponential term.
 Exercise 12.2.1: Adding Exponentials
Add 5.00 × 10−5 and 3.00 × 10−3.
Solution
−3 −5
3.00 × 10 = 300 × 10
−5 −5 −5 −3
(5.00 × 10 ) + (300 × 10 ) = 305 × 10 = 3.05 × 10
Subtraction of Exponentials
Convert all numbers to the same power of 10, take the difference of the digit terms, and if appropriate, convert the digit term back
to a number between 1 and 10 by adjusting the exponential term.
 Exercise 12.2.2: Subtracting Exponentials

Subtract 4.0 × 10−7 from 5.0 × 10−6.
Solution
−7 −6
4.0 × 10 = 0.40 × 10
−6 −6 −6
(5.0 × 10 ) − (0.40 × 10 ) = 4.6 × 10
Multiplication of Exponentials
Multiply the digit terms in the usual way and add the exponents of the exponential terms.

 Exercise 12.2.3: Multiplying Exponentials
Multiply 4.2 × 10−8 by 2.0 × 103.
Solution
−8 3 (−8)+(+3) −5
(4.2 × 10 ) × (2.0 × 10 ) = (4.2 × 2.0) × 10 = 8.4 × 10
Division of Exponentials
Divide the digit term of the numerator by the digit term of the denominator and subtract the exponents of the exponential terms.
 Exercise 12.2.4: Dividing Exponentials
Divide 3.6 × 105 by 6.0 × 10−4.
Solution
−5
3.6 × 10 3.6
(−5)−(−4) −1 −2
=( ) × 10 = 0.60 × 10 = 6.0 × 10
−4
6.0 × 10 6.0
Squaring of Exponentials
Square the digit term in the usual way and multiply the exponent of the exponential term by 2.
 Exercise 12.2.5: Squaring Exponentials
Square the number 4.0 × 10−6.
Solution
−6 2 2×(−6) −12 −11
(4.0 × 10 ) = 4 × 4 × 10 = 16 × 10 = 1.6 × 10
Cubing of Exponentials
Cube the digit term in the usual way and multiply the exponent of the exponential term by 3.
 Exercise 12.2.6: Cubing Exponentials
Cube the number 2 × 104.
Solution
4 3 3×4 12
(2 × 10 ) = 2 × 2 × 2 × 10 = 8 × 10
Taking Square Roots of Exponentials

If necessary, decrease or increase the exponential term so that the power of 10 is evenly divisible by 2. Extract the square root of
the digit term and divide the exponential term by 2.
 Exercise 12.2.7: Finding the Square Root of Exponentials

Find the square root of 1.6 × 10−7.

Solution
−7 −8
1.6 × 10 = 16 × 10
− −−−− −−− −− −−−− −−
8
−
√ 16 × 10−8 = √16 × √10−8 = √16 × 10 2
−4
= 4.0 × 10
Significant Figures
A beekeeper reports that he has 525,341 bees. The last three figures of the number are obviously inaccurate, for during the time the
keeper was counting the bees, some of them died and others hatched; this makes it quite difficult to determine the exact number of
bees. It would have been more accurate if the beekeeper had reported the number 525,000. In other words, the last three figures are
not significant, except to set the position of the decimal point. Their exact values have no meaning useful in this situation. In
reporting any information as numbers, use only as many significant figures as the accuracy of the measurement warrants.
The importance of significant figures lies in their application to fundamental computation. In addition and subtraction, the sum or
difference should contain as many digits to the right of the decimal as that in the least certain of the numbers used in the
computation (indicated by underscoring in the following example).
 Exercise 12.2.8: Addition and Subtraction with Significant Figures
Add 4.383 g and 0.0023 g.
Solution
4.38 3 g
–
0.002 3 g
––
–––––––
4.38 5 g
–
In multiplication and division, the product or quotient should contain no more digits than that in the factor containing the least
number of significant figures.
 Exercise 12.2.9: Multiplication and Division with Significant Figures
Multiply 0.6238 by 6.6.
Solution
0.623 8 × 6. 6 = 4. 1
– – –
When rounding numbers, increase the retained digit by 1 if it is followed by a number larger than 5 (“round up”). Do not change
the retained digit if the digits that follow are less than 5 (“round down”). If the retained digit is followed by 5, round up if the
retained digit is odd, or round down if it is even (after rounding, the retained digit will thus always be even).
The Use of Logarithms and Exponential Numbers

The common logarithm of a number (log) is the power to which 10 must be raised to equal that number. For example, the common
logarithm of 100 is 2, because 10 must be raised to the second power to equal 100. Additional examples follow.
Logarithms and Exponential Numbers
Number Number Expressed Exponentially Common Logarithm
1000 103 3
10 101 1
1 100 0
0.1 10−1 −1

Number Number Expressed Exponentially Common Logarithm
0.001 10−3 −3
What is the common logarithm of 60? Because 60 lies between 10 and 100, which have logarithms of 1 and 2, respectively, the
logarithm of 60 is 1.7782; that is,
1.7782
60 = 10
The common logarithm of a number less than 1 has a negative value. The logarithm of 0.03918 is −1.4069, or
−1.4069
1
0.03918 = 10 =
1.4069
10
To obtain the common logarithm of a number, use the log button on your calculator. To calculate a number from its logarithm, take
the inverse log of the logarithm, or calculate 10x (where x is the logarithm of the number).
The natural logarithm of a number (ln) is the power to which e must be raised to equal the number; e is the constant 2.7182818. For
example, the natural logarithm of 10 is 2.303; that is,
2.303 2.303
10 = e = 2.7182818
To obtain the natural logarithm of a number, use the ln button on your calculator. To calculate a number from its natural logarithm,
enter the natural logarithm and take the inverse ln of the natural logarithm, or calculate ex (where x is the natural logarithm of the
number).
Logarithms are exponents; thus, operations involving logarithms follow the same rules as operations involving exponents.
1. The logarithm of a product of two numbers is the sum of the logarithms of the two numbers. \[\log xy= \log x + \log y, \textrm{
and }\ln xy=\ln x + \ln y \nonumber \]
2. The logarithm of the number resulting from the division of two numbers is the difference between the logarithms of the two
numbers. \[\log\dfrac{x}{y}=\log x-\log y,\textrm{ and } \ln\dfrac{x}{y}=\ln x-\ln y \nonumber \]
3. The logarithm of a number raised to an exponent is the product of the exponent and the logarithm of the number.
n n
log x = n log x and ln x = n ln x
The Solution of Quadratic Equations

Mathematical functions of this form are known as second-order polynomials or, more commonly, quadratic functions.
2
ax + bx + c = 0
The solution or roots for any quadratic equation can be calculated using the following formula:
− − −−−−−
2
−b ± √ b − 4ac
x =
2a
Solving Quadratic Equations Solve the quadratic equation 3x2 + 13x − 10 = 0.

Solution Substituting the values a = 3, b = 13, c = −10 in the formula, we obtain
−−−−−−−−−−−−−−−− −
2
−13 ± √ (13 ) − 4 × 3 × (−10)
x =
2 ×3
− −−−−− −− −−−
−13 ± √ 169 + 120 −13 ± √289 −13 ± 17
x = = =
6 6 6
The two roots are therefore

−13 + 17 2 −13 − 17
x = = and x = = −5
6 3 6
Quadratic equations constructed on physical data always have real roots, and of these real roots, often only those having positive
values are of any significance.

Two-Dimensional (x-y) Graphing
The relationship between any two properties of a system can be represented graphically by a two-dimensional data plot. Such a
graph has two axes: a horizontal one corresponding to the independent variable, or the variable whose value is being controlled (x),
and a vertical axis corresponding to the dependent variable, or the variable whose value is being observed or measured (y).
When the value of y is changing as a function of x (that is, different values of x correspond to different values of y), a graph of this
change can be plotted or sketched. The graph can be produced by using specific values for (x,y) data pairs.
 Exercise 12.2.10
Graphing the Dependence of y on x

Table for Exercise 10
x y
1 5
2 10
3 7
4 14
This table contains the following points: (1,5), (2,10), (3,7), and (4,14). Each of these points can be plotted on a graph and
connected to produce a graphical representation of the dependence of y on x.
If the function that describes the dependence of y on x is known, it may be used to compute x,y data pairs that may subsequently be
plotted.
 Exercise 12.2.11
Plotting Data Pairs If we know that y = x2 + 2, we can produce a table of a few (x,y) values and then plot the line based on the
data shown here.
Table for Exercise 11
x y = x2 + 2
1 3
2 6
3 11
4 18

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Formation Constants for Complex Ions
Formation Constants for Complex Ions
Equilibrium Kf
Al
3+
+6F
−
⇌ [AlF ]
6
3−
7 × 1019
Cd
2+
+ 4 NH
3
⇌ [Cd(NH ) ]
3 4
2+
1.3 × 107
Cd
2+
+ 4 CN
−
⇌ [Cd(CN) ]
4
2−
3 × 1018
Co
2+
+ 6 NH
3
⇌ [Co (NH ) ]
3 6
2+
1.3 × 105
Co
3+
+ 6 NH
3
⇌ [Co (NH ) ]
3 6
3+
2.3 × 1033
1.0 × 1016
+ −
Cu + 2 CN ⇌ [Cu(CN) ]
2
Cu
2+
+ 4 NH
3
⇌ [Cu(NH ) ]
3 4
2+
1.7 × 1013
Fe
2+
+ 6 CN
−
⇌ [Fe(CN) ]
6
4−
1.5 × 1035
Fe
3+
+ 6 CN
−
⇌ [Fe(CN) ]
6
3−
2 × 1043
Fe
3+
+ 6 SCN
−
⇌ [Fe(SCN) ]
6
3−
3.2 × 103
Hg
2+
+ 4 Cl
−
⇌ [HgCl ]
4
2−
1.1 × 1016
Ni
2+
+ 6 NH
3
⇌ [Ni(NH ) ]
3 6
2+
2.0 × 108
1.8 × 105
+ − −
Ag + 2 Cl ⇌ [AgCl ]
2
1 × 1021
+ − −
Ag + 2 CN ⇌ [Ag (CN) ]
2
1.7 × 107
+ +
Ag + 2 NH ⇌ [Ag (NH ) ]
3 3 2
Zn
2+
+ 4 CN
−
⇌ [Zn(CN) ]
4
2−
2.1 × 1019
Zn
2+
+ 4 OH
−
⇌ [Zn(OH) ]
4
2−
2 × 1015
Fe
3+
+ SCN
−
⇌ [Fe(SCN)]
2+
8.9 × 102
Ag
+
+ 4 SCN
−
⇌ [Ag (SCN) ]
4
3−
1.2 × 1010
Pb
2+
+4I
−
⇌ [PbI ]
4
2−
3.0 × 104
Pt
2+
+ 4 Cl
−
⇌ [PtCl ]
4
2−
1 × 1016
Cu
2+
+ 4 CN ⇌ [Cu(CN) ]
4
2−
1.0 × 1025
Co
2+
+ 4 SCN
−
⇌ [Co (SCN) ]
4
2−
1 × 103
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Fundamental Physical Constants
Fundamental Physical Constants
Name and Symbol Value
atomic mass unit (amu) 1.6605402 × 10−27 kg
Avogadro’s number 6.0221367 × 1023 mol−1
Boltzmann’s constant (k) 1.380658 × 10−23 J K−1
charge-to-mass ratio for electron (e/me) 1.75881962 × 1011 C kg−1
electron charge (e) 1.60217733 × 10−19 C
electron rest mass (me) 9.1093897 × 10−31 kg
Faraday’s constant (F) 9.6485309 × 104 C mol−1
gas constant (R) 8.205784 × 10−2 L atm mol−1 K−1 = 8.314510 J mol−1 K−1
molar volume of an ideal gas, 1 atm, 0 °C 22.41409 L mol–1
molar volume of an ideal gas, 1 bar, 0 °C 22.71108 L mol–1
neutron rest mass (mn) 1.6749274 × 10−27 kg
Planck’s constant (h) 6.6260755 × 10−34 J s
proton rest mass (mp) 1.6726231 × 10−27 kg
Rydberg constant (R) 1.0973731534 × 107 m−1 = 2.1798736 × 10−18 J
speed of light (in vacuum) (c) 2.99792458 × 108 m s−1
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Ionization Constants of Weak Acids
Acid Formula Ka at 25 °C Lewis Structure
acetic CH3CO2H 1.8 × 10−5
H3AsO4 5.5 × 10−3
1.7 × 10−7
arsenic
5.1 × 10−12
arsenous H3AsO3 5.1 × 10−10
boric H3BO3 5.4 × 10−10
H2CO3 4.3 × 10−7
carbonic
4.7 × 10−11
cyanic HCNO 2 × 10−4
formic HCO2H 1.8 × 10−4
hydrazoic HN3 2.5 × 10−5
hydrocyanic HCN 4.9 × 10−10
hydrofluoric HF 3.5 × 10−4
hydrogen peroxide H2O2 2.4 × 10−12
H2Se 1.29 × 10−4

hydrogen selenide
HSe– 1 × 10−12

Acid Formula Ka at 25 °C Lewis Structure
hydrogen sulfate ion 1.2 × 10−2
H2S 8.9 × 10−8

hydrogen sulfide
HS– 1.0 × 10−19
H2Te 2.3 × 10−3

hydrogen telluride
HTe– 1.6 × 10−11
hypobromous HBrO 2.8 × 10−9
hypochlorous HClO 2.9 × 10−8
nitrous HNO2 4.6 × 10−4
H2C2O4 6.0 × 10−2

oxalic
6.1 × 10−5
H3PO4 7.5 × 10−3
6.2 × 10−8
phosphoric
4.2 × 10−13
H3PO3 5 × 10−2
phosphorous
2.0 × 10−7
H2SO3 1.6 × 10−2
sulfurous
6.4 × 10−8
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Ionization Constants of Weak Bases
Ionization Constants of Weak Bases
Base Lewis Structure Kb at 25 °C
ammonia 1.8 × 10−5
dimethylamine 5.9 × 10−4
methylamine 4.4 × 10−4
phenylamine (aniline) 4.3 × 10−10
trimethylamine 6.3 × 10−5
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Solubility Products
Solubility Products
Substance Ksp at 25 °C
aluminum
Al(OH)3 2 × 10−32
barium
BaCO3 1.6 × 10−9
BaC2O4·2H2O 1.1 × 10−7
BaSO4 2.3 × 10−8
BaCrO4 8.5 × 10−11
BaF2 2.4 × 10−5
Ba(OH)2·8H2O 5.0 × 10−3
Ba3(PO4)2 6 × 10−39
Ba3(AsO4)2 1.1 × 10−13
bismuth
BiO(OH) 4 × 10−10
BiOCl 1.8 × 10−31
Bi2S3 1 × 10−97
cadmium
Cd(OH)2 5.9 × 10−15
CdS 1.0 × 10−28
CdCO3 5.2 × 10−12
calcium
Ca(OH)2 1.3 × 10−6
CaCO3 8.7 × 10−9
CaSO4·2H2O 6.1 × 10−5
CaC2O4·H2O 1.96 × 10−8
Ca3(PO4)2 1.3 × 10−32
CaHPO4 7 × 10−7
CaF2 4.0 × 10−11
chromium
Cr(OH)3 6.7 × 10−31
cobalt
Co(OH)2 2.5 × 10−16
CoS(α) 5 × 10−22
CoS(β) 3 × 10−26
CoCO3 1.4 × 10−13
Co(OH)3 2.5 × 10−43

Solubility Products
copper
CuCl 1.2 × 10−6
CuBr 6.27 × 10−9
CuI 1.27 × 10−12
CuSCN 1.6 × 10−11
Cu2S 2.5 × 10−48
Cu(OH)2 2.2 × 10−20
CuS 8.5 × 10−45
CuCO3 2.5 × 10−10
iron
Fe(OH)2 1.8 × 10−15
FeCO3 2.1 × 10−11
FeS 3.7 × 10−19
Fe(OH)3 4 × 10−38
lead
Pb(OH)2 1.2 × 10−15
PbF2 4 × 10−8
PbCl2 1.6 × 10−5
PbBr2 4.6 × 10−6
PbI2 1.4 × 10−8
PbCO3 1.5 × 10−15
PbS 7 × 10−29
PbCrO4 2 × 10−16
PbSO4 1.3 × 10−8
Pb3(PO4)2 1 × 10−54
magnesium
Mg(OH)2 8.9 × 10−12
MgCO3·3H2O ca 1 × 10−5
MgNH4PO4 3 × 10−13
MgF2 6.4 × 10−9
MgC2O4 7 × 10−7
manganese
Mn(OH)2 2 × 10−13
MnCO3 8.8 × 10−11
MnS 2.3 × 10−13
mercury
Hg2O·H2O 3.6 × 10−26

Solubility Products
Hg2Cl2 1.1 × 10−18
Hg2Br2 1.3 × 10−22
Hg2I2 4.5 × 10−29
Hg2CO3 9 × 10−15
Hg2SO4 7.4 × 10−7
Hg2S 1.0 × 10−47
Hg2CrO4 2 × 10−9
HgS 1.6 × 10−54
nickel
Ni(OH)2 1.6 × 10−16
NiCO3 1.4 × 10−7
NiS(α) 4 × 10−20
NiS(β) 1.3 × 10−25
potassium
KClO4 1.05 × 10−2
K2PtCl6 7.48 × 10−6
KHC4H4O6 3 × 10−4
silver
1
2
Ag O(Ag
2
+
+ OH
−
) 2 × 10−8
AgCl 1.6 × 10−10
AgBr 5.0 × 10−13
AgI 1.5 × 10−16
AgCN 1.2 × 10−16
AgSCN 1.0 × 10−12
Ag2S 1.6 × 10−49
Ag2CO3 8.1 × 10−12
Ag2CrO4 9.0 × 10−12
Ag4Fe(CN)6 1.55 × 10−41
Ag2SO4 1.2 × 10−5
Ag3PO4 1.8 × 10−18
strontium
Sr(OH)2·8H2O 3.2 × 10−4
SrCO3 7 × 10−10
SrCrO4 3.6 × 10−5
SrSO4 3.2 × 10−7
SrC2O4·H2O 4 × 10−7
thallium

Solubility Products
TlCl 1.7 × 10−4
TlSCN 1.6 × 10−4
Tl2S 6 × 10−22
Tl(OH)3 6.3 × 10−46
tin
Sn(OH)2 3 × 10−27
SnS 1 × 10−26
Sn(OH)4 1.0 × 10−57
zinc
ZnCO3 2 × 10−10
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Standard Electrode (Half-Cell) Potentials
Half-Reaction E° (V)
Ag
+
+e
−
⟶ Ag +0.7996
AgCl + e
−
⟶ Ag + Cl
−
+0.22233
−
[Ag (CN) ]
2
+e
−
⟶ Ag + 2 CN
−
−0.31
Ag CrO
2 4
+2e
−
⟶ 2 Ag + CrO
2−
4
+0.45
+
[Ag (NH ) ]
3 2
+e
−
⟶ Ag + 2 NH
3
+0.373
[Ag (S O ) ]
2 3 2
3+
+e
−
⟶ Ag + 2 S O
2
2−
3
+0.017
[AlF ]
6
3−
+3e
−
⟶ Al + 6 F
−
−2.07
Al
3+
+3e
−
⟶ Al −1.662
Am
3+
+3e
−
⟶ Am −2.048
Au
3+
+3e
−
⟶ Au +1.498
Au
+
+e
−
⟶ Au +1.692
Ba
2+
+2e
−
⟶ Ba −2.912
Be
2+
+2e
−
⟶ Be −1.847
Br (aq) + 2 e
2
−
⟶ 2 Br
−
+1.0873
Ca
2+
+2e
−
⟶ Ca −2.868
Ce
3
+3e
−
⟶ Ce −2.483
Ce
4+
+e
−
⟶ Ce
3+
+1.61
Cd
2+
+2e
−
⟶ Cd −0.4030
[Cd(CN) ]
4
2−
+2e
−
⟶ Cd + 4 CN
−
−1.09
[Cd(NH ) ]
3 4
2+
+2e
−
⟶ Cd + 4 NH
3
−0.61
CdS + 2 e
−
⟶ Cd + S
2−
−1.17
Cl
2
+2e
−
⟶ 2 Cl
−
+1.35827
ClO
−
4
+H O+2e
2
−
⟶ ClO
−
3
+ 2 OH
−
+0.36
ClO
−
3
+H O+2e
2
−
⟶ ClO
−
2
+ 2 OH
−
+0.33
ClO
−
2
+H O+2e
2
−
⟶ ClO
−
+ 2 OH
−
+0.66
ClO
−
+H O+2e
2
−
⟶ Cl
−
+ 2 OH
−
+0.89
ClO
−
4
+2H O
3
+
+2e
−
⟶ ClO
−
3
+3H O
2
+1.189
ClO
−
3
+3H O
3
+
+2e
−
⟶ HClO
2
+4H O
2
+1.21
HClO + H O
3
+
+2e
−
⟶ Cl
−
+2H O
2
+1.482
1
HClO + H O
3
+
+e
−
⟶ Cl
2
+2H O
2
+1.611
2
HClO
2
+2H O
3
+
+2e
−
⟶ HClO + 3 H O
2
+1.628
Co
3+
+e
−
⟶ Co
2+
(2 mol // H SO )
2 4
+1.83
Co
2+
+2e
−
⟶ Co −0.28
[Co (NH ) ]
3 6
3+
+e
−
⟶ [Co (NH ) ]
3 6
2+
+0.1
Co (OH)
3
+e
−
⟶ Co (OH)
2
+ OH
−
+0.17

Cr
3
+3e
−
⟶ Cr −0.744
Cr
3+
+e
−
⟶ Cr
2+
−0.407
Cr
2+
+2e
−
⟶ Cr −0.913
−
[Cu(CN) ]
2
+e
−
⟶ Cu + 2 CN
−
−0.43
CrO
2−
4
+4H O+3e
2
−
⟶ Cr(OH)
3
+ 5 OH
−
−0.13
Cr O
2
2−
7
+ 14 H O
3
+
+6e
−
⟶ 2 Cr
3+
+ 21 H O
2
+1.232
−
[Cr(OH) ]
4
+3e
−
⟶ Cr + 4 OH
−
−1.2
Cr(OH)
3
+3e
−
⟶ Cr + 3 OH
−
−1.48
Cu
2+
+e
−
⟶ Cu
+
+0.153
Cu
2+
+2e
−
⟶ Cu +0.34
Cu
+
+e
−
⟶ Cu +0.521
F
2
+2e
−
⟶ 2F
−
+2.866
Fe
2+
+2e
−
⟶ Fe −0.447
Fe
3+
+e
−
⟶ Fe
2+
+0.771
[Fe(CN) ]
6
3−
+e
−
⟶ [Fe(CN) ]
6
4−
+0.36
Fe(OH)
2
+2e
−
⟶ Fe + 2 OH
−
−0.88
FeS + 2 e
−
⟶ Fe + S
2−
−1.01
Ga
3+
+3e
−
⟶ Ga −0.549
Gd
3+
+3e
−
⟶ Gd −2.279
1
H
2
+e
−
⟶ H
−
−2.23
2
2H O+2e
2
−
⟶ H
2
+ 2 OH
−
−0.8277
H O
2 2
+2H O
3
+
+2e
−
⟶ 4H O
2
+1.776
2H O
3
+
+2e
−
⟶ H
2
+2H O
2
0.00
HO
−
2
+H O+2e
2
−
⟶ 3 OH
−
+0.878
Hf
4+
+4e
−
⟶ Hf −1.55
Hg
2+
+2e
−
⟶ Hg +0.851
2 Hg
2+
+2e
−
⟶ Hg
2+
2
+0.92
Hg
2+
2
+2e
−
⟶ 2 Hg +0.7973
[HgBr ]
4
2−
+2e
−
⟶ Hg + 4 Br
−
+0.21
Hg Cl
2 2
+2e
−
⟶ 2 Hg + 2 Cl
−
+0.26808
[Hg (CN) ]
4
2−
+2e
−
⟶ Hg + 4 CN
−
−0.37
[HgI ]
4
2−
+2e
−
⟶ Hg + 4 I
−
−0.04
HgS + 2 e
−
⟶ Hg + S
2−
−0.70
I
2
+2e
−
⟶ 2I
−
+0.5355
In
3+
+3e
−
⟶ In −0.3382
K
+
+e
−
⟶ K −2.931
La
3+
+3e
−
⟶ La −2.52

Li
+
+e
−
⟶ Li −3.04
Lu
3+
+3e
−
⟶ Lu −2.28
Mg
2+
+2e
−
⟶ Mg −2.372
Mn
2+
+2e
−
⟶ Mn −1.185
MnO
2
+2H O+2e
2
−
⟶ Mn(OH)
2
+ 2 OH
−
−0.05
MnO
−
4
+2H O+3e
2
−
⟶ MnO
2
+ 4 OH
−
+0.558
MnO
2
+4H
+
+2e
−
⟶ Mn
2+
+2H O
2
+1.23
MnO
−
4
+8H
+
+5e
−
⟶ Mn
2+
+4H O
2
+1.507
Na
+
+e
−
⟶ Na −2.71
Nd
3+
+3e
−
⟶ Nd −2.323
Ni
2+
+2e
−
⟶ Ni −0.257
[Ni(NH ) ]
3 6
2+
+2e
−
⟶ Ni + 6 NH
3
−0.49
NiO
2
+4H
+
+2e
−
⟶ Ni
2+
+2H O
2
+1.593
NiO
2
+2H O+2e
2
−
⟶ Ni(OH)
2
+ 2 OH
−
+0.49
NiS + 2 e
−
⟶ Ni + S
2−
+0.76
NO
−
3
+4H
+
+3e
−
⟶ NO + 2 H O
2
+0.957
NO
−
3
+3H
+
+2e
−
⟶ HNO
2
+H O
2
+0.92
NO
−
3
+H O+2e
2
−
⟶ NO
−
2
+ 2 OH
−
+0.10
Np
3+
+3e
−
⟶ Np −1.856
O
2
+2H O+4e
2
−
⟶ 4 OH
−
+0.401
O
2
+2H
+
+2e
−
⟶ H O
2 2
+0.695
O
2
+4H
+
+4e
−
⟶ 2H O
2
+1.229
Pb
2+
+2e
−
⟶ Pb −0.1262
PbO
2
+ SO
2−
4
+4H
+
+2e
−
⟶ PbSO
4
+2H O
2
+1.69
PbS + 2 e
−
⟶ Pb + S
2−
−0.95
PbSO
4
+2e
−
⟶ Pb + SO
2−
4
−0.3505
Pd
2+
+2e
−
⟶ Pd +0.987
[PdCl ]
4
2−
+2e
−
⟶ Pd + 4 Cl
−
+0.591
Pt
2+
+2e
−
⟶ Pt +1.20
[PtBr ]
4
2−
+2e
−
⟶ Pt + 4 Br
−
+0.58
[PtCl ]
4
2−
+2e
−
⟶ Pt + 4 Cl
−
+0.755
[PtCl ]
6
2−
+2e
−
⟶ [PtCl ]
4
2−
+ 2 Cl
−
+0.68
Pu
3
+3e
−
⟶ Pu −2.03
Ra
2+
+2e
−
⟶ Ra −2.92
Rb
+
+e
−
⟶ Rb −2.98
[RhCl
6
]
3−
+3e
−
⟶ Rh + 6 Cl
−
+0.44
S+2 e
−
⟶ S
2−
−0.47627

S+2 H
+
+2e
−
⟶ H S
2
+0.142
Sc
3+
+3e
−
⟶ Sc −2.09
Se + 2 H
+
+2e
−
⟶ H Se
2
−0.399
[SiF ]
6
2−
+4e
−
⟶ Si + 6 F
−
−1.2
SiO
2−
3
+3H O+4e
2
−
⟶ Si + 6 OH
−
−1.697
SiO
2
+4H
+
+4e
−
⟶ Si + 2 H O
2
−0.86
Sm
3+
+3e
−
⟶ Sm −2.304
Sn
4+
+2e
−
⟶ Sn
2+
+0.151
Sn
2+
+2e
−
⟶ Sn −0.1375
[SnF ]
6
2−
+4e
−
⟶ Sn + 6 F
−
−0.25
SnS + 2 e
−
⟶ Sn + S
2−
−0.94
Sr
2+
+2e
−
⟶ Sr −2.89
TeO
2
+4H
+
+4e
−
⟶ Te + 2 H O
2
+0.593
Th
4+
+4e
−
⟶ Th −1.90
Ti
2+
+2e
−
⟶ Ti −1.630
U
3+
+3e
−
⟶ U −1.79
V
2+
+2e
−
⟶ V −1.19
Y
3+
+3e
−
⟶ Y −2.37
Zn
2+
+2e
−
⟶ Zn −0.7618
[Zn(CN) ]
4
2−
+2e
−
⟶ Zn + 4 CN
−
−1.26
[Zn(NH ) ]
3 4
2+
+2e
−
⟶ Zn + 4 NH
3
−1.04
Zn(OH)
2
+2e
−
⟶ Zn + 2 OH
−
−1.245
[Zn(OH) ]
4
2
+2e
−
⟶ Zn + 4 OH
−
−1.199
ZnS + 2 e
−
⟶ Zn + S
2−
−1.40
Zr
4
+4e
−
⟶ Zr −1.539
This page titled 12.8: Standard Electrode (Half-Cell) Potentials is shared under a CC BY license and was authored, remixed, and/or curated by
OpenStax.
Standard Electrode (Half-Cell) Potentials is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

Standard Thermodynamic Properties for Selected Substances
Substance ΔH
∘
f
(kJ mol–) ΔG
∘
f
(kJ mol–1) S
298
∘
(J K–1 mol–1)
aluminum
Al(s) 0 0 28.3
Al(g) 324.4 285.7 164.54
Al
3 +
(aq) -531 -485 -321.7
Al2O3(s) –1676 –1582 50.92
AlF3(s) –1510.4 –1425 66.5
AlCl3(s) –704.2 –628.8 110.67
AlCl3·6H2O(s) –2691.57 –2269.40 376.56
Al2S3(s) –724.0 –492.4 116.9
Al2(SO4)3(s) –3445.06 –3506.61 239.32
antimony
Sb(s) 0 0 45.69
Sb(g) 262.34 222.17 180.16
Sb4O6(s) –1440.55 –1268.17 220.92
SbCl3(g) –313.8 –301.2 337.80
SbCl5(g) –394.34 –334.29 401.94
Sb2S3(s) –174.89 –173.64 182.00
SbCl3(s) –382.17 –323.72 184.10
SbOCl(s) –374.0 — —
arsenic
As(s) 0 0 35.1
As(g) 302.5 261.0 174.21
As4(g) 143.9 92.4 314
As4O6(s) –1313.94 –1152.52 214.22
As2O5(s) –924.87 –782.41 105.44
AsCl3(g) –261.50 –248.95 327.06
As2S3(s) –169.03 –168.62 163.59
AsH3(g) 66.44 68.93 222.78
H3AsO4(s) –906.3 — —
barium
Ba(s) 0 0 62.5
Ba(g) 180 146 170.24
Ba
2 +
(aq) -537.6 -560.8 9.6
BaO(s) –548.0 –520.3 72.1
BaCl2(s) –855.0 –806.7 123.7

Substance ΔH
f
∘
(kJ mol–) ΔG
∘
f
(kJ mol–1) S
∘
298
(J K–1 mol–1)
BaSO4(s) –1473.2 –1362.3 132.2
beryllium
Be(s) 0 0 9.50
Be(g) 324.3 286.6 136.27
BeO(s) –609.4 –580.1 13.8
bismuth
Bi(s) 0 0 56.74
Bi(g) 207.1 168.2 187.00
Bi2O3(s) –573.88 –493.7 151.5
BiCl3(s) –379.07 –315.06 176.98
Bi2S3(s) –143.1 –140.6 200.4
boron
B(s) 0 0 5.86
B(g) 565.0 521.0 153.4
B2O3(s) –1273.5 –1194.3 53.97
B2H6(g) 36.4 87.6 232.1
H3BO3(s) –1094.33 –968.92 88.83
BF3(g) –1136.0 –1119.4 254.4
BCl3(g) –403.8 –388.7 290.1
B3N3H6(l) –540.99 –392.79 199.58
HBO2(s) –794.25 –723.41 37.66
bromine
Br2(l) 0 0 152.23
Br2(g) 30.91 3.142 245.5
Br(g) 111.88 82.429 175.0
Br
−
(aq) -120.9 -102.82 80.71
BrF3(g) –255.60 –229.45 292.42
HBr(g) –36.3 –53.43 198.7
cadmium
Cd(s) 0 0 51.76
Cd(g) 112.01 77.41 167.75
Cd
2 +
(aq) -75.90 -77.61 -73.2
CdO(s) –258.2 –228.4 54.8
CdCl2(s) –391.5 –343.9 115.3
CdSO4(s) –933.3 –822.7 123.0
CdS(s) –161.9 –156.5 64.9
calcium

Substance ΔH
f
∘
(kJ mol–) ΔG
∘
f
(kJ mol–1) S
∘
298
(J K–1 mol–1)
Ca(s) 0 0 41.6
Ca(g) 178.2 144.3 154.88
Ca
2 +
(aq) -542.96 -553.04 -55.2
CaO(s) –634.9 –603.3 38.1
Ca(OH)2(s) –985.2 –897.5 83.4
CaSO4(s) –1434.5 –1322.0 106.5
CaSO4·2H2O(s) –2022.63 –1797.45 194.14
CaCO3(s) (calcite) –1220.0 –1081.4 110.0
CaSO3·H2O(s) –1752.68 –1555.19 184.10
carbon
C(s) (graphite) 0 0 5.740
C(s) (diamond) 1.89 2.90 2.38
C(g) 716.681 671.2 158.1
CO(g) –110.52 –137.15 197.7
CO2(g) –393.51 –394.36 213.8
CO
2 −
3
(aq) -677.1 -527.8 -56.9
CH4(g) –74.6 –50.5 186.3
CH3OH(l) –239.2 –166.6 126.8
CH3OH(g) –201.0 –162.3 239.9
CCl4(l) –128.2 –62.5 214.4
CCl4(g) –95.7 –58.2 309.7
CHCl3(l) –134.1 –73.7 201.7
CHCl3(g) –103.14 –70.34 295.71
CS2(l) 89.70 65.27 151.34
CS2(g) 116.9 66.8 238.0
C2H2(g) 227.4 209.2 200.9
C2H4(g) 52.4 68.4 219.3
C2H6(g) –84.0 –32.0 229.2
CH3CO2H(l) –484.3 –389.9 159.8
CH3CO2H(g) –434.84 –376.69 282.50
C2H5OH(l) –277.6 –174.8 160.7
C2H5OH(g) –234.8 –167.9 281.6
HCO
−
3
(aq) -691.11 -587.06 95
C3H8(g) –103.8 –23.4 270.3
C6H6(g) 82.927 129.66 269.2
C6H6(l) 49.1 124.50 173.4
CH2Cl2(l) –124.2 –63.2 177.8

Substance ΔH
∘
f
(kJ mol–) ΔG
∘
f
(kJ mol–1) S
∘
298
(J K–1 mol–1)
CH2Cl2(g) –95.4 –65.90 270.2
CH3Cl(g) –81.9 –60.2 234.6
C2H5Cl(l) –136.52 –59.31 190.79
C2H5Cl(g) –112.17 –60.39 276.00
C2N2(g) 308.98 297.36 241.90
HCN(l) 108.9 125.0 112.8
HCN(g) 135.5 124.7 201.8
cesium
Cs
+
(aq) -248 -282.0 133
chlorine
Cl2(g) 0 0 223.1
Cl(g) 121.3 105.70 165.2
Cl
−
(aq) -167.2 -131.2 56.5
ClF(g) –54.48 –55.94 217.78
ClF3(g) –158.99 –118.83 281.50
Cl2O(g) 80.3 97.9 266.2
Cl2O7(l) 238.1 — —
Cl2O7(g) 272.0 — —
HCl(g) –92.307 –95.299 186.9
HClO4(l) –40.58 — —
chromium
Cr(s) 0 0 23.77
Cr(g) 396.6 351.8 174.50
CrO
2 −
4
(aq) -881.2 -727.8 50.21
Cr O
2
2 −
7
(aq) -1490.3 -1301.1 261.9
Cr2O3(s) –1139.7 –1058.1 81.2
CrO3(s) –589.5 — —
(NH4)2Cr2O7(s) –1806.7 — —
cobalt
Co(s) 0 0 30.0
Co
2 +
(aq) -67.4 -51.5 -155
Co
3 +
(aq) 92 134 -305.0
CoO(s) –237.9 –214.2 52.97
Co3O4(s) –910.02 –794.98 114.22
Co(NO3)2(s) –420.5 — —
copper
Cu(s) 0 0 33.15

Substance ΔH
f
∘
(kJ mol–) ΔG
∘
f
(kJ mol–1) S
∘
298
(J K–1 mol–1)
Cu(g) 338.32 298.58 166.38
Cu
+
(aq) 51.9 50.2 -26
Cu
2 +
(aq) 64.77 65.49 -99.6
CuO(s) –157.3 –129.7 42.63
Cu2O(s) –168.6 –146.0 93.14
CuS(s) –53.1 –53.6 66.5
Cu2S(s) –79.5 –86.2 120.9
CuSO4(s) –771.36 –662.2 109.2
Cu(NO3)2(s) –302.9 — —
fluorine
F2(g) 0 0 202.8
F(g) 79.4 62.3 158.8
F
−
(aq) -332.6 -278.8 -13.8
F2O(g) 24.7 41.9 247.43
HF(g) –273.3 –275.4 173.8
hydrogen
H2(g) 0 0 130.7
H(g) 217.97 203.26 114.7
H
+
(aq) 0 0 0
OH
−
(aq) -230.0 -157.2 -10.75
H O
3
+
(aq) -285.8 69.91
H2O(l) –285.83 –237.1 70.0
H2O(g) –241.82 –228.59 188.8
H2O2(l) –187.78 –120.35 109.6
H2O2(g) –136.3 –105.6 232.7
HF(g) –273.3 –275.4 173.8
HCl(g) –92.307 –95.299 186.9
HBr(g) –36.3 –53.43 198.7
HI(g) 26.48 1.70 206.59
H2S(g) –20.6 –33.4 205.8
H2Se(g) 29.7 15.9 219.0
iodine
I2(s) 0 0 116.14
I2(g) 62.438 19.3 260.7
I(g) 106.84 70.2 180.8
I
−
(aq) -55.19 -51.57 11.13
IF(g) 95.65 –118.49 236.06

Substance ΔH
∘
f
(kJ mol–) ΔG
∘
f
(kJ mol–1) S
∘
298
(J K–1 mol–1)
ICl(g) 17.78 –5.44 247.44
IBr(g) 40.84 3.72 258.66
IF7(g) –943.91 –818.39 346.44
HI(g) 26.48 1.70 206.59
iron
Fe(s) 0 0 27.3
Fe(g) 416.3 370.7 180.5
Fe
2 +
(aq) -89.1 -78.90 -137.7
Fe
3 +
(aq) -48.5 -4.7 -315.9
Fe2O3(s) –824.2 –742.2 87.40
Fe3O4(s) –1118.4 –1015.4 146.4
Fe(CO)5(l) –774.04 –705.42 338.07
Fe(CO)5(g) –733.87 –697.26 445.18
FeCl2(s) –341.79 –302.30 117.95
FeCl3(s) –399.49 –334.00 142.3
FeO(s) –272.0 –255.2 60.75
Fe(OH)2(s) –569.0 –486.5 88.
Fe(OH)3(s) –823.0 –696.5 106.7
FeS(s) –100.0 –100.4 60.29
Fe3C(s) 25.10 20.08 104.60
lead
Pb(s) 0 0 64.81
Pb(g) 195.2 162. 175.4
Pb
2 +
(aq) -1.7 -24.43 10.5
PbO(s) (yellow) –217.32 –187.89 68.70
PbO(s) (red) –218.99 –188.93 66.5
Pb(OH)2(s) –515.9 — —
PbS(s) –100.4 –98.7 91.2
Pb(NO3)2(s) –451.9 — —
PbO2(s) –277.4 –217.3 68.6
PbCl2(s) –359.4 –314.1 136.0
lithium
Li(s) 0 0 29.1
Li(g) 159.3 126.6 138.8
Li
+
(aq) -278.5 -293.3 13.4
LiH(s) –90.5 –68.3 20.0
Li(OH)(s) –487.5 –441.5 42.8

Substance ΔH
f
∘
(kJ mol–) ΔG
∘
f
(kJ mol–1) S
∘
298
(J K–1 mol–1)
LiF(s) –616.0 –587.5 35.7
Li2CO3(s) –1216.04 –1132.19 90.17
magnesium
Mg
2 +
(aq) -466.9 -454.8 -138.1
manganese
Mn(s) 0 0 32.0
Mn(g) 280.7 238.5 173.7
Mn
2 +
(aq) -220.8 -228.1 -73.6
MnO(s) –385.2 –362.9 59.71
MnO2(s) –520.03 –465.1 53.05
Mn2O3(s) –958.97 –881.15 110.46
Mn3O4(s) –1378.83 –1283.23 155.64
MnO
−
4
(aq) -541.4 -447.2 191.2
MnO
2 −
4
(aq) -653.0 -500.7 59
mercury
Hg(l) 0 0 75.9
Hg(g) 61.4 31.8 175.0
Hg
2 +
(aq) 164.8
Hg
2 +
2
(aq) 172.4 153.9 84.5
HgO(s) (red) –90.83 –58.5 70.29
HgO(s) (yellow) –90.46 –58.43 71.13
HgCl2(s) –224.3 –178.6 146.0
Hg2Cl2(s) –265.4 –210.7 191.6
HgS(s) (red) –58.16 –50.6 82.4
HgS(s) (black) –53.56 –47.70 88.28
HgSO4(s) –707.51 –594.13 0.00
nitrogen
N2(g) 0 0 191.6
N(g) 472.704 455.5 153.3
NO(g) 90.25 87.6 210.8
NO2(g) 33.2 51.30 240.1
N2O(g) 81.6 103.7 220.0
N2O3(g) 83.72 139.41 312.17
NO
−
3
(aq) -205.0 -108.7 146.4
N2O4(g) 11.1 99.8 304.4
N2O5(g) 11.3 115.1 355.7
NH3(g) –45.9 –16.5 192.8

Substance ΔH
∘
f
(kJ mol–) ΔG
∘
f
(kJ mol–1) S
∘
298
(J K–1 mol–1)
NH
+
4
(aq) -132.5 -79.31 113.4
N2H4(l) 50.63 149.43 121.21
N2H4(g) 95.4 159.4 238.5
NH4NO3(s) –365.56 –183.87 151.08
NH4Cl(s) –314.43 –202.87 94.6
NH4Br(s) –270.8 –175.2 113.0
NH4I(s) –201.4 –112.5 117.0
NH4NO2(s) –256.5 — —
HNO3(l) –174.1 –80.7 155.6
HNO3(g) –133.9 –73.5 266.9
oxygen
O2(g) 0 0 205.2
O(g) 249.17 231.7 161.1
O3(g) 142.7 163.2 238.9
phosphorus
P4(s) 0 0 164.4
P4(g) 58.91 24.4 280.0
P(g) 314.64 278.25 163.19
PH3(g) 5.4 13.5 210.2
PCl3(g) –287.0 –267.8 311.78
PCl5(g) –374.9 –305.0 364.4
P4O6(s) –1640.1 — —
P4O10(s) –2984.0 –2697.0 228.86
PO
3 −
4
(aq) -1277 -1019 -222
HPO3(s) –948.5 — —
HPO
2 −
4
(aq) -1292.1 -1089.3 -33
H PO
2
−
4
(aq) -1296.3 -1130.4 90.4
H3PO2(s) –604.6 — —
H3PO3(s) –964.4 — —
H3PO4(s) –1279.0 –1119.1 110.50
H3PO4(l) –1266.9 –1124.3 110.5
H4P2O7(s) –2241.0 — —
POCl3(l) –597.1 –520.8 222.5
POCl3(g) –558.5 –512.9 325.5
potassium
K(s) 0 0 64.7
K(g) 89.0 60.5 160.3

Substance ΔH
f
∘
(kJ mol–) ΔG
∘
f
(kJ mol–1) S
∘
298
(J K–1 mol–1)
K
+
(aq) -252.4 -283.3 102.5
KF(s) –576.27 –537.75 66.57
KCl(s) –436.5 –408.5 82.6
rubidium
Rb
+
(aq) -246 -282.2 124
silicon
Si(s) 0 0 18.8
Si(g) 450.0 405.5 168.0
SiO2(s) –910.7 –856.3 41.5
SiH4(g) 34.3 56.9 204.6
H2SiO3(s) –1188.67 –1092.44 133.89
H4SiO4(s) –1481.14 –1333.02 192.46
SiF4(g) –1615.0 –1572.8 282.8
SiCl4(l) –687.0 –619.8 239.7
SiCl4(g) –662.75 –622.58 330.62
SiC(s, beta cubic) –73.22 –70.71 16.61
SiC(s, alpha hexagonal) –71.55 –69.04 16.48
silver
Ag(s) 0 0 42.55
Ag(g) 284.9 246.0 172.89
Ag
+
(aq) 105.6 77.11 72.68
Ag2O(s) –31.05 –11.20 121.3
AgCl(s) –127.0 –109.8 96.3
Ag2S(s) –32.6 –40.7 144.0
sodium
Na(s) 0 0 51.3
Na(g) 107.5 77.0 153.7
Na
+
(aq) -240.1 -261.9 59
Na2O(s) –414.2 –375.5 75.1
NaCl(s) –411.2 –384.1 72.1
strontium
Sr
2 +
(aq) -545.8 -557.3 -32.6
sulfur
S8(s) (rhombic) 0 0 256.8
S(g) 278.81 238.25 167.82
S
2 −
(aq) 41.8 83.7 22
SO2(g) –296.83 –300.1 248.2

Substance ΔH
∘
f
(kJ mol–) ΔG
∘
f
(kJ mol–1) S
∘
298
(J K–1 mol–1)
SO3(g) –395.72 –371.06 256.76
SO
2 −
4
(aq) -909.3 -744.5 20.1
S O
2
2 −
3
(aq) -648.5 -522.5 67
H2S(g) –20.6 –33.4 205.8
HS
−
(aq) -17.7 12.6 61.1
H2SO4(l) –813.989 690.00 156.90
HSO
−
4
(aq) -885.75 -752.87 126.9
H2S2O7(s) –1273.6 — —
SF4(g) –728.43 –684.84 291.12
SF6(g) –1220.5 –1116.5 291.5
SCl2(l) –50 — —
SCl2(g) –19.7 — —
S2Cl2(l) –59.4 — —
S2Cl2(g) –19.50 –29.25 319.45
SOCl2(g) –212.55 –198.32 309.66
SOCl2(l) –245.6 — —
SO2Cl2(l) –394.1 — —
SO2Cl2(g) –354.80 –310.45 311.83
tin
Sn(s) 0 0 51.2
Sn(g) 301.2 266.2 168.5
SnO(s) –285.8 –256.9 56.5
SnO2(s) –577.6 –515.8 49.0
SnCl4(l) –511.3 –440.1 258.6
SnCl4(g) –471.5 –432.2 365.8
titanium
Ti(s) 0 0 30.7
Ti(g) 473.0 428.4 180.3
TiO2(s) –944.0 –888.8 50.6
TiCl4(l) –804.2 –737.2 252.4
TiCl4(g) –763.2 –726.3 353.2
tungsten
W(s) 0 0 32.6
W(g) 849.4 807.1 174.0
WO3(s) –842.9 –764.0 75.9
zinc
Zn(s) 0 0 41.6

Substance ΔH
f
∘
(kJ mol–) ΔG
∘
f
(kJ mol–1) S
∘
298
(J K–1 mol–1)
Zn(g) 130.73 95.14 160.98
Zn
2 +
(aq) -153.9 -147.1 -112.1
ZnO(s) –350.5 –320.5 43.7
ZnCl2(s) –415.1 –369.43 111.5
ZnS(s) –206.0 –201.3 57.7
ZnSO4(s) –982.8 –871.5 110.5
ZnCO3(s) –812.78 –731.57 82.42
complexes
[Co(NH3)4(NO2)2]NO3, cis –898.7 — —
[Co(NH3)4(NO2)2]NO3, trans –896.2 — —
NH4[Co(NH3)2(NO2)4] –837.6 — —
[Co(NH3)6][Co(NH3)2(NO2)4]3 –2733.0 — —
[Co(NH3)4Cl2]Cl, cis –874.9 — —
[Co(NH3)4Cl2]Cl, trans –877.4 — —
[Co(en)2(NO2)2]NO3, cis –689.5 — —
[Co(en)2Cl2]Cl, cis –681.2 — —
[Co(en)2Cl2]Cl, trans –677.4 — —
[Co(en)3](ClO4)3 –762.7 — —
[Co(en)3]Br2 –595.8 — —
[Co(en)3]I2 –475.3 — —
[Co(en)3]I3 –519.2 — —
[Co(NH3)6](ClO4)3 –1034.7 –221.1 615
[Co(NH3)5NO2](NO3)2 –1088.7 –412.9 331
[Co(NH3)6](NO3)3 –1282.0 –524.5 448
[Co(NH3)5Cl]Cl2 –1017.1 –582.5 366.1
[Pt(NH3)4]Cl2 –725.5 — —
[Ni(NH3)6]Cl2 –994.1 — —
[Ni(NH3)6]Br2 –923.8 — —
[Ni(NH3)6]I2 –808.3 — —
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Units of Length
Units of Length
= 39.37 inches (in.) = 1.094 yards = 10–8 cm (exact, definition) = 10–

meter (m) angstrom (Å) 10
(yd) m (exact, definition)
centimeter (cm) = 0.01 m (exact, definition) yard (yd) = 0.9144 m
millimeter (mm) = 0.001 m (exact, definition) inch (in.) = 2.54 cm (exact, definition)
kilometer (km) = 1000 m (exact, definition) mile (US) = 1.60934 km
Units of Volume
Units of Volume
= 0.001 m3 (exact, definition) = = 32 (US) liquid ounces (exact,

liter (L) 1000 cm3 (exact, definition) = liquid quart (US) definition) = 0.25 (US) gallon
1.057 (US) quarts (exact, definition) = 0.9463 L
= 0.001 L (exact, definition) = 1

milliliter (mL) dry quart = 1.1012 L
cm3 (exact, definition)
= 10–6 L (exact, definition) = 10–3

microliter (μL) cubic foot (US) = 28.316 L
cm3 (exact, definition)
Units of Mass
Units of Mass
gram (g) = 0.001 kg (exact, definition) ounce (oz) (avoirdupois) = 28.35 g
milligram (mg) = 0.001 g (exact, definition) pound (lb) (avoirdupois) = 0.4535924 kg
= 1000 g (exact, definition) = =2000 lb (exact, definition) =

kilogram (kg) ton (short)
2.205 lb 907.185 kg
=1000 kg (exact, definition) = = 2240 lb (exact, definition) =

ton (metric) ton (long)
2204.62 lb 1.016 metric ton
Units of Energy
Units of Energy
4.184 joule (J) = 1 thermochemical calorie (cal)
1 thermochemical calorie (cal) = 4.184 × 107 erg
erg = 10–7 J (exact, definition)
electron-volt (eV) = 1.60218 × 10−19 J = 23.061 kcal mol−1
liter·atmosphere = 24.217 cal = 101.325 J (exact, definition)
nutritional calorie (Cal) = 1000 cal (exact, definition) = 4184 J
British thermal unit (BTU) = 1054.804 J1
Units of Pressure
Units of Pressure
torr = 1 mm Hg (exact, definition)
pascal (Pa) = N m–2 (exact, definition) = kg m–1 s–2 (exact, definition)
= 760 mm Hg (exact, definition) = 760 torr (exact, definition) = 101,325

atmosphere (atm)
N m–2 (exact, definition) = 101,325 Pa (exact, definition)
bar = 105 Pa (exact, definition) = 105 kg m–1 s–2 (exact, definition)

Footnotes
1. 1 BTU is the amount of energy needed to heat one pound of water by one degree Fahrenheit. Therefore, the exact relationship
of BTU to joules and other energy units depends on the temperature at which BTU is measured. 59 °F (15 °C) is the most
widely used reference temperature for BTU definition in the United States. At this temperature, the conversion factor is the one
provided in this table.
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Water Density (kg/m3) at Different Temperatures (°C)
Temperature1 Density
0 999.8395
4 999.9720 (density maximum)
10 999.7026
15 999.1026
20 998.2071
22 997.7735
25 997.0479
30 995.6502
40 992.2
60 983.2
80 971.8
100 958.4
Water Vapor Pressure at Different Temperatures (°C)

Temperature Vapor Pressure (torr) Vapor Pressure (Pa)
0 4.6 613.2812
4 6.1 813.2642
10 9.2 1226.562
15 12.8 1706.522
20 17.5 2333.135

Temperature Vapor Pressure (torr) Vapor Pressure (Pa)
22 19.8 2639.776
25 23.8 3173.064
30 31.8 4239.64
35 42.2 5626.188
40 55.3 7372.707
45 71.9 9585.852
50 92.5 12332.29
55 118.0 15732
60 149.4 19918.31
65 187.5 24997.88
70 233.7 31157.35
75 289.1 38543.39
80 355.1 47342.64
85 433.6 57808.42
90 525.8 70100.71
95 633.9 84512.82
100 760.0 101324.7
Water Kw and pKw at Different Temperatures (°C)

Temperature Kw 10–14 pKw2
0 0.112 14.95
5 0.182 14.74
10 0.288 14.54
15 0.465 14.33
20 0.671 14.17

Temperature Kw 10–14 pKw2
25 0.991 14.00
30 1.432 13.84
35 2.042 13.69
40 2.851 13.55
45 3.917 13.41
50 5.297 13.28
55 7.080 13.15
60 9.311 13.03
75 19.95 12.70
100 56.23 12.25
Specific Heat Capacity for Water

Specific Heat Capacity for Water
C°(H2O(l)) = 4184 J·K−1·kg−1 = 4.184 J·g-1·°C-1

C°(H2O(s)) = 1864 J·K−1·kg−1
C°(H2O(g)) = 2093 J·K−1·kg−1
Standard Water Melting and Boiling Temperatures and Enthalpies of the Transitions
Standard Water Melting and Boiling Temperatures and Enthalpies of the Transitions
Temperature (K) ΔH (kJ/mol)
melting 273.15 6.088
boiling 373.15 40.656 (44.016 at 298 K)
Water Cryoscopic (Freezing Point Depression) and Ebullioscopic (Boiling Point Elevation) Constants
Water Cryoscopic (Freezing Point Depression) and Ebullioscopic (Boiling Point Elevation) Constants
Kf = 1.86°C·kg·mol−1 (cryoscopic constant)

Kb = 0.51°C·kg·mol−1 (ebullioscopic constant)

<figure class="ui-has-child-figcaption" >
Water full-range spectral absorption curve. This curve shows the full-range spectral absorption for water. The y-axis signifies the
absorption in 1/cm. If we divide 1 by this value, we will obtain the length of the path (in cm) after which the intensity of a light
beam passing through water decays by a factor of the base of the natural logarithm e (e = 2.718281828).
Footnotes
1. 1 Data for t < 0 °C are for supercooled water
2. 2 pKw = –log10(Kw)
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Index
A B chemical equation
absolute zero balanced equation 7.2: Writing and Balancing Chemical Equations
8.2: Relating Pressure, Volume, Amount, and 7.2: Writing and Balancing Chemical Equations chemical property
Temperature- The Ideal Gas Law bar 1.3: Physical and Chemical Properties
accuracy 8.1: Gas Pressure chemical symbol
1.5: Measurement Uncertainty, Accuracy, and barometer 2.4: Atomic Structure and Symbolism
Precision
8.1: Gas Pressure chemical thermodynamics
Actinide binary acid 9.4: Enthalpy
2.8: Chemical Nomenclature chemistry
actual yield binary compound 1.1: Chemistry in Context
2.8: Chemical Nomenclature coefficient
adhesive force blackbody 7.2: Writing and Balancing Chemical Equations
3.1: Electromagnetic Energy cohesive force
alkali metal Bohr's model of the hydrogen atom 10.3: Properties of Liquids
3.2: The Bohr Model colligative property
alkaline earth metal boiling point 11.5: Colligative Properties
10.4: Phase Transitions colloid
alloy boiling point elevation 11.6: Colloids
11.5: Colligative Properties combustion analysis
alpha particle boiling point elevation constant 7.6: Quantitative Chemical Analysis
11.5: Colligative Properties Combustion Reaction
Amonton's law bomb calorimeter 7.3: Classifying Chemical Reactions
8.2: Relating Pressure, Volume, Amount, and
9.3: Calorimetry complete ionic equation
Temperature- The Ideal Gas Law
bond angle 7.2: Writing and Balancing Chemical Equations
amorphous solid compound
bond dipole moment 1.2: Phases and Classification of Matter
amphiphilic compressibility factor
11.6: Colloids
bond distance 8.6: Non-Ideal Gas Behavior
amplitude concentrated
bond energy 6.3: Molarity
analyte concentration
bond length 6.3: Molarity
angular momentum quantum number condensation
Boyle's Law 10.4: Phase Transitions
anion continuous spectrum
Temperature- The Ideal Gas Law 3.1: Electromagnetic Energy
aqueous solution Bragg equation conversion factors
6.3: Molarity
10.7: Lattice Structures in Crystalline Solids 1.6: Mathematical Treatment of Measurement
atmosphere Buret Results
8.1: Gas Pressure
7.6: Quantitative Chemical Analysis coordination number
atom 10.7: Lattice Structures in Crystalline Solids
C core electron
atomic mass 3.4: Electronic Structure of Atoms (Electron
calorie Configurations)
9.2: Energy Basics
atomic mass unit covalent bond
calorimeter 2.7: Molecular and Ionic Compounds
9.3: Calorimetry 4.3: Covalent Bonding
atomic number
calorimetry covalent compound
9.3: Calorimetry 2.7: Molecular and Ionic Compounds
atomic orbital
capillary action covalent network solid
10.3: Properties of Liquids 10.6: The Solid State of Matter
aufbau principle
3.4: Electronic Structure of Atoms (Electron
cation covalent radius
Configurations) 2.4: Atomic Structure and Symbolism 3.5: Periodic Variations in Element Properties
Avogadro's law Celsius crenation
8.2: Relating Pressure, Volume, Amount, and 1.4: Measurements 11.5: Colligative Properties
Temperature- The Ideal Gas Law chalcogen critical point
Avogadro's number 2.6: The Periodic Table 10.5: Phase Diagrams
6.1: Formula Mass and the Mole Concept Charles's Law crystalline solid
axial position 8.2: Relating Pressure, Volume, Amount, and 10.6: The Solid State of Matter
4.7: Molecular Structure and Polarity cubic centimeter
chemical change 1.4: Measurements
cubic closest packing electron configuration freezing point depression
10.7: Lattice Structures in Crystalline Solids 3.4: Electronic Structure of Atoms (Electron 11.5: Colligative Properties
cubic meter Configurations) freezing point depression constant
1.4: Measurements electron density 11.5: Colligative Properties
3.3: Development of Quantum Theory frequency
D electronegativity 3.1: Electromagnetic Energy
4.3: Covalent Bonding fundamental unit of charge
d orbital
element 2.4: Atomic Structure and Symbolism
Dalton unit
empirical formula G
Dalton's atomic theory gas
empirical formula mass 1.2: Phases and Classification of Matter
Dalton's Law of Partial Pressure gel
8.3: Stoichiometry of Gaseous Substances, Mixtures,
emulsifying agent 11.6: Colloids
and Reactions 11.6: Colloids
goiter
density emulsion 2.4: Atomic Structure and Symbolism
1.4: Measurements 11.6: Colloids
Graham's law
deposition End point 8.4: Effusion and Diffusion of Gases
10.4: Phase Transitions 7.6: Quantitative Chemical Analysis
gravimetric analysis
diffraction endothermic process 7.6: Quantitative Chemical Analysis
10.7: Lattice Structures in Crystalline Solids 9.2: Energy Basics
ground state
diffusion energy 3.2: The Bohr Model
8.4: Effusion and Diffusion of Gases 9.2: Energy Basics
group
diluted enthalpy 2.6: The Periodic Table
6.3: Molarity 9.4: Enthalpy
dilution Enthalpy change H
6.3: Molarity 9.4: Enthalpy
halogen
Dimensional Analysis equatorial position
1.6: Mathematical Treatment of Measurement 4.7: Molecular Structure and Polarity
heat
Results equivalence point
9.2: Energy Basics
dipole moment 7.6: Quantitative Chemical Analysis
Heat capacity
4.7: Molecular Structure and Polarity exact number
9.2: Energy Basics
dispersed phase 1.5: Measurement Uncertainty, Accuracy, and
11.6: Colloids Precision Heisenberg Uncertainty Principle
excess reactant 3.3: Development of Quantum Theory
dispersion
10.2: Intermolecular Forces 7.5: Reaction Yields hemolysis
excited state 11.5: Colligative Properties
dispersion medium
11.6: Colloids 3.2: The Bohr Model Henry's law
exothermic process 11.4: Solubility
dissociation
11.3: Electrolytes 9.2: Energy Basics hertz
expansion work 3.1: Electromagnetic Energy
dissolved
6.3: Molarity 9.4: Enthalpy Hess's law
extensive property 9.4: Enthalpy
double bond
4.4: Lewis Symbols and Structures 1.3: Physical and Chemical Properties heterogeneous mixture
dynamic equilibrium
10.4: Phase Transitions F hexagonal closest packing
f orbital
E 3.3: Development of Quantum Theory
hole
effective nuclear charge Fahrenheit
1.6: Mathematical Treatment of Measurement
homogeneous mixture
Results 1.2: Phases and Classification of Matter
effusion Hund's rule
first law of thermodynamics
9.4: Enthalpy 3.4: Electronic Structure of Atoms (Electron
electrolyte Configurations)
11.3: Electrolytes
formal charge
hybrid orbital
electromagnetic radiation 5.3: Hybrid Atomic Orbitals
formula mass
hybridization
electromagnetic spectrum 5.3: Hybrid Atomic Orbitals
Free radical
hydrocarbon
electron 9.4: Enthalpy
freezing
hydrogen bonding
electron affinity 10.2: Intermolecular Forces
freezing point
hydrostatic pressure
8.1: Gas Pressure
hypertonic isomers manometer
11.5: Colligative Properties 2.5: Chemical Formulas 8.1: Gas Pressure
hypervalent molecule isomorphous mass
4.4: Lewis Symbols and Structures 10.7: Lattice Structures in Crystalline Solids 1.2: Phases and Classification of Matter
hypothesis isotonic mass number
1.1: Chemistry in Context 11.5: Colligative Properties 2.4: Atomic Structure and Symbolism
hypotonic isotope mass percentage
11.5: Colligative Properties 2.3: Evolution of Atomic Theory 6.4: Other Units for Solution Concentrations
mean free path
I J 8.4: Effusion and Diffusion of Gases
ideal gas joule melting
8.2: Relating Pressure, Volume, Amount, and 9.2: Energy Basics 10.4: Phase Transitions
Temperature- The Ideal Gas Law melting point
ideal gas constant K 10.4: Phase Transitions
kelvin metal
Temperature- The Ideal Gas Law 2.6: The Periodic Table
1.4: Measurements
ideal gas law metallic solid
kilogram
1.4: Measurements 10.6: The Solid State of Matter
kinetic energy metalloid
ideal solution
9.2: Energy Basics 2.6: The Periodic Table
kinetic molecular theory meter
immiscible
8.5: The Kinetic-Molecular Theory 1.4: Measurements
11.4: Solubility
microscopic domain
indicator
7.6: Quantitative Chemical Analysis L 1.1: Chemistry in Context
lanthanide milliliter
induced dipole
1.4: Measurements
10.2: Intermolecular Forces 2.6: The Periodic Table
Lattice Energy miscible
inert gas
11.4: Solubility
2.6: The Periodic Table 4.6: Strengths of Ionic and Covalent Bonds
law mixture
inert pair effect
4.2: Ionic Bonding 1.1: Chemistry in Context
law of conservation of matter molality
inner transition metal
2.6: The Periodic Table 1.2: Phases and Classification of Matter
law of constant composition molar mass
instantaneous dipole
10.2: Intermolecular Forces 2.2: Early Ideas in Atomic Theory
law of definite proportions molarity
intensity
6.3: Molarity
3.1: Electromagnetic Energy 2.2: Early Ideas in Atomic Theory
Law of multiple proportions mole
intensive property
1.3: Physical and Chemical Properties 2.2: Early Ideas in Atomic Theory
length mole fraction
interference pattern
8.3: Stoichiometry of Gaseous Substances, Mixtures,
3.1: Electromagnetic Energy 1.4: Measurements
and Reactions
intermolecular force Lewis structure molecular compound
10.2: Intermolecular Forces 4.4: Lewis Symbols and Structures
internal energy Lewis symbol molecular equation
9.4: Enthalpy 4.4: Lewis Symbols and Structures
International System of Units limiting reactant molecular formula
1.4: Measurements 7.5: Reaction Yields
interstitial sites line spectrum molecular orbital theory
10.6: The Solid State of Matter 3.1: Electromagnetic Energy
ion Linear molecular solid
2.4: Atomic Structure and Symbolism 4.7: Molecular Structure and Polarity
ion pair liquid Molecular Structure
11.5: Colligative Properties 1.2: Phases and Classification of Matter
ionic bond liter 4.7: Molecular Structure and Polarity
2.7: Molecular and Ionic Compounds 1.4: Measurements molecule
4.2: Ionic Bonding lone pair 1.2: Phases and Classification of Matter
ionic compound 4.4: Lewis Symbols and Structures monatomic ion
2.7: Molecular and Ionic Compounds 2.7: Molecular and Ionic Compounds
ionic solid M
10.6: The Solid State of Matter macroscopic domain N
ionization energy 1.1: Chemistry in Context net ionic equation
3.5: Periodic Variations in Element Properties magnetic quantum number 7.2: Writing and Balancing Chemical Equations
isoelectronic 3.3: Development of Quantum Theory neutron
noble gas percent yield quantum number
2.6: The Periodic Table 7.5: Reaction Yields 3.2: The Bohr Model
node period
3.1: Electromagnetic Energy 2.6: The Periodic Table R
5.2: Valence Bond Theory periodic law Raoult's Law
nomenclature 2.6: The Periodic Table 11.5: Colligative Properties
2.8: Chemical Nomenclature periodic table rate of diffusion
nonelectrolyte 2.6: The Periodic Table 8.4: Effusion and Diffusion of Gases
11.3: Electrolytes phase diagram reactant
nonmetal 10.5: Phase Diagrams 7.2: Writing and Balancing Chemical Equations
2.6: The Periodic Table photon reduction
nonpolar covalent bond 3.1: Electromagnetic Energy 7.3: Classifying Chemical Reactions
4.3: Covalent Bonding Physical change representative element
normal boiling point 1.3: Physical and Chemical Properties 2.6: The Periodic Table
10.4: Phase Transitions physical property resonance
nucleus 1.3: Physical and Chemical Properties 4.5: Formal Charges and Resonance
2.3: Evolution of Atomic Theory pi bond 5.4: Multiple Bonds
nutritional calorie 5.2: Valence Bond Theory resonance forms
9.3: Calorimetry plasma 4.5: Formal Charges and Resonance
1.2: Phases and Classification of Matter resonance hybrid
O pnictogen 4.5: Formal Charges and Resonance
Octahedral 2.6: The Periodic Table root mean square velocity
4.7: Molecular Structure and Polarity polar covalent bond 8.5: The Kinetic-Molecular Theory
octahedral hole 4.3: Covalent Bonding rounding
10.7: Lattice Structures in Crystalline Solids polar molecule 1.5: Measurement Uncertainty, Accuracy, and
octet rule 4.7: Molecular Structure and Polarity Precision
4.4: Lewis Symbols and Structures polarizability
orbital diagram 10.2: Intermolecular Forces S
3.4: Electronic Structure of Atoms (Electron polyatomic ion s orbital
Configurations) 2.7: Molecular and Ionic Compounds 3.3: Development of Quantum Theory
osmosis Potential Energy saturated
11.5: Colligative Properties 9.2: Energy Basics 11.4: Solubility
osmotic pressure pounds per square inch scientific method
11.5: Colligative Properties 8.1: Gas Pressure 1.1: Chemistry in Context
overlap precipitate second
5.2: Valence Bond Theory 7.3: Classifying Chemical Reactions 1.4: Measurements
oxidation Precipitation reaction semipermeable membrane
7.3: Classifying Chemical Reactions 7.3: Classifying Chemical Reactions 11.5: Colligative Properties
oxidizing agent precision series
7.3: Classifying Chemical Reactions 1.5: Measurement Uncertainty, Accuracy, and 2.6: The Periodic Table
oxyacid Precision shell
2.8: Chemical Nomenclature pressure 3.3: Development of Quantum Theory
oxyanion 8.1: Gas Pressure SI units
2.7: Molecular and Ionic Compounds principal quantum number 1.4: Measurements
3.3: Development of Quantum Theory sigma bond
P product 5.2: Valence Bond Theory
p orbital 7.2: Writing and Balancing Chemical Equations significant figures
3.3: Development of Quantum Theory proton 1.5: Measurement Uncertainty, Accuracy, and
partial pressure 2.3: Evolution of Atomic Theory Precision
8.3: Stoichiometry of Gaseous Substances, Mixtures, psi simple cubic structure
and Reactions 8.1: Gas Pressure 10.7: Lattice Structures in Crystalline Solids
partially miscible pure covalent bond simple cubic unit cell
11.4: Solubility 4.3: Covalent Bonding 10.7: Lattice Structures in Crystalline Solids
parts per billion pure substance single bond
6.4: Other Units for Solution Concentrations 1.2: Phases and Classification of Matter 4.4: Lewis Symbols and Structures
Parts per million solid
6.4: Other Units for Solution Concentrations Q 1.2: Phases and Classification of Matter
pascal Quantitative Analysis solubility
8.1: Gas Pressure 7.6: Quantitative Chemical Analysis 11.4: Solubility
Pauli exclusion principle Quantization solute
3.3: Development of Quantum Theory 3.1: Electromagnetic Energy 6.3: Molarity
percent composition quantum mechanics solvation
6.2: Determining Empirical and Molecular Formulas 3.3: Development of Quantum Theory 11.2: The Dissolution Process
solvent subshell unit
6.3: Molarity 3.3: Development of Quantum Theory 1.4: Measurements
sp hybrid orbital supercritical fluid unit cell
5.3: Hybrid Atomic Orbitals 10.5: Phase Diagrams 10.7: Lattice Structures in Crystalline Solids
sp2 hybrid orbital supersaturated unsaturated
5.3: Hybrid Atomic Orbitals 11.4: Solubility 11.4: Solubility
sp3 hybrid orbital surface tension
5.3: Hybrid Atomic Orbitals 10.3: Properties of Liquids V
sp3d hybrid orbital surroundings vacancy
5.3: Hybrid Atomic Orbitals 9.3: Calorimetry 10.6: The Solid State of Matter
sp3d2 hybrid orbital symbolic domain Valence Bond Theory
5.3: Hybrid Atomic Orbitals 1.1: Chemistry in Context 5.2: Valence Bond Theory
space lattice system Valence Electrons
10.7: Lattice Structures in Crystalline Solids 9.3: Calorimetry 3.4: Electronic Structure of Atoms (Electron
spatial isomers Configurations)
2.5: Chemical Formulas T valence shell
specific heat capacity temperature 3.4: Electronic Structure of Atoms (Electron
9.2: Energy Basics Configurations)
9.2: Energy Basics
spectator ion Tetrahedral valence shell electron pair repulsion
7.2: Writing and Balancing Chemical Equations 4.7: Molecular Structure and Polarity theory
spin quantum number tetrahedral hole 4.7: Molecular Structure and Polarity
3.3: Development of Quantum Theory 10.7: Lattice Structures in Crystalline Solids van der Waals equation
spontaneous process theoretical yield 8.6: Non-Ideal Gas Behavior
11.2: The Dissolution Process 7.5: Reaction Yields van der Waals force
standard conditions of temperature and theory 10.2: Intermolecular Forces
pressure 1.1: Chemistry in Context van't Hoff factor
8.2: Relating Pressure, Volume, Amount, and thermal energy 11.5: Colligative Properties
Temperature- The Ideal Gas Law 9.2: Energy Basics vapor pressure
standard enthalpy of combustion thermochemistry 10.4: Phase Transitions
9.4: Enthalpy 9.2: Energy Basics vapor pressure of water
Standard Enthalpy of Formation titrant 8.3: Stoichiometry of Gaseous Substances, Mixtures,
9.4: Enthalpy and Reactions
standard molar volume titration analysis vaporization
8.2: Relating Pressure, Volume, Amount, and 10.4: Phase Transitions
torr viscosity
standard state 8.1: Gas Pressure
9.4: Enthalpy
transition metal volume
standing wave 2.6: The Periodic Table
1.4: Measurements
trigonal bipyramidal volume percentage
state function 4.7: Molecular Structure and Polarity
9.4: Enthalpy
Trigonal Planar VSEPR
stoichiometric factor 4.7: Molecular Structure and Polarity
triple bond
stoichiometry 4.4: Lewis Symbols and Structures
W
triple point Wave
STP 10.5: Phase Diagrams 3.1: Electromagnetic Energy
Tyndall effect wavefunction
Temperature- The Ideal Gas Law 3.3: Development of Quantum Theory
11.6: Colloids
strong electrolyte wavelength
11.3: Electrolytes
structural formula U 3.1: Electromagnetic Energy
uncertainty weak electrolyte

2.5: Chemical Formulas 11.3: Electrolytes
structural isomers 1.5: Measurement Uncertainty, Accuracy, and
Precision weight
2.5: Chemical Formulas 1.2: Phases and Classification of Matter
unified atomic mass unit
sublimation work
10.4: Phase Transitions 9.2: Energy Basics
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NASSAU COMMUNITY

Flowers, Theopold and Langley

1: Essential Ideas of Chemistry

2: Atoms, Molecules, and Ions

3: Electronic Structure and Periodic Properties

4: Chemical Bonding and Molecular Geometry

5: Advanced Theories of Covalent Bonding

6: Composition of Substances and Solutions

7: Stoichiometry of Chemical Reactions

10: Liquids and Solids

11: Solutions and Colloids

1: Essential Ideas of Chemistry

A general chemistry Libretexts Textbook remixed and remastered from

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The Scientific Method

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The Domains of Chemistry

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Key Concepts and Summary

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Atoms and Molecules

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oxygen O 49.20 chlorine Cl 0.19

silicon Si 25.67 phosphorus P 0.11

aluminum Al 7.50 manganese Mn 0.09

iron Fe 4.71 carbon C 0.08

calcium Ca 3.39 sulfur S 0.06

sodium Na 2.63 barium Ba 0.04

potassium K 2.40 nitrogen N 0.03

magnesium Mg 1.93 fluorine F 0.03

hydrogen H 0.87 strontium Sr 0.02

titanium Ti 0.58 all others - 0.47

Decomposition of Water / Production of Hydrogen

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Chemistry of Cell Phones

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law of conservation of matter

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electric current ampere A

amount of substance mole mol

luminous intensity candela cd

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1 femtosecond (fs) = 1 × 10−15 s

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iron 7.9 g/cm3 acetone 0.79 g/cm3 nitrogen 1.14 g/L

silver 10.5 g/cm3 gasoline 0.70–0.77 g/cm3 neon 0.83 g/L

gold 19.3 g/cm3 mercury 13.6 g/cm3 radon 9.1 g/L