Mole Concept and Stoichiometry

Boyle's Law and Charle's Law

Boyle’s Law

• Relation between pressure (p) and volume (V)

• Statement − At constant temperature, the pressure of a fixed amount (number of

moles, n) of a gas is inversely proportional to its volume.

• Explanation − Based on kinetic theory:

• Number of particles and their average kinetic energy is constant for a given mass of
gas.

• When volume of a certain mass of gas is reduced to half, the particles have lesser
space to move around.

• The number of collision of the particles with the walls of the container doubles, thus
increasing the pressure to twice the original value.

• Mathematically,

, where = Proportionality constant

• From the above equation, it is found that at constant temperature, the product of
pressure and volume of a fixed amount of a gas is constant.

• The value of depends upon

• amount of the gas

• temperature of the gas
• units of p and V

Graphical representation of Boyle's law

 • Each line is called isotherm (at constant temperature plot).

• If at constant temperature,

V1 = Volume of a gas at pressure p1

V2 = Volume of the same gas at pressure p2

Then,

p1V1 = p2V2 = Constant

• Relationship between density (d) and pressure (p):

We know that,

Where, m = Mass of a gas

V = Volume of the gas

• From the above equation, it is known that density is proportional to the pressure of a
fixed amount of a gas.

• Significance of Boyle's law:

• Mountaineers carry oxygen cylinders with them as at higher altitudes as the pressure is
low.

Example

Rita has two cylinders. One is empty and the other contains compressed nitrogen at 25
atm. She wants to distribute the gas in the two cylinders. To do so, she connects the
two cylinders. If the volume of the cylinder containing the gas is 50 L and that of the
empty one is 80 L, then what will be the pressure inside the two cylinders?

Solution:

According to Boyle’s law,

Given, p1 = 25 atm

V1 = 50 L

V2 = (50 + 80) L = 130 L

Now, 25 atm × 50 L = p2 × 130 L

Hence, the pressure inside the cylinders is 9.62 atm.

 Charles’ Law

• Relation between temperature (T) and volume (V)

• Statement − At constant pressure, the volume of a fixed amount of a gas is directly

proportional to its absolute temperature.

• Explanation − On the basis of kinetic theory

• Average kinetic energy of the particles of a gas is directly proportional to the absolute
temperature of the gas

• When temperature is increased at constant pressure, the kinetic energy of the particles
increases.

• The number and intensity of collisions with the walls of the container increase, thereby
increasing the volume at constant pressure.

• Mathematically,

, where = Proportionality constant

• The value of depends upon

• pressure of the gas

• amount of the gas
• unit of volume

• Graphical representation
 • Straight line
• Interception on zero volume at 273.15°C
• Each line is called isobar (constant pressure plot).

• Derivation

For each degree rise in temperature, volume of a gas increases by of the original
volume of the gas at 0°C.

Suppose, V0 = Volume of a gas at 0°C

Vt = Volume of the same gas at t°C

Then,

According to Kelvin temperature scale (also called absolute temperature scale or

thermodynamic scale),

T = 273.15 + t

T0 = 273.15

From equation (i), we obtain

Or, we can write

• Significance of Charle's law:
• Hot air is filled in the balloons used for meteorological purposes.

Example

It is desired to increase the volume of 5 L of a gas by 40% without changing the pressure.
To what temperature should the gas be heated if its initial temperature is 298 K?

Solution:

Desired increase in the volume of gas = 40% of 5 L

=2L

Therefore, final volume of the gas = (5 + 2 ) L = 7 L

Applying Charles’ law,

Now, V1 = 5 L

T1 = 298 K

V2 = 7 L
 Therefore,

Standard Temperature and Pressure(STP)

The pressure and temperature of the gas keeps varying frequently. Hence, we choose a
standard value for temperature and pressure to which the gas volumes can be referred.
The standard value chosen are 0°0°C or 273K for temperature and 1 atm or 760 mm of
Hg for pressure and are commonly known as S.T.P.

Diffusion

Diffusion is defined as the random movement of gaseous molecules from regions of

higher concentration to regions of lower concentration. It is a physical process and can
only occur if the gases do not react with each other.

Graham's Law of Diffusion:

It states that the rate of diffusion of gas is inversely proportional to the square root of its
density at the given temperature and pressure.

It means that the rate of diffusion is inversely proportional to the square root of mass of
 the gas.

The Mole Concept

The Mole Concept: A Brief Overview

Mole defines the quantity of a substance.

One mole of any substance will always contain 6.022 × 1023 particles, no matter what
that substance is.

Therefore, we can say:

• 1 mole of sodium atoms (Na) contains 6.022 × 1023 sodium atoms.

• 1 mole of sodium ions (Na+) contains 6.022 × 1023 sodium ions.
• 1 mole of hydrogen atoms (H) contains 6.022 × 1023 hydrogen atoms.
• 1 mole of hydrogen molecules (H2) contains 6.022 × 1023 hydrogen molecules.

The word ‘mole’ is derived from the Latin word ‘moles’ which means ‘heap’ or ‘pile’. It
was first used by the German chemist Wilhelm Ostwald in 1896. It was accepted
universally much later, in 1967, as a way of indicating the number of atoms or
molecules in a sample.

Thus, mole can be defined as a unit of measurement used for determining the
number of atoms or molecules or ions in a given sample. It is also used to
express the number of reactants and products in a chemical reaction.

The Mole Concept: A Brief Overview

Consider the formation of water by the combination of hydrogen and oxygen.

2H2 + O2 → 2H2O

This reaction implies that 2 moles of hydrogen molecules combine with 1 mole oxygen
molecules to form 2 moles of water molecules.

When carbon (C) reacts with oxygen (O), carbon dioxide is produced. Can you write
the chemical equation for the same?

The chemical equation for the reaction is:

In this reaction, one atom of carbon combines with one molecule (or two atoms) of
oxygen to form one molecule of carbon dioxide. We can also say that in this chemical
reaction, 12 u of carbon combines with 32 u of oxygen to give 44 u of carbon dioxide.
Clearly, we can represent the quantities of substances in terms of their masses.

However, a chemical equation only indicates the numbers of atoms or molecules taking
part in the chemical reaction. Therefore, it is easier to represent the quantities of
substances involved in a chemical reaction by the numbers of their atoms or molecules
rather than their masses. In order to do the same, the concept of mole is used.

Mole Concept

In 1909, the French physicist Jean Perrin found that one gram atom of any element
contains the same number of atoms and one gram molecule of any substance contains
the same number of molecules, which is equal to 6.022 × 1023.

He proposed naming this number in honour of the Italian physicist Amedeo Avogadro.
Hence, 6.022 × 1023 is known as Avogadro’s number (or Avogadro’s constant) and the
amount of a substance containing 6.022 × 1023 atoms/molecules/ions is called a mole.

Mole is a counting unit in chemistry as it is used to express large numbers of atoms or

molecules. One mole of any substance can be defined as the amount of a substance
that contains as many particles (atoms, molecules or ions) as there are atoms in 12 g of
carbon-12 isotope. So,

1 mole of oxygen atoms (O) = 6.022 × 1023 oxygen atoms

1 mole of oxygen molecules (O2) = 6.022 × 1023 oxygen molecules

Know Your Scientist

Jean Perrin (1870-1942) was a French physicist. He was awarded the Nobel Prize in
Physics in 1962, for his contribution to the establishment of the atomic nature of matter,
while conducting research on Brownian motion. In 1895, he showed that cathode rays
are made up of negatively charged particles. He is also known for explaining the origin
of solar energy through thermonuclear reaction of hydrogen (nuclear fusion) in the sun.
In 1908, he studied Brownian motion using an ultramicroscope and gave experimental
confirmation to the hypothesis that the random motion of suspended particles is due to
the particulate nature of matter and the inter-particle interactions. He is also credited
with estimating the size of a water molecule and the number of molecules of water
present in a given amount of water.

Amedeo Avogadro (1776-1856) was an Italian lawyer; however, his interest in the
natural sciences led him to study physics and mathematics privately. In 1809, while
teaching the natural sciences in Vercelli, he hypothesized that under the same
conditions of temperature and pressure, equal volumes of gases contain the same
number of particles. This hypothesis later came to be known as Avogadro’s law.

Mole Concept

The molar mass of a substance can be defined as the mass of one mole of a substance
in grams. It is numerically equal to atomic/molecular/formula unit mass in u.

The mass of one atom is called atomic mass and its unit is unified mass (u), while the
mass of one mole of atoms is called molar mass of atoms and its unit is gram (g).
Molar mass of atoms is also called gram atomic mass.

For example, the atomic mass of nitrogen (N) is 14 u, while its gram atomic mass is 14
g. So, while 14 u of nitrogen contains only 1 atom of nitrogen, 14 g of nitrogen contains
1 mole of nitrogen atoms, i.e., 6.022 × 1023 nitrogen atoms.

The mass of one molecule is called molecular mass and its unit is unified mass (u),
while the mass of one mole of molecules is called molecular mass and its unit is gram
(g). When molecular mass is expressed in grams, it is called gram molecular
mass or gram molecule.
For example, the molecular mass of oxygen (O2) is 32 u, while its gram molecular mass
is 32 g. So, while 32 u of oxygen contains only 1 molecule of oxygen, 32 g of oxygen
contains 1 mole of oxygen molecules, i.e., 6.022 × 10 23 oxygen molecules.

The volume of one mole of any substance is called its molar volume.

The molar volume of a gas at STP is numerically equal to 22.4 L.

Mole Concept

Solved Examples

Easy

Example 1:

Calculate the mass of 3.3 moles of ammonia molecule.

Solution:

Molar mass of ammonia molecule (NH3) = 17 g

Number of moles of ammonia molecule = 3.3

We know that:

So,

Medium

Example 2:

Calculate the volume of 14 g of nitrogen gas at STP.

Solution:

Mass of nitrogen gas (N2) = 14 g

 Molar mass of nitrogen gas = 28 g

We know that:

So,

The volume of 1 mole of a gas at STP is 22.4 L.

Therefore,

Volume of 0.5 mole of nitrogen gas at STP =

Avogadro’s Law

In 1811, Avogadro hypothesized that under the same conditions of temperature and
pressure, equal volumes of all gases contain an equal number of moles. For example,
at the same temperature and pressure, the two gases, oxygen and nitrogen possessing
the same volume contain the same number of molecules. This hypothesis is named
Avogadro’s law. The mole concept provides the following information.

• If one mole of a substance (atoms, molecules or ions) is present, then the number of
elementary particles present in that substance is equal to 6.022 × 1023.

• The mass of one mole of a substance (atoms, molecules or ions) is equal to its molar
mass.

• While carrying out reactions, scientists require the number of atoms and molecules.
This requirement is fulfilled by the use of the mole concept as follows:

1 mole = 6.022 × 1023 = Relative mass in grams.

Avogadro’s Law

Relationship between Mole, Avogadro’s Number and Mass

 The relationship between mole, Avogadro’s number and mass is summarized in the
given figure.

Applications of Avogadro's Law

• It provides an explanation for Gay-Lussac's law.

The volumes of different combining gases bear a simple ratio to one another because
according to Avogadro's law at constant temperature and pressure equal volumes of
gases contain the same number of molecules.

• It helps in determination of atomicity of gases.

Consider the formation of hydrogen chloride gas by the direct combination of hydrogen
and chlorine gases:

H2 + Cl2 → 2 HCl

According to Avogadro's law:

1 molecule of H2 + 1 molecule of Cl2 → 2 molecules of HCl

Or, 1/2 molecule of H2 + 1/2 molecule of Cl2 → 1 molecule of HCl

As atoms are indivisible, therefore, half a molecule of H2 and Cl2 indicate they both
contain two atoms per molecule.

• It helps in determination of molecular formula of a gas.

 Consider the formation of hydrogen chloride gas by the direct combination of hydrogen
and chlorine gases:

H2 + Cl2 → 2 HCl

According to Avogadro's law:

1 molecule of H2 + 1 molecule of Cl2 → 2 molecules of HCl

Or, 1/2 molecule of H2 + 1/2 molecule of Cl2 → 1 molecule of HCl

Or, 1 atom of H + 1 atom of Cl → 1 molecule of HCl

Hydrogen chloride gas has one atom of hydrogen and one atom of chlorine. Therefore,
its molecular formula is HCl.

• It helps in the establishment of the relationship between molecular mass and vapour
density (VD).

• It provides the relation between gram molecular mass and gram molecular volume.

Molar volume of a gas = 22.4 L

Gram molecular mass of a gas occupies 22.4 L and contains 6.02 ×

1023 molecules/atoms of the gas.

Gay-Lussac’s Law

This law gives the relationship between pressure and temperature. According to this
law, at constant volume, the pressure of a fixed amount of a gas is directly proportional
to the temperature. It can be represented mathematically as,
 Mathematically,

p ∝T

= constant = k3

If at constant volume,

p1 = Pressure of a gas at T1

p2 = Pressure of the same gas at T2

Then,

Mole Concept and Molar Masses

• 1 mole of any substance can be defined as:

• Amount of a substance that contains as many particles (atoms, molecules or ions) as

there are atoms in 12 g of the 12C isotope

• Avogadro number or Avogadro constant (NA); it is equal to 6.022 × 1023 particles

• Example − 1 mole of oxygen atoms = 6.022 × 1023 atoms of oxygen

1 mole of carbon dioxide molecules = 6.022 × 1023 molecules of carbon dioxide

1 mole of sodium chloride = 6.022 × 1023 formula units of sodium chloride

• Relative atomic mass: Relative atomic mass of an element is the ratio of the average
mass of one atom of an element to one-twelfth of the mass of an atom of carbon-12.

Molar mass of a substance can be defined as:

• Mass of one mole of a substance in grams

• Numerically equal to atomic/molecular/formula mass in u.

• Example − Molar mass of CO2 = 44.011 g mol−1

• Relative molecular mass: It is defined as the ratio of the mass of a molecule to the
atomic mass unit of the molecule. It is a unitless quantity.

Molar mass of NaCl = 58.5 g mol−1

Examples

1. What number of moles contains 3.011 × 1023 molecules of glucose?

Solution:

1 mole of glucose is equivalent to 6.022 × 1023 molecules of glucose.

Hence, 3.011 × 1023 molecules of glucose will be present in

mol = 0.5 mol (of glucose)

Thus, 0.5 mole of glucose contains 3.011 × 1023 molecules of glucose.

2. What is the mass of a fluorine molecule?

Solution:

1 mole of fluorine molecule contains 6.022 × 1023 molecules and weighs 38 g.

Therefore, mass of a fluorine molecule = g

= 6.31 × 10−23 g

Atomicity

• It is defined as the total number of atoms of constituent elements which combine to form
a molecule.
• One molecule of hydrogen combines with one molecule of chlorine to form two
molecules of hydrogen chloride.
• One molecule of hydrogen or chlorine contains two atoms of each.

Percentage Composition

Mass percent of an element =

Example

What is the mass percent of oxygen in potassium nitrate? (Atomic mass of K = 39.10 u,
atomic mass of N = 14.007 u, atomic mass of O = 16.00 u)

Solution:

Atomic mass of K = 39.10 u (Given)

Atomic mass of N = 14.007 u (Given)

Atomic mass of O = 16.00 u (Given)

Therefore, molar mass of potassium nitrate (KNO3)

= 39.10 + 14.007 + 3(16.00)

= 101.107 g

Therefore, mass percent of oxygen in KNO3

= 47.47% (approx)

• Empirical formula and molecular formula:

 Empirical formula Molecular formula

Represents the simplest whole Represents the exact number of

number ratio of various atoms different types of atoms present in a
present in a compound molecule of a compound

• Empirical formula is determined if mass % of various elements are known.

• Molecular formula is determined from empirical formula if molar mass is known.

Example

A compound contains 92.26% carbon and 7.74% hydrogen. If the molar mass of the
compound is 26.038 g mol−1, then what are its empirical and molecular formulae?

Solution:

Mass percent of carbon (C) = 92.26% (Given)

Mass percent of hydrogen (H) = 7.74% (Given)

Therefore, 100 g of the compound contains 92.26 g and 7.74 g of of hydrogen

Number of moles of carbon present in the compound =

= 7.68 mol

Number of moles of hydrogen present in the compound

= 7.68 mol

Thus, in the given compound, carbon and hydrogen are present in the ratio C : H =
7.68 : 7.68

=1:1

Therefore, the empirical formula of the compound is CH.

Empirical formula mass of CH = (12.011 + 1.008)g

= 13.019 g

Molar mass of the compound = 26.038 g (Given)

Therefore, n =

=2

Hence, the molecular mass of the compound is (CH)n, i.e., (CH)2 or C2H2.

Interconversion Among Number of Moles, Mass and Number of Molecules

 Stoichiometric Calculations in Balanced Chemical Equations

• An example of a balanced chemical equation is given below.

From the above balanced chemical equation, the following information is obtained:

• One mole of C3H8(g) reacts with five moles of O2(g) to give three moles of CO2(g) and
four moles of H2O(l).

• One molecule of C3H8(g) reacts with five molecules of O2(g) to give three molecules
of CO2(g) and four molecules of H2O(l).

• 44 g of C3H8(g) reacts with (5 × 32 = 160) g of O2(g) to give (3 × 44 = 132) g of CO2(g)

and (4 × 18 = 72) g of H2O(l).

• 22.4 L of C3H8(g) reacts with (5 × 22.4 = 112) L of O2(g) to give (3 × 22.4 = 67.2) L
of CO2(g) and (4 × 22.4 = 89.6) L of H2O(l).
 Example

Nitric acid (HNO3) is commercially manufactured by reacting nitrogen dioxide (NO2)

with water (H2O). The balanced chemical equation is represented as follows:

Calculate the mass of NO2 required for producing 5 moles of HNO3.

Solution:

According to the given balanced chemical equation, 3 moles of NO2 will produce 2
moles of HNO3.

Therefore, 2 moles of HNO3 require 3 moles of NO2.

Hence, 5 moles of HNO3 require moles of NO2

= 7.5 moles of NO2

Molar mass of NO2 = (14 + 2 × 16) g mol-1

= 46 g mol-1

Thus, required mass of NO2 = (7.5 × 46) g

= 345 g

• Limiting reagent or limiting reactant:

• Reactant which gets completely consumed when a reaction goes to completion

• So called because its concentration limits the amount of the product formed
 Example

Lead nitrate reacts with sodium iodide to give lead iodide and sodium nitrate in the
following manner:

What amount of sodium nitrate is obtained when 30 g of lead nitrate reacts with 30 g of
sodium iodide?

Solution:

Molar mass of

= 331 g mol-1

Molar mass of NaI = (23 + 127) = 150 g mol-1

According to the given equation, 1 mole of Pb(NO3)2 reacts with 2 moles of NaI, i.e.

331 g of Pb(NO3)2 reacts with 300 g of NaI to give PbI2 and NaNO3

Thus, 30 g of Pb(NO3)2 will react with (30 × 300) / 331 g of NaI = 27.19g of NaI

However, we have 30 g of NaI. So, NaI is present in excess and Pb(NO3)2 is the limiting
reagent.

Now, number of moles in 30 g of Pb(NO3)2 30 g mole

According to the equation, 1 mole of Pb(NO3)2 gives 2 moles of NaNO3. So

0.09 moles of Pb(NO3)2 will give (2 × 0.09) moles of NaNO3 = 0.18 moles of NaNO3.

• Reactions in solutions:

Ways for expressing the concentration of a solution −

• Mass per cent or weight per cent (w/w%)

 Mass per cent

Example

4.4 g of oxalic acid is dissolved in 200 mL of a solution. What is the mass per cent of oxalic
acid in the solution? (Density of the solution = 1.1 g mL−1)

Solution:

Density of the solution = 1.1 g mL−1

So the mass of the solution = (200 mL) × (1.1 g mL−1)

= 220 g

Mass of oxalic acid = 4.4 g

Therefore, mass per cent of oxalic acid in the solution

• Mole fraction:

If a substance ‘A’ dissolves in a substance ‘B’, then mole fraction of

Mole fraction of B
 nA − Number of moles of A

nB − Number of moles of B

Example

A solution is prepared by dissolving 45 g of a substance X (molar mass = 25 g mol−1) in

235 g of a substance Y (molar mass = 18 g mol−1). Calculate the mole fractions
of X and Y.

Solution:

Moles of X, nX =

= 1.8 mol

Moles of Y, nY =

= 13.06 mol

Therefore, mole fraction of X, nX

And, mole fraction of Y, nY = 1 − nX

= 1 − 0.121

= 0.879

• Molarity:
Number of moles of solute in 1 L of solution

Molarity (M) =

For a given solution, the molarity equation is as follows:

M1V1 = M2V2

M1 = Molarity of a solution when its volume is V1

M2 = Molarity of the same solution when its volume is V2

Examples

1. 10g of HCl is dissolved in enough water to form 500 mL of the solution. Calculate the
molarity of the solution.

Solution:

Molar mass of HCl = 36.5 g mol−1

So the moles of HCl = mol

= 0.274 mol

Volume of the solution = 500 mL = 0.5 L

Therefore, molarity =

= 0.548 M

2. Commercially available concentrated HCl contains 38% HCl by mass. What volume of
concentrated HCl is required to make 2.5 L of 0.2 M HCl? (Density of the solution = 1.19
g mL−1)
Solution:

38% HCl by mass means that 38g of HCl is present in 100 g of the solution.

Moles of HCl =

Volume of the solution

= 84.03 mL

= 0.08403L

Therefore, molarity of the solution =

= 12.38 M

According to molarity equation,

M1V1 = M2V2

Here,

M1 = 12.38 M

M2 = 0.2 M

V2 = 2.5 L

Now, M1V1 = M2V2

 Hence, required volume of HCl = 0.0404 L

• Molality:

Number of moles of solute present in 1 kg of solvent

Molality (m) =

Example

What is the molality of a solution of glucose in water, which is labelled as 15% (w/w)?

Solution:

15% (w/w) solution means that 15 g of glucose is present in 100 g of the solution, i.e.
(100 − 15) g = 85 g of water = 0.085 kg of water

Moles of glucose =

= 0.083 mol

Therefore, molality of the solution

= 0.976 m