CHM 111

GENERAL CHEMISTRY I

1. Atoms, molecules, chemical reactions and modern electronic theory of atoms.

2. Electronic configuration, periodicity and building up of the periodic table
3. Hybridization and shapes of simple molecules, valence forces, structure, structure of solids.
Chemical equations and stoichiometry chemical bonding and intermolecular forces.
4. Acids bases and salts. Properties of gases, redox reactions and introduction to electrochemistry.
Radioactivity
5. Elementary thermochemistry, rates of reaction, equilibrium and thermodynamics, Kinetic theory
of matter.

ATOMS AND MOLECULES

The universe is made of matter and energy.

Matter has mass, occupies space and consist of basic elements

Elements consists of atoms.

An atom is defined as the smallest particle into which an element can be divided, e.g. hydrogen, carbon,
iron, etc.

MODERN ATOMIC THEORY

The concept that atoms play a fundamental role in chemistry is formalized by the modern atomic
theory, first stated by John Dalton, an English scientist, in 1808. It consists of the following parts:

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
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 number of atoms of each of its elements is always present in the
same ratio.
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. THE LAW OF
CONSERVATION OF MASS states that: In the process of a chemical reaction, the amount of
matter involved remains the same before and after the reaction occurs.
PROTON - Located in the center (or nucleus) of an atom, each atom has at least one proton. Protons
have a charge of +1, and a mass of approximately 1 atomic mass unit (amu). Elements differ from each
other in the number of protons they have, e.g. Hydrogen has 1 proton; Helium has 2

NEUTRON - Located in the atomic nucleus (except in Hydrogen). The neutron has no charge, and a mass
of slightly over 1 amu. The neutron is made up of a proton and electron-like particle

ELECTRON - Very small particle located outside the nucleus. Electrons occupy orbitals, or areas where
they have a high statistical probability of occurring. they move at speeds near the speed of light the
precise location of electrons is hard to pin down. The charge on an electron is -1. Its mass is negligible
(approximately 1800 electrons are needed to equal the mass of one proton)

ATOMIC NUMBER – Number of protons in an atom. It is characteristic and unique for each element.

ATOMIC MASS/WEIGHT - Number of protons and neutrons in an atom.

ISOTOPES - are atoms of an element that have differing numbers of neutrons but a constant atomic
number, e.g. Hydrogen – 1H; Deuterium – 2H; Tritium - 3H, Carbon – 12C and 14C. Some isotopes are
radioisotopes, which spontaneously decay, releasing radioactivity, e.g. 14C and 2H. Stable isotopes are
12C and 1H

PERIODIC TABLE - The periodic table arranges the elements in order of increasing atomic number.
Elements that exhibit similar chemistry appear in vertical columns called groups (numbered 1–18 from
left to right); the seven horizontal rows are called periods. The elements can be broadly divided into
metals, nonmetals, and semimetals. Semimetals exhibit properties intermediate between those of
metals and nonmetals.

The periodic law was developed independently by Dmitri Mendeleev and Lothar Meyer. The Periodic
Law states that:

The physical and chemical properties of the elements recur in a systematic and predictable way when
the elements are arranged in order of increasing atomic number.

MOLECULES

A molecule is an electrically neutral group of two or more atoms held together by chemical bonds.
A molecule may be homonuclear, that is, it consists of atoms of one chemical element, as with two
atoms in the oxygen molecule (O2); or it may be heteronuclear, a chemical compound composed of
more than one element, as with water (two hydrogen atoms and one oxygen atom; H2O).

Molecular shape (ESBM9)

Many of the properties of molecules come from the particular shape that a molecule has.

The shape of a covalent molecule can be predicted using the Valence Shell Electron Pair
Repulsion (VSEPR) theory.

VSEPR theory says that the valence electron pairs in a molecule will arrange themselves around
the central atom(s) of the molecule so that the repulsion between their negative charges is as
small as possible i. e. the valence electron pairs arrange themselves so that they are as far apart as
they can be.

Determining molecular shape

The shapes below give the common molecular shapes. In this table we use A to represent the
central atom, X to represent the terminal atoms (i.e. the atoms around the central atom) and E to
represent any lone pairs.

The common molecular shapes.

BONDING:

Important Theories on Chemical Bonding

Lewis Theory of Chemical Bonding

 An atom can be viewed as a positively charged ‘Kernel’ (the nucleus plus the inner electrons)
and the outer shell.
 The outer shell can accommodate a maximum of eight electrons only.
 The eight electrons present in the outer shell occupy the corners of a cube which surround the
‘Kernel’.
 The atoms having octet configuration, i.e. 8 electrons in the outermost shell, thus symbolize a
stable configuration.
 Atoms can achieve this stable configuration by forming chemical bonds with other atoms. This
chemical bond can be formed either by gaining or losing an electron(s) (NaCl, MgCl2) or in some
cases due to the sharing of an electron (F2).
 Only the electrons present in the outer shell, also known as the valence electrons take part in
the formation of chemical bonds. Gilbert Lewis used specific notations better known as Lewis
symbols to represent these valence electrons.
 Generally, the valency of an element is either equal to the number of dots in the corresponding
Lewis symbol or 8 minus the number of dots (or valence electrons).
Lewis symbols for lithium (1 electron), oxygen (6 electrons), neon (8 electrons) are given below:

Here, the number of dots that surround the respective symbol represents the number of valence
electrons in that atom.

Kossel’s theory of Chemical Bonding

 Noble gases separate the highly electronegative halogens and the highly electropositive alkali
metals.
 Halogens can form negatively charged ions by gaining an electron. Whereas alkali metals can
form positively charged ions by losing an electron.
 These negatively charged ions and positively charged ions have a noble gas configuration that is
8 electrons in the outermost shell. The general electronic configuration of noble gases (except
helium) is given by ns2np6.
  As unlike charges attract each other these unlike charged particles are held together by a
strong force of electrostatic attraction existing between them. For example, MgCl2, the
magnesium ion, and chlorine ions are held together by force of electrostatic attraction. This
kind of chemical bonding existing between two unlike charged particles is known as an
electrovalent bond.

Types of Chemical Bonds

Covalent Bond:

A covalent bond is a chemical bond that involves the sharing of electron pairs between atoms. These
electron pairs are termed shared pairs or bonding pairs, and the stable balance of attractive and
repulsive forces between atoms, when they share electrons, is termed covalent bonding, e.g. H2

Ionic Bond:

Ionic bonding is a type of chemical bond that involves the electrostatic attraction between oppositely
charged ions, and is the primary interaction occurring in ionic compounds. The ions are atoms that have
lost one or more electrons (termed cations) and atoms that have gained one or more electrons (termed
anions). This transfer of electrons is termed electrovalence e.g. Na+ F-; NH4+ SO4-

Hydrogen Bonding
Compared to ionic and covalent bonding, Hydrogen bonding is a weaker form of chemical bonding. It is a
type of polar covalent bonding between oxygen and hydrogen wherein the hydrogen develops a partial
positive charge. This implies that the electrons are pulled closer to the more electronegative oxygen
atom.
This creates a tendency for the hydrogen to be attracted towards the negative charges of any
neighbouring atom. This type of chemical bonding is called a hydrogen bond and is responsible for many
of the properties exhibited by water.

Hydrogen Bonding

Bond Characteristics

1. Bond Length
The equilibrium distance between the centers of the nuclei of the two bonded atoms is called its Bond
length.
It is expressed in terms of an angstrom (A0) or picometer (pm). It is determined experimentally by x-ray
diffraction or electron diffraction method or spectroscopic method. The bond length in chemical
bonding is the sum of their ionic radii, in an ionic compound. In a covalent compound, it is the sum of
their covalent radii.
Factors Affecting the Bond length

 Size of the atoms: The bond length increases with increase in the size of the atom. HI > HBr > HCl
> HF

 The multiplicity of Bond: The bond length decreases with an increase in bond order.

 Type of hybridization: A‘s’ orbital is smaller in size, greater the ‘s’ character, shorter is the bond
length.

2. Bond Enthalpy
The amount of energy required to break one mole of bonds of a type so as to separate the molecule into
individual gaseous atoms is called bond dissociation enthalpy or Bond enthalpy. Bond enthalpy is usually
expressed in KJ mol-1.
Greater is the bond dissociation enthalpy, greater is the bond strength. For diatomic molecules like H2,
Cl2, O2, N2, HCl, HBr, HI the bond enthalpies are equal to their dissociation enthalpy.
In the case of polyatomic molecules, bond enthalpies are usually the average values, because the
dissociation energy varies with each type of bond.
In H20, first O-H bond enthalpy = 502 KJ/mol; Second bond enthalpy = 427 KJ/mol Average bond
enthalpy = (502 + 427) / 2 = 464.5 KJ/mol

Factors Affecting Bond Enthalpy in Chemical Bonding

Size of the Atom
Greater the size of the atom, greater is the bond length and less is the bond dissociation enthalpy i.e.
less is the bond strength during chemical bonding.
Multiplicity of Bonds
Greater is the multiplicity of the bond, greater is the bond dissociation enthalpy.
Number of Lone Pair of Electrons Present
More the number of lone pair of electrons present on the bonded atoms, greater is the repulsion
between the atoms and thus less is the bond dissociation enthalpy of the chemical bond.
3. Bond Angle
A bond is formed by the overlap of atomic orbitals. The direction of overlap gives the direction of the
bond. The angle between the lines representing the direction of the bond i.e. the orbitals containing the
bonding electrons is called the bond angle.

Factors Affecting Bond Enthalpy in Chemical Bonding

4. Bond Order
In Lewis representation, the number of bonds present between two atoms is called the bond order.
Greater the bond order, greater is the stability of the bond during chemical bonding i.e. greater is the
bond enthalpy. Greater the bond order, shorter is the bond length.

Molecular Formula and molecular mass:

Molecular formula shows the exact number of atoms that compose the molecule and so characterizes
different molecules. different isomers can have the same atomic composition while being different
molecules.
CHEMICAL REACTIONS

A chemical reaction is a reaction in which the bonds are broken within reactant molecules, and new
bonds are formed within product molecules in order to form a new substance.

Compounds that interact to produce new compounds are called reactants whereas the newly formed
compounds are called products

In a chemical reaction, a chemical change must occur which is generally observed with physical changes
like precipitation, heat production, colour change etc.

The reactants are on the left-hand side whereas products formed on the right-hand side connected by a
one-headed or two-headed arrows. For example, a reaction

A+B→C+D

Here, A and B are the reactants, which react to form the products C and D. In an actual chemical
equation, reactants are denoted by their chemical formula. In order to assure the law of conservation of
mass, a chemical equation must be balanced i.e. the number of atoms on both sides must be equal. This
is the balancing of the equation, e.g. Combustion of methane.

CH4 + O2 CO2 + 2H20

Balancing Chemical Equations

A balanced equation is an equation for a chemical reaction in which the number of atoms for each
element in the reaction and the total charge are the same for both the reactants and the products. In
other words, the mass and the charge are balanced on both sides of the reaction.
Matter cannot be created or destroyed in chemical reactions. This is the law of conservation of mass.

Examples:
1. 6CO2 + 6H2O → C6H12O6 + 6O2
2. SiCl4 + 4H2O → H4SiO4 + 4HCl

3. Na2CO3 + 2HCl → 2NaCl + H2O + CO2

Chemical Equilibrium:

CO2 (g) + CaO (s)⇌CaCO3 (s)

Most chemical reactions are reversible; that is, they can and do run in both directions. The forward and
reverse reactions are competing with each other and differ in reaction rates. These rates depend on the
concentration and therefore change with the time of the reaction: the reverse rate gradually increases
and becomes equal to the rate of the forward reaction, establishing the so-called chemical equilibrium.
The time to reach equilibrium depends on parameters such as temperature, pressure, and the materials
involved, and is determined by the minimum free energy.
The reaction yield stabilizes at equilibrium but can be increased by removing the product from the
reaction mixture or changed by increasing the temperature or pressure. A change in the concentrations
of the reactants does not affect the equilibrium constant but does affect the equilibrium position.

Reaction Thermodynamics
Chemical reactions are determined by the laws of thermodynamics. Reactions can proceed by
themselves if they are exergonic, that is if they release free energy. The associated free energy change
of the reaction is composed of the changes of two different thermodynamic
quantities, enthalpy and entropy:[17]

G: free energy, H: enthalpy, T: temperature, S: entropy, Δ: difference (change between original

and product)
Reactions can be exothermic, where ΔH is negative and energy is released. Typical examples of
exothermic reactions are combustion, precipitation and crystallization, in which ordered solids are
formed from disordered gaseous or liquid phases. In contrast, in endothermic reactions, heat is
consumed from the environment. This can occur by increasing the entropy of the system, often
through the formation of gaseous or dissolved reaction products, which have higher entropy. Since
the entropy term in the free-energy change increases with temperature, many endothermic
reactions preferably take place at high temperatures. On the contrary, many exothermic reactions
such as crystallization occur preferably at lower temperatures. A change in temperature can
sometimes reverse the sign of the enthalpy of a reaction, as for the carbon monoxide reduction
of molybdenum dioxide:

This reaction to form carbon dioxide and molybdenum is endothermic at low temperatures,
becoming less so with increasing temperature. ΔH° is zero at 1855 K, and the reaction
becomes exothermic above that temperature.
Changes in temperature can also reverse the direction tendency of a reaction. For example,
the water gas shift reaction

is favored by low temperatures, but its reverse is favored by high temperatures. The
shift in reaction direction tendency occurs at 1100 K.[18]
Reaction Kinetics
The speed at which reactions take place is studied by reaction kinetics. The rate depends on various
parameters, such as:

 Reactant concentrations, which usually make the reaction happen at a faster rate if raised through
increased collisions per unit of time. Some reactions, however, have rates that are independent of
reactant concentrations, due to a limited number of catalytic sites. These are called zero order
reactions.
 Surface area available for contact between the reactants, in particular solid ones in heterogeneous
systems. Larger surface areas lead to higher reaction rates.
 Pressure – increasing the pressure decreases the volume between molecules and therefore
increases the frequency of collisions between the molecules.
 Activation energy, which is defined as the amount of energy required to make the reaction start and
carry on spontaneously. Higher activation energy implies that the reactants need more energy to
start than a reaction with lower activation energy.
 Temperature, which hastens reactions if raised, since higher temperature increases the energy of
the molecules, creating more collisions per unit of time,
 The presence or absence of a catalyst. Catalysts are substances that make weak bonds with
reactants or intermediates and change the pathway (mechanism) of a reaction which in turn
increases the speed of a reaction by lowering the activation energy needed for the reaction to take
place. A catalyst is not destroyed or changed during a reaction, so it can be used again.
 For some reactions, the presence of electromagnetic radiation, most notably ultraviolet light, is
needed to promote the breaking of bonds to start the reaction. This is particularly true for reactions
involving radicals.
Several theories allow calculating the reaction rates at the molecular level. This field is referred to as
reaction dynamics. The rate v of a first-order reaction, which could be the disintegration of a substance
A, is given by:

Basic concepts of chemical reactions

Synthesis

Reactants are converted to products, and the process is symbolized by a chemical equation. For
example, iron (Fe) and sulfur (S) combine to form iron sulfide

Fe(s) + S(s) → FeS(s)

The state of matter of reactants and products is designated with the symbols (s) for solids, (l) for liquids,
and (g) for gases.
Classifying chemical reactions
A. Classification by type of product

1. Gas-forming reactions
Calcium carbonate (CaCO3, the chief component of limestone, seashells,
and marble) is mixed with hydrochloric acid (HCl) to produce carbon
dioxide.

CaCO3(s) + 2 HCl(aq) → CaCl2(aq) + CO2(g) + H2O (l)

2. Precipitation reactions
Compounds having anions such
as sulfide (S2−), hydroxide (OH−), carbonate (CO32−), and phosphate (PO43−)
are often insoluble in water. A precipitate will form if a solution containing
one of these anions is added to a solution containing a metal cation such as
Fe2+, Cu2+, or Al3+.

Fe2+(aq) + 2 OH−(aq) → Fe(OH)2(s)

Al3+(aq) + PO43−(aq) → AlPO4(s)

B. Classification by types of reactants

3. Oxidation-reduction reactions
A common redox reaction is one step in the rusting of iron in damp air.

2Fe(s) + 2H2O(l) + O2(g) → 2Fe(OH)2(s)

Here iron metal is oxidized to iron dihydroxide (Fe(OH) 2); elemental oxygen
(O2) is the oxidizing agent.

4. Acid-base reactions
The Arrhenius theory
The Arrhenius theory: acid is a substance that increases the concentration
of the hydronium ion (H3O+) in an aqueous solution and a base is a
substance that increases the hydroxide ion (OH−) concentration. Well-known
acids include hydrochloric acid (HCl), sulfuric acid (H2SO4), nitric
acid (HNO3), and acetic acid (CH3COOH). Bases includes such common
substances as caustic soda (sodium hydroxide, NaOH) and slaked lime
(calcium hydroxide, Ca(OH)2). Another common base is ammonia (NH3),
which reacts with water to give a basic solution according to the following
balanced equation.

NH3(aq) + H2O(l) → NH4+(aq) + OH−(aq)

Aqueous solutions of sodium hydroxide and hydrochloric acid.

HCl(aq) + NaOH(aq) → NaCl(aq) + H2O (l)

The Brønsted-Lowry theory

Brønsted-Lowry theory defines an acid as a proton donor and a base as a
proton acceptor. In this theory, the reaction of an acid and base is
represented as an equilibrium reaction.

acid (1) + base (2) ⇌ base (1) + acid (2)

(The double arrows, ⇌, indicate that the products can re-form the reactants
in a dynamic process.)

Acid (1) and base (1) are called a conjugate acid-base pair, as are acid (2)
and base (2).

Hydrochloric acid, a strong acid, ionizes completely in water to form the

hydronium and chlorine (Cl−) ions in a product-favoured reaction.

HCl(aq) + H2O (l) → H3O+(aq) +Cl−(aq)

Using the Brønsted-Lowry theory, the reaction of ammonia and hydrochloric

acid in water is represented by the following equation:

NH3(aq) + HCl(aq) → NH4+(aq) + Cl−(aq)

The Lewis theory
In the Lewis theory, bases are defined as electron-pair donors and acids as
electron-pair acceptors. Acid-base reactions involve the combination of the
Lewis acid and base through sharing of the base’s electron pair.

Ammonia is an example of a Lewis base. A pair of electrons located on

the nitrogen atom may be used to form a chemical bond to a Lewis acid
such as boron trifluoride (BF3) to form ammonium boron trifloride. (In the
following equation, the colon represents an electron pair.)

H3N: + BF3 → H3N― BF3

C. Classification by reaction outcome

5. Decomposition reactions
Decomposition reactions are processes in which chemical species break up
into simpler parts. Usually, decomposition reactions require energy input.
For example, a common method of producing oxygen gas in the laboratory
is the decomposition of potassium chlorate (KClO3) by heat.

2KClO3(s) → 2KCl(s) + 3O2(g)

6. Substitution, elimination, and addition

reactions
These terms are particularly useful in describing organic reactions. In
a substitution reaction, an atom or group of atoms in a molecule is replaced
by another atom or group of atoms. For example, methane (CH4) reacts with
chlorine (Cl2) to produce chloromethane (CH3Cl), a compound used as a
topical anesthetic. In this reaction, a chlorine atom is substituted for
a hydrogen atom.

CH4 + Cl2 ---------CH3Cl + HCl

Methane + chlorine--------chloromethane + hydrogen cholide

Elimination:
Substitution reactions are widely used in industrial chemistry. For example,
substituting two of the chlorine atoms on chloroform (CHCl3)
with fluorine atoms produces chlorodifluoromethane (CHClF2). This product
undergoes a further reaction when heated strongly.

2CHClF2(g) → F2C=CF2(g) + 2HCl(g)

This latter reaction is an example of an elimination reaction, a hydrogen

atom and a chlorine atom being eliminated from the starting material
as hydrochloric acid (HCl). The other product is tetrafluoroethylene,
a precursor to the polymer known commercially as Teflon.

Addition:

Addition reactions are the opposite of elimination reactions. As the name

implies, one molecule is added to another. An example is the common
industrial preparation of ethanol (CH3CH2OH). Historically, this compound
was made by fermentation. However, since the early 1970s, it has also been
made commercially by the addition of water to ethylene.

C2H4+ H2O → CH3CH2OH

Ethylene + water -----ethanol

7. Polymerization reactions
Polymers are high-molecular-weight compounds, fashioned by the
aggregation of many smaller molecules called monomers.

There are two basic ways to form polymers: (a) linking

small molecules together, a type of addition reaction, and (b) combining two
molecules (of the same or different type) with the elimination of a stable
small molecule such as water. This latter type of polymerization combines
addition and elimination reactions and is called a condensation reaction .

Addition Polymerization

An example of the first type of reaction is the union of thousands

of ethylene molecules that gives polyethylene.

nH2C=CH2 → [―CH2CH2―]n

In both starch and cellulose, molecules of glucose are joined together

with concomitant elimination of a molecule of water for every linkage
formed.
nC6H12O6 → ―[―C6H10O5―]―n + nH2O

8. Solvolysis and hydrolysis

A solvolysis reaction is one in which the solvent is also a reactant. Solvolysis
reactions are generally named after the specific solvent—for example, the
term hydrolysis when water is involved.

Hydrolysis of an organic compound is illustrated by the reaction of water

with esters. Esters have the general formula RCOOR′, R and R′ being
combining groups (such as CH3). The hydrolysis of an ester produces an
acid and an alcohol. The equation for the reaction of methyl acetate and
water is

CH3COOCH3(aq) + H2O(l) → CH3COOH(aq) + CH3OH(aq).

Ester Acid Alcohol

D. Classification by reaction
mechanism
9. Chain reactions
Chain reactions occur in a sequence of steps, in which the product of each
step is a reagent for the next. Chain reactions generally involve three
distinct processes: an initiation step that begins the reaction, a series of
chain-propagation steps, and, eventually, a termination step.

Polymerization reactions are chain reactions, and the formation of Teflon

from tetrafluoroethylene is one example. In this reaction, a peroxide (a
compound in which two oxygen atoms are joined together by a
single covalent bond) may be used as the initiator. Peroxides readily form
highly reactive free-radical species (a species with an unpaired electron)
that initiate the reaction. There are a number of different ways
to terminate the chain, only one of which is shown. (In the following
equations, the dots represent unpaired electrons, and R is a generic organic
group.)

1. Decomposition of a peroxide to radicals:ROOR → 2 RO∙

 2. Chain initiation:RO∙ + F2C=CF2 → ROCF2CF2∙
3. Chain-propagation steps:ROCF2CF2∙ + F2C=CF2 →
ROCF2CF2CF2CF2∙ROCF2CF2CF2CF2∙ + (n−2)F2C=CF2 → RO―(CF2CF2∙)n―
4. A possible chain-termination step:RO―(CF 2CF2∙)n― + ∙OR →
RO(CF2CF2)nOR

10. Photolysis reactions

Photolysis reactions are initiated or sustained by the absorption
of electromagnetic radiation. One example, the decomposition
of ozone to oxygen in the atmosphere, is mentioned above in the
section Kinetic considerations. Another example is the synthesis of
chloromethane from methane and chlorine, which is initiated by light. The
overall reaction is

CH4(g) + Cl2(g) + hυ → CH3Cl(g) + HCl(g),

where hυ represents light.