CHEMICAL BONDING: INTRODUCTION

All the atoms, except those of inert gases, participate readily in the formation of chemical
bonding. It is necessary to understand the formation and nature of chemical bonds to arrive at
the structures of molecules; study the interactions between them; and to understand the chemical
reactivity.
Let us start with a few fundamental questions:
What is a chemical bond?
In simple words, the attraction between two atoms or ions that holds them together is known
as chemical bond.
How is it formed?
A chemical bond may be formed either by sharing of electrons or by transfer of electrons between
atoms i.e., by reorganization of electrons between atoms.
This is the major difference between intermolecular forces of attractions (van der Waals forces)
and chemical bonds. In case of van der Waals forces of attractions, there will be no reorganization
of electrons occurring between two atoms.
Why a chemical bond is formed?
A chemical bond is formed by an atom to get more stability. Every atom tries to get more
stability by lowering its potential energy. This can be achieved by making a bond.
The potential energy decreases when two atoms attract each other. Hence energy is liberated
during the formation of a chemical bond i.e., it is an exothermic process.

Note: Read the graph from right to left.

The potential energy of the atoms is arbitrarily fixed as zero when there is no attraction between
them. As the two atoms start overlapping with each other, the potential energy also decreases and
reaches minima (move your eye from right to left). The distance between the nuclei of two atoms
at this point is called bond length. The forces of attraction between two atoms are maximum at
this point.
However the potential energy starts increasing again if the atoms are bring more closer than this
distance, since repulsion forces start dominating the forces of attractions.
What is the connection between stability and electronic configuration?
The noble gas atoms with octet configuration in their outer shells are very stable. Hence every
atom tries to get octet configuration either by losing or gaining or sharing electrons. This is also
called as octet rule.
However this rule may not be followed always by the atoms.

TYPES OF CHEMICAL BONDS : A BRIEF INTRODUCTION

The chemical bonds are broadly divided into:
1) Ionic bond
2) Covalent bond

3) Metallic bond
The electrostatic force of attraction between two oppositely charged ions is called ionic bond.
An ionic bond is formed due to transfer of electrons from one atom to another.
The atom that loses electrons will form a cation and the atom that gains electrons will form
an anion. These oppositely charged ions come closer to each other due to electrostatic
force of attraction and thus by forming an ionic bond.
An ionic bond is formed between two atoms when their electronegativity difference is
greater than 1.7 on Pauling's scale.
In general, an ionic bond is formed between a metal atom and a non-metal atom.
E.g., NaCl, LiF, MgCl2 etc.,
2) Covalent Bond: The chemical bond formed between two atoms due to the sharing of
electron pair(s) is called covalent bond.
It is formed between two atoms for which the electronegativity difference is less than
1.7 on Pauling's scale.
Usually two non-metal atoms form a covalent bond.
E.g. H2, F2, HCl, H2O etc.
The shared pair of electrons, also known as bond pair, is either formed due to equal
contribution of electrons by each atom participating in the bond formation; or
contributed by only one atom. In the later case, the bond is also known as co-ordinate
covalent bond or dative bond.
3) Metallic bond: It is the attraction between metal atoms in a metallic crystal. It is formed
between electropositive metal atoms of same or different elements. It is also considered as highly
delocalized covalent bond.
E.g. the metal atoms Na, Cu, Ag, Fe etc. are bound to each other in their crystals by metallic bond.

THEORIES OF CHEMICAL BONDING

Several theories were put forwarded to explain the chemical bonding. The important theories of
chemical bonding are:
1. Electronic theory of chemical bonding: According to this theory proposed independently
by Kossel & Lewis, a chemical bond between atoms is formed in order to get nearest inert
gas configuration. This can be achieved by either losing or gaining or sharing electrons.
2. Valence bond theory: This theory of chemical bonding was first proposed by Heitler &
London and developed by Linus Pauling. It explained the formation of covalent bonds
between atoms, which is supposed to be formed due to overlapping of atomic orbitals.
3. Molecular orbital theory: This is rather an advanced treatment for chemical bonding.
According to this theory, the atomic orbitals of bonding atoms combine with each other by
giving rise to molecular orbitals.

IONIC BOND
The ionic bond is the electrostatic force of attraction between two oppositely charged ions i.e., a
positively charged cation and a negatively charged anion. It is formed due to complete transfer of
electrons from one atom to another atom.
The steps involved in the formation of ionic bond can be summarized as:
a.

An electropositive atom (metal) loses electron(s) to form a positively charged ion called as
cation.

b.

An electronegative atom accepts the electron(s) to form a negatively charged ion, otherwise
known as anion.

c.

Thus formed oppositely charged ions come closer to each other due to electrostatic force of
attraction and get stability.
The formation of ionic bond between two atoms can be visualized as follows:

An ionic bond is formed when the electronegativity difference between two bonding atoms
is greater than 1.7 on Pauling's scale.

It can be observed that an ionic bond is formed between an electropositive metal atom and
an electronegative non-metal atom.

KOSSELL'S ELECTRONIC THEORY OF CHEMICAL BONDING

The formation of ionic bond was explained by Kossell as follows:

The atoms of inert gases are stable due to octet configuration (ns2np6) in their outer shell.
Hence atoms must possess eight electrons in their outer shell to get more stability. This is
referred to as octet rule.

However, Helium is also highly stable due to 1s2 configuration.

Therefore every atom tries to get nearest inert gas configuration either by losing or gaining
electrons to form ionic bond.

Only the electrons in the outer shell participate in bond formation. These electrons are also
called as valence electrons.

The electrons in the inner shell are called as core electrons and do not participate in the bond
formation.
Electrovalency: The number of valence electrons either lost or gained by an atom during the
ionic bond formation is called electrovalency.

ILLUSTRATIONS
1) LiF (Lithium fluoride):

In the formation of Lithium fluoride, the Lithium atom loses one electron to get nearest
inert gas: Helium's configuration, 1s2.

Whereas, the Fluorine atom gains one electron to get nearest inert gas: Neon's
configuration, 1s22s22p6.

Thus formed Li+ and F- ions get attracted towards each other to form the ionic compound
LiF.

The electrovalency of Lithium is one since it loses one electron.

The electrovalency of Fluorine is also one since it gains one electron.

Note: The electronegativity difference between Li (1.0) and F (4.0) is 3.0, which is greater than
1.7. Hence they form ionic bond.
2) MgCl2 (Magnesium chloride):

The Magnesium chloride is an ionic compound. The formation of ionic bond in this
compound can be explained as follows.

The Magnesium atom loses two electrons to get Neon's configuration, [He]2s22p6.

Each Chlorine atom gains one electron to get Argon's configuration, [Ne]3s23p6.

Thus formed Mg2+ and two Cl- ions combine together by forming MgCl2.

The electrovalency of Mg is 2 and that of Cl is 1.

Note: The electronegativity difference between Mg (1.2) and Cl (3.0) is 1.8. Hence they form ionic
bond.
3) AlF3 (Aluminium Fluoride) :

The Aluminium atom loses 3 electrons and each Fluorine atom gains 1 electron to get their
nearest inert gas: Neon's configuration, [He]2s22p6.

Thus formed Al3+ and three F- ions combine together to give AlF3.

The electrovalency of Al is 3 and that of F is 1.

Note: The bond between Al (e.n = 1.5) and F (e.n = 4.0) is ionic since the electronegativity
difference between them is 2.5.
4) Na2O (Sodium monoxide) :

In the formation of Sodium monoxide, the each sodium atom loses 1 electron and oxygen
gains 2 electrons. While doing so, both atoms will get the nearest inert gas: Neon's
configuration, [He]2s22p6.

Thus formed two Na+ and O2- ions combine to form Na2O.

The electrovalency of 'Na' is 1 and that of 'O' is 2.

Note: The bond between Na (e.n = 0.9) and O (e.n = 3.5) is ionic since the electronegativity
difference between them is 2.6.

FACTORS FAVORING THE FORMATION OF IONIC BOND

In general, the bond between two atoms gets ionic nature when the electronegativity difference
between them is large (greater than 1.7 on Pauling's scale). Since the Ionic bond is electrostatic
force of attraction between cation and anion, the factors favouring their formation also favour the
formation of ionic bond.
Factors favouring the formation of cation :
1.

Large atomic size: In larger atoms, the nuclear attraction over the outer electrons is
less. Hence they lose electrons readily to form cations.
E.g. the ease of formation of cation increases from Li+ to Cs+ in IA group with increase in
size.

2.

Low ionization energy : The removal of electrons is easy from atoms with low ionization
energy values. Hence these atoms form cation easily.
E.g. IA and IIA group elements readily form cations due to low ionization energies.

3.

Low charge on cation : Since the successive ionization energies are increased (i.e., from
IE1 to IE2 to IE3_ _ _), the formation of cations with high charge require more energy.
Hence the cations with low charge are formed easily, whereas those with high charge are
formed with difficulty.
E.g. Among Na+, Mg2+ and Al3+ , the order of ease of formation is: Na+ > Mg2+ > Al3+
i.e., Na+ is formed more readily than Mg2+ and Al3+

4.

Octet electronic configuration : The cations with 8 electrons in the outer shell (octet
configuration) are highly stable and hence are formed readily. Whereas cations with 18
electrons in outer shell (Pseudo inert gas configuration) are comparatively less stable and
hence are not formed easily.

E.g. The electronic configuration of Ca2+ is [Ne]3s23p6. There are 8 electrons in the outer shell
(octet configuration) Hence it is formed easily.
Whereas the electronic configuration of Zn2+ is [Ne]3s23p63d10 (pseudo inert gas configuration).
Hence Zn2+ is formed less easily than Ca2+.

Factors favouring the formation of anion :

1.

Small atomic size: Atoms with small atomic size attract electrons strongly and hence can
form anions readily.

2.

High electron affinity and electronegativity: The atoms, with high electron affinity and
electronegativity, gain electrons easily and hence form anions readily.
E.g., The halogens (VIIA group elements) can form anions readily due to small size, high
electron affinity and high electronegativity.

3.

Low charge on anion: The formation of highly charged anions is difficult since the
addition of successive electrons to the atoms becomes difficult due to repulsion from
electrons within the atom. Hence anion with low charge is formed readily.

E.g., Among C4-, N3-, O2- and F- ions, the anion with low charge i.e., F- is formed readily, whereas
the formation of anion with higher charge (C4-) is difficult.
i.e., The order of ease of formation of these anions is: C4- < N3- < O2- < F-

PROPERTIES OF IONIC COMPOUNDS

1.

Physical state and properties: The ionic compounds contain oppositely charged ions
which are strongly attracted to each other. Hence these are hard substances existing as
crystalline solids at room temperature. Their melting and boiling points are very high due
to strong electrostatic forces of attractions between the ions.

2.

Direction of bond: The ionic bond is direction less and the electrostatic forces of
attraction are present in all directions around an ion. Hence there is no isolated discrete
molecule in the ionic crystal. Entire crystal is considered as the giant molecule.
The ionic compounds do not exhibit isomerism due to non-directional nature of ionic bond.

3.

Electrical conductivity: In the solid state, the ions cannot move freely and hence they do
not conduct electricity. However in the fused state or in aqueous solutions, the ionic
compounds show electrical conductivity due to presence of freely moving ions.

4.

Solubility: Ionic compounds are polar in nature and hence they are soluble in polar
solvents like water. However these are not soluble in non-polar solvents like benzene,
carbon tetrachloride etc.

5.

Reactivity: The reactions between ionic compounds in aqueous solutions occur very fast
due to presence of separated ions.

e.g. A white precipitate of AgCl is formed instantly when aqueous solution of NaCl and AgNO3 are
mixed.
Formula weight: The ionic compounds contain only ions which are attracted towards oppositely
charged ions in all directions. There are no discrete molecules in it. Hence their molar mass is
denoted as formula weight instead of molecular weight.

ENERGETICS OF FORMATION OF IONIC COMPOUNDS

The major steps likely to be involved in the formation of ionic compounds can be summarized as:
Formation of gaseous atoms: The atom that is participating in the ionic bond formation is to be
isolated from other atoms. This is achieved by converting the metal into gaseous state from either
solid or liquid state by supplying energy.

In case of non metals, which usually exist in molecular form, an additional step of conversion of
gaseous molecules into atoms is required. The energy required for this process is known as bond
dissociation energy.

Note: Depending on the state of metal or non-metal under the reaction conditions, all of these
steps may or may not be required.
Formation of cation from gaseous electropositive atom: A cation is formed when electron(s)
are removed from the atom by supplying energy. The minimum amount of energy required for this
process is called ionization energy.

Formation of anions from gaseous electronegative atom: An anion is formed when

electron(s) are added to the atom. In this step, energy is liberated. This is called electron gain
enthalpy or electron affinity.

Formation of ionic crystal from gaseous ions: The gaseous cations and anions come closer to
each other due to electrostatic forces of attractions and form ionic crystal along with the liberation
of energy, which is otherwise called as lattice energy.

The amount of energy required during the initial steps like fusion, vaporization, sublimation, bond
dissociation, removal electrons etc., is usually more than compensated partly by electron gain
enthalpy and mostly by lattice energy.

The amount of energy liberated i.e. lattice energy will be greater if the attraction between the
oppositely charged ions is stronger.
Greater the lattice energy, greater is the ease of formation of that ionic compound. The magnitude
of lattice energy depends on the charge density on ions and the distance between them.
Greater the charge density on the ion, greater is its attraction with oppositely charged ions.
Shorter the distance between ions, stronger is the attraction and hence greater is the lattice
energy.
Lattice energy of crystal (U): The amount of energy liberated when one mole of the crystalline
substance is formed from the constituent gaseous ions is called lattice energy (U) of the crystal.
The determination of lattice energy of NaCl by using Born-Haber cycle is shown below.

CALCULATION OF LATTICE ENERGY OF NaCl: BORN-HABER CYCLE

The principle involved in Born-Haber cylcle is Hess's law of constant heat summation which can
be stated as follows:

Hess's Law : The total energy change in a reaction remains same whether the reaction takes
place in one step or in several steps.
The NaCl crystals can be obtained from sodium metal and chlorine gas either in one step or in
several steps indirectly as shown below.
Direct step : One mole of NaCl crystals are formed by combining one mole of Na metal with half
mole of chlorine gas in one step. The energy evolved during this reaction is called heat of
formation, Hf.

Indirect method : The formation of NaCl crystals may occur in several steps as follows.
i.

Sublimation of sodium : One mole of solid sodium is first converted gaseous sodium by
absorbing 108.7 kJ/mole of energy. This is called sublimation energy represented by
Hs or S.

ii.

Ionization of sodium : Gaseous sodium atoms are ionized by absorbing 492.82 kJ/mole
of energy. It is called ionization energy (Hi or I).

a.

a.
Dissociation of chlorine molecule : One mole of gaseous chlorine molecules are
dissociated into two moles of chlorine atoms by absorbing energy equal to 239.1 kJ/mole.
This is called dissociation energy (Hd or D).

iii.

a.
But the energy required to get one mole of chlorine atoms is equal to:

b.
i.e.,

c.
Chloride ion formation : The gaseous chlorine atoms are added with electrons to get
gaseous chloride ions. The energy liberated in this process is called electron affinity
(He or E).

iv.

a.
Formation of NaCl Crystals : The gaseous Na+ and Cl- ions unite to form one mole of
NaCl crystals. The energy liberated during this process is called lattice energy (Hu or U).

v.

The lattice energy, U can be calculated by using Hess's law as follows:

According to Hess's law, the energy change in the direct step is equal to the sum of energy
changes that occur in steps involved in indirect method.

or

BORN LANDE EQUATION

The lattice energy of an ionic crystal is equal to the sum of attractive and repulsive forces in the
crystal. It can be calculated by using Born Lande equation as follows:

Where
A = Madelung constant (which depends on geometry of the crystal)

The repulsion coefficient depends on the structure and approximately proportional to the
number of nearest neighbours
No = Avogadro's number
Z+ & Z- = Charges on the positive and negative ions respectively.
e = Charge of an electron.
r = Distance between the oppositely charged ions
n = Born exponent (a constant which is usually taken as 9)
Born Lande equation can be written as follows: