UNIT – I

CHEMICAL BONDING

Ionic Bond

An ionic bond (also called electrovalent bond) is that bond which is formed
when one or more electrons from the valence shell of an atom (usually a highly
electropositive element) are completely transferred to the valence shell of another
atom (usually a highly electronegative element).

✓ An ionic bond is established between the two atoms whose electronegativity difference is very
high.
✓ The atom that loses electrons becomes positively charged (cation) while the atom that accepts
electrons becomes negatively charged (anion).
✓ The cations and anions thus obtained are then attracted towards each other by the electrostatic
force of attraction and are thus linked together by an ionic bond.

Thus,

An ionic bond can also be defined as the electrostatic force of attraction existing
between the cations and anions of an ionic compound.

✓ The cations and anions obtained by the loss or gain of electrons attain the nearest noble gas
configuration.

Example:

Formation of NaCl

Formation of MgO

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Favourable conditions for the formation of an ionic bond

1. Low ionization energy of atom M

The ionization energy of atom M should be low so that this atom may lose the electron readily
to form the cation, M+

2. High electron affinity of atom X

The electron affinity of atom X should be high so that this atom may accept the electron (lose by
M) ready to form the anion, X-

3. High value of lattice energy of the ionic crystal M+X-

Greater is the force of attraction between the constituent ions in an ionic solid, greater is the
stability of the ionic solid.

Greater is the magnitude of lattice energy of an ionic solid, greater is the electrostatic force of
attraction between the ions (lattice energy is the direct measure of the electrostatic force of attraction
between the ions) and hence greater is the stability of the ionic solid.

Thus, in order to get strong ionic bond in an ionic solid, its lattice energy should be very high.

4. Electronegativity difference between the atoms M and X should be very high

The electronegativity difference between the atoms M and X should be very high so that
complete transfer of electrons from M to X may be possible.

Properties of Ionic Compounds

1) They are soluble in polar solvents like water and insoluble in non-polar solvents like benzene
and ether.
2) They conduct electricity in solution and in molten states due the presence of ions.
3) They possess very melting and boiling points because the ions are held together by strong
electrostatic attraction.
4) The ionic crystals have high value of lattice energy.
5) Ionic solids are highly hard and brittle.

Inert Pair Effect

➢ Some of the heavier elements of p-block like those of groups III-A (Ga, In, Tl), IV-A (Ge, Sn, Pb),
V-A (As, Sb, Bi) and VI-A (Te, Po) show two oxidation states. These oxidation states differ from
each other by two units.
➢ The higher oxidation state for most of the elements is equal to their group number G, while the
lower one is equal to (G-2) as shown below:

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 III-A IV-A V-A VI-A
(ns2p1) (ns2p2) (ns2p3) (ns2p4)
G=3 G=4 G=5 G=6
Ga Ge As -
+1, +3 +2, +4 +3, +5
In Sn Sb Te
+1, +3 +2, +4 +3, +5 +4, +6
Tl Pb Bi Po
+1, +3 +2, +4 +3, +5 +2, +4

➢ Group number oxidation state G (i.e., higher oxidation state) is obtained when all the ns and np
electrons from ns2px configuration of p-block elements are lost, while the lower oxidation state
equal to (G-2) is obtained when only np-electrons are lost.
➢ Due to the extra stability of the ns-electron pair, it remains inert i.e., it is not lost. Such a pair of
ns-electrons is called inert electron pair and the effect caused by it is known as inert pair effect.

There are certain heavy elements having many electrons in their valence shells. But
they are reluctant to lose all these electrons, more precisely they do not easily part with the
pair of ‘s’ electrons in the valence shell. This is due to the greater penetration of the s-
electrons towards the nucleus, compared to p-electrons. This effect is known as inert pair
effect.

Lattice Energy

The lattice energy of an ionic solid is defined as the energy released when one mole
of gaseous cations and one mole of gaseous anions are brought together from infinite
distance to form one mole of an ionic solid.

The formation of one molecule of an ionic solid A+B- from its constituent gaseous ions A+(g) and
B-(g) may be represented as follows.

The energy released in the above equation is known as lattice energy. It is usually denoted by U.

According to the convention of the ‘First Law of Thermodynamics’ the energy released, i.e., the
lattice energy has a negative sign.

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Born-Haber Cycle (Experimental Determination of Lattice Energy)

This cycle devised by Born and Haber in 1919 relates the lattice energy of a crystal to other
thermochemical data.

Born-Haber cycle can be explained taking the formation of sodium chloride from elementary
solid sodium and elementary gaseous chlorine. Let us make the following assumptions,

1) Sodium metal is evaporated to sodium atom, Na(g). The energy of sublimation is +S.
2) The diatomic chlorine gas is dissociated to chlorine atom Cl(g). The energy of dissociation for
chlorine molecule is +D.
3) The sodium atoms are ionized to form Na+. The ionization energy of sodium atom is +I.
4) The electrons obtained from sodium atoms are transferred to chlorine atoms to form negative
chloride ions Cl-. The electron affinity of chlorine atom is –E.
5) The lattice energy of sodium chloride is –U0.
6) The heat of formation of the crystals from its element is –Q.

All these changes can be represented by the Born-Haber cycle as follows.

The total energy of formation of the crystal from its elementary components is given by the
equation.

So,

Importance of Born-Haber Cycle

1. It is used in the determination of electron affinities.

2. It is also useful in analyzing and correlating the stability of various ionic solids.

3. It also provides an explanation for why most metals fail to form stable ionic compounds in low
valence states.

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Polarizing Power & Polarisability

✓ Let us consider two oppositely charged ions A+ and B- which are adjacently placed in an ionic
crystal. Although the charges on the ions are equal, but charge densities are different.
✓ Charge density is higher on cation (due to smaller size) than on anion and hence the electron
cloud of the outermost shell of anion is electrostatically attracted by the cation. As a result, the
anion (B-) is polarized or deformed or distorted.
✓ The outer electrons of the anion B- are attracted in the middle of the nuclei of A+ and B-.
✓ It seems as the electrons are shared between the two atoms, a characteristic of the covalent
bond. Hence the ionic bond is tending to acquire some covalent character. This deviation is due
to polarization of anion by cation.

Polarizing Power

The ability of a cation to polarize a nearby anion is called polarizing power.

Polarizability

The tendency of an anion to get polarized or distorted by a cation is called its

polarizability.

Factors Affecting Polarisation of Ions

The main factors are,

1. Charge of cation or anion

✓ Generally speaking, the polarizing power of a cation increases with its charge, the higher the
charge on a cation the greater the polarizing power.
✓ The reason for this is that a cation having higher charge can attract electrons more effectively.
Thus, Ca2+ ion has greater polarizing power than Na+ ion.
✓ Similarly, the polarisability of anion increases with its charge, the higher the charge on anion,
the greater is its polarisability. The reason is that with an increase in negative charge, the anion
will be able to repel its outer electrons more effectively.

2. Size of cation or anion

✓ The polarizing power of a cation increases if its size is smaller while the polarisability of an anion
increases if the size is larger.

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Importance of Polarisation of Ions

This concept is quite successful in deciding about the nature of bond between two bonded
atoms.

1. If the polarization is quite small, the bonding is ionic.

2. If the polarization is very high, the bond is a pure covalent bond.

3. If the polarization is in between the two values expressed in (1) and (2), the bond is partial
covalent bond.

Fajan’s Rules

The various factors that affect the magnitude of the polarizing power of a cation and the
polarizability of the anion are suggested by Fajan. These are called Fajan’s rules.

1. Size of cation

If the cation is small, it will have greater polarizing power on anion.

2. Size of anion

If the anion is large, it will have greater tendency to get polarized by cations. When an anion is
small, the valency electrons are nearer to the nucleus and hence the tendency to get polarized by the
cation will be less.

3. Charge on ions

As the ionic charge on cation increases the polarizing capacity also increases.

Explanation

(i) Let us consider Ag+ and K+ whose ionic radii are 1.13Å and 1.33Å respectively. Because of
smaller size Ag+ will have greater polarizing power.

(ii) Let us consider Na+ and Al3+. Since Al3+ has got more ionic charge it will have greater
polarizing power.

Applications of Fajan’s Rules

1. Ease of formation of ions

For ions which have inert gas structure the predominant factors in their formation are the ionic
size and the ionic charge.

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 The effect of these two factors on the formation of common cations and anions can be
summarized as follows.

2. Physical properties of Chlorides

The physical properties (melting point, boiling point, electrical conductivity etc.,) of compounds
like chlorides are affected by the size of the cation.

3. Diagonal relationships

The so called diagonal relationships in the periodic table have been shown below.

These are due to the comparative ease of ionization of the elements joined by arrows.

Any increase in ease of ionization in passing down a group is counteracted by a decrease in the
ease of ionization passing from left to right.

4. Strengths of hydracids

Due to the increasing size of anions in sixth and seventh groups, the acidic character increases as
we go down the group.

For example, due to the larger size of S- -, H2S is stronger acid than H2O.

Covalent Bond

✓ Covalent bond is formed between two non-metallic atoms of comparable electronegativity.

✓ In the formation of a covalent bond, equal number of electron(s) is (are) shared between the
two concerned atoms.

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 ✓ The atoms involved in the covalent bond formation make equal contribution of electrons and
achieves the stable electronic configuration of the nearest noble gas.
1) When each atom contributes one electron and hence two contributed electrons (one pair) are
shared by each atom. The bond formed is known as single bond.

Other common examples are NH3, BF3, alkanes etc.,

2) When each atom contributes two electrons and hence four contributed electrons (two pairs) are
shared by two atoms. The bond formed is known as double bond.

Common examples are CO2, O2, Olefins etc.,

3) Similarly, triple bond is formed by the sharing of three pairs of electrons.

Common examples are N2, alkynes etc.,

✓ Compounds having covalent bond are known as covalent compounds.

Properties of covalent compounds

1) These compounds are molecular in nature.

2) Covalent bond is a weaker bond. The strength of the covalent bond decreases with the increase
in bond length
3) Due to intermolecular forces, covalent compounds have low melting and boiling points.
4) These are insoluble in water and soluble in non-polar solvents like benzene.

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Orbital Overlap

A covalent bond is formed by the sharing of a pair of electrons between two atoms. For this, to
happen the orbital of one of the combining atoms overlap with the orbital of the other atom.

Types of Orbital Overlapping

1. s-s Overlapping:- If one s-orbital of an atom overlaps with one s-orbital of another atom to form a
covalent bond, it is called s-s overlapping.

A molecule of hydrogen is formed by the overlapping of one 1s orbital of a hydrogen atom with
one 1s orbital of another hydrogen atom.

2. s-p Overlapping:- If one s-orbital of an atom overlaps with one p-orbital of another atom to form a
covalent bond, it is called s-p overlapping.

A molecule of hydrogen fluoride is formed by the overlapping of one s-orbital of a hydrogen

atom with one p-orbital of fluorine atom.

3. p-p Overlapping:- If one p-orbital of an atom overlaps with one p-orbital of another atom to form a
covalent bond then it is called p-p overlapping.

A molecule of fluorine is formed by the overlapping of one 2p orbital of a fluorine atom with one
2p orbital of another fluorine atom.

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σ-bond and π-bonds

σ-Bond

When two bonding orbitals overlap to form a molecular orbital (MO) which is symmetrically
distributed about the nuclear axis (the line joining the nuclei of the two atoms) then the bond so formed
is called a sigma bond.

Sigma bonds are formed as the result of the orbital overlaps of

1. s-orbital of one atom and s-orbital of the other;

Eg., Formation of H2 molecule; s-s overlap

2. s-orbital of one atom and p-orbital of the other;

Eg., Formation of HF molecule; s-p overlap

3. p-orbital of one atom and p-orbital of the other (in a linear fashion)

Eg., Formation of F2 molecule; p-p overlap

π-Bond

When two p-orbitals overlap in a sidewise fashion or laterally to form a molecular orbital (MO),
then the bond so formed is called a π-bond.

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 For a lateral overlap, the two p-orbitals must be held parallel. The MO thus formed lies above
and below the nuclear axis.

Formation of O2 molecule

1. Head on overlap – σ bond

2. Sidewise (lateral) overlap – π bond

Thus in oxygen molecule there are two bonds: one σ-bond and one π-bond. Both of them together
are called a double bond. In practice two horizontal lines are used to indicate a double bond.

O=O

Formation of N2 molecule

1. Head on overlap – σ bond

2 and 3. lateral overlaps – two π bonds

Thus in nitrogen molecule there are three bonds: one σ-bond and two π-bonds. All the three bonds
put together are called a triple bond. In practice three horizontal lines are used to indicate a triple bond.

N≡N

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Valence Bond Theory

✓ To explain the formation of covalent bond Heitler and London in 1927 put forward the Valence
bond theory. This theory was developed by Linus Pauling. Salient features of this theory are
summed up below:
1) According to this theory atoms maintain their individuality even in the molecule. The bond is
formed by the interaction of half-filled orbitals belonging to the valence shells of the
participating atoms.
2) The overlapping atomic orbitals must contain the electrons with opposite spins.
3) The strength of the bond depends upon the extent of overlapping. The greater the overlap
stronger is the bond.
4) As a result of overlapping and therefore pairing of electrons energy is released and hence the
system acquires a state of lower energy.
5) The stability of the molecule is further explained in terms of the exchange of electrons between
the atoms participating in bond formation.
6) The valency of an element is equal to the number of half-filled orbitals in the valence shell of its
atom.

Pauling-Slater’sTheory

✓ The idea that atoms form covalent bonds by sharing pairs of electrons was first proposed by
G.N. Lewis in 1902, however, Walter Heitler and Fritz London in 1927 showed how the sharing
of pairs of electron holds a covalent molecule together. The last major step in the evolution of
this theory was by Pauling and Slater in 1931. Pauling Slater theory is the modified form of
Heitler London theory.

The main postulates of the theory are:

1) An atom must possess one or more unpaired electrons to enter into a chemical combination.
The atomic orbitals of the valence shell which have paired electrons, do not contribute to the
bond formation. The electron pairs in these orbitals are called non-bonding electron pairs or
lone pairs of electrons.
2) Atoms with unpaired electrons tend to combine with other atoms which also have unpaired
electrons.
3) The new orbital which is formed due to overlapping of atomic orbitals is more stable.
4) The strength of the bond is determined by the extent of overlapping of two half-filled orbitals.
More is the overlapping, more is the decrease in energy and stronger is the bond formed.
5) The relative strength of the covalent bonds obtained by s-s, p-s and p-p overlap is as s-s < p-s <
p-p. Covalent bond formed by s-s overlap is weak, because these have spherical distribution of
electron density whereas the p-s overlap is comparatively better as p-orbitals are concentrated
in a particular direction and their lobes are longer than the radius of the corresponding s-orbital.
6) The shape of the molecule is determined by the directions in which orbitals point.
7) According to this theory, an electron moves under the influence of only one nucleus of an atom.

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 8) The number of bonds formed by an atom is equal to the number of unpaired electrons it has.

Molecular Orbital Theory (MO Theory)

✓ Molecular orbital theory was put forward by Hund and Mulliken in 1932. It assumes that in
molecules atomic orbitals lose their identity and the electrons in molecules are present in new
orbitals called molecular orbitals.

The salient features of this theory are given below:

1) In molecules, electrons are present in new orbitals called molecular orbitals. Molecular orbitals
like atomic orbitals are characterized by a set of quantum numbers.
2) Molecular orbitals are formed by combination of atomic orbitals of nearly same energies.
3) Molecular orbitals are not associated with a particular atom but belong to nuclei of all the atoms
constituting molecule. Nuclei of different atoms in the molecule behave as a polycentric
nucleus.
4) The number of molecular orbitals formed is equal to the number of atomic orbitals undergoing
combination. Among the new molecular orbitals formed, half are of lower energy than
combining atomic orbitals (bonding molecular orbitals) and the other half are of energy greater
than combining atomic orbitals (anti-bonding molecular orbitals).
5) The shapes of the molecular orbitals depend upon the shapes of combining atomic orbitals.
6) The molecular orbitals are filled in the increasing order of their energies, starting with the
orbital of least energy. (Aufbau rule)
7) A molecular orbital like atomic orbitals can accommodate only two electrons and these
electrons must have opposite spin. (Pauli’s principle)
8) While filling molecular orbitals of equal energy pairing of electrons does not take place until all
such orbitals are singly occupied. (Hund’s rule)

Bonding and Anti-Bonding Orbitals

✓ Two atomic orbitals, one from each bonded atom, whose energies are comparable in value and
which possess a large amount of overlap, coalesce (mix together) to form two molecular
orbitals.
✓ One of these molecular orbitals is lower in energy than either of the atomic orbitals from which
it was formed and hence gives rise to an attractive state as depicted in Fig.

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 ✓ The other molecular orbital is higher in energy and, therefore, gives rise to a repulsive state. This
high energy molecular orbital is termed as the anti-bonding molecular orbital, since electrons
placed in this kind of orbital decrease the stability of the bond. The anti-bonding orbitals are
represented by superscript asterisks.
✓ The lower energy molecular orbital is called bonding molecular orbital, since electrons placed in
such an orbital increase the stability of the bond.

Linear Combination of Atomic Orbitals (LCAO) method

✓ The formation of molecular orbitals from atomic orbitals can be explained by the Linear
Combination of Atomic Orbitals (LCAO) method.
✓ Molecular orbitals are formed by the combination of atomic orbitals of bonded atoms. In wave
mechanics atomic orbitals are expressed by wave functions (Ψ).
✓ To understand the significance of bonding and anti-bonding molecular orbitals in terms of wave
functions, it is necessary to know the electronic charge distribution of these orbitals. A simple
method for this consists in the derivation of molecular orbitals by the linear combination of
atomic orbitals (LCAO method).

✓ Let us apply this theory to homo nuclear diatomic molecules such as hydrogen molecule. Let us
consider the two atoms of hydrogen in the molecule as A and B.
✓ Each hydrogen atom has one electron in 1s orbital in ground state. These atomic orbitals may be
represented by the wave functions ΨA and ΨB. Then according to LCAO method, the molecular
orbitals in the H2 molecules are given by linear combination of ΨA and ΨB as shown below.

✓ The molecular orbital Ψb formed by the addition overlap of atomic orbitals is called bonding
molecular orbital and the molecular orbital Ψa formed by the subtraction overlap of atomic
orbitals is called anti-bonding molecular orbital.

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 Differences between bonding and anti-bonding molecular orbitals

Bonding Molecular Orbital Anti-bonding Molecular Orbital

1. Bonding molecular orbital is formed by the 1. Anti-bonding molecular orbital is formed by the
addition overlap of atomic orbitals. subtraction overlap of atomic orbitals.

2. It may or may not have a node. 2. It always has a node in between the nuclei of
bonded atoms.
3. Electrons in this orbital lead to attraction 3. Electrons in this orbital lead to repulsion
between atoms. between atoms.
4. Its energy is less than the energy of the atomic 4. Its energy is more than the energy of the atomic
orbitals. orbitals.

Tabulation of various M.O.s formed from atomic orbitals

Molecular Orbitals Atomic orbitals from which the molecular orbitals are
Bonding Anti-bonding formed
σ1s σ*1s 1s orbitals of the two atoms
σ2s σ*2s 2s orbitals of the two atoms
σ2p σ*2p 2px orbitals of the two atoms
πy2p πy*2p 2py orbitals of the two atoms
πz2p πz*2p 2pz orbitals of the two atoms

The energy of these molecular orbitals increases as we move from left to right in the following
list:

σ(1s) < σ*(1s) < σ(2s) < σ*(2s) < σ(2p) < [πy(2p) , πz(2p)] < [πy*(2p), πz*(2p)] < σ*(2p)

Thus, σ(1s) possesses the lowest and σ*(2p) possesses the highest energy. This sequence of
increasing energy level is shown in the Fig.

Two orbitals which have the same energy are referred to as doubly degenerate. For example,
πy2p = πz(2p) and πy*(2p) = πz*(2p)

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