UNIT 4

CHEMICAL BONDING AND MOLECULAR STRUCTURE

Topics as per the syllabus 2020-21

* Valence electrons
* Ionic bond
* Covalent bond
* Bond parameters
* Lewis structure
* Polar character of covalent bond
* Covalent character of ionic bond
* Valence bond theory
* Resonance
* Geometry of covalent molecules
* VSEPR theory
* Concept of hybridisation involving s, p, d orbitals and shapes of some simple
molecules
* MOT of homo nuclear diatomic molecules
* Hydrogen bond

Valence electrons
The electrons in the outermost shell.

Lewis structures.

The structures in which dot represent electrons are called Lewis structures.
Conditions for stability of an atom
Duplet (For atoms with only 1 shell): 2 electrons
Octet (For atoms with more than one shell): 8 electrons in the outermost shell.

Why do atoms combine?

Inorder to complete the respective octet (or duplet for single shelled atoms) and
thereby attain stable configuration like noble gases.

How do atoms combine?

 By the complete transference of one or more electrons from one atom to
another.
 By sharing of electrons equally by both the combining atoms
 By contributing electrons entirely by one of the atoms but shared by both.

ELECTROVALENT OR IONIC BOND

When a bond is shared by the complete transference of electrons from one atom to
another so as to complete the stable octet condition is called ionic bond or
electrovalent bond.
 Formed between metals and non-metals.
Method
Atoms are electrically neutral. Therefore they have equal number of protons and
electrons.
On losing electron, atom becomes positive in charge as the number of protons are
greater than number of protons.
M -> M+ + e

Eg:

On gaining an electron, atom becomes negatively charged as the number of

electrons become greater than that of protons.
X + e -> X-
Eg:
The oppositely charged particles formed above attract each other by electrostatic
force of attraction. A bond is formed thus and is known as ionic bond.

The electrostatic force of attraction that holds the oppositely charged ions
together is called ionic bond.
  Ionic bonds will be formed more easily between elements with comparatively
low ionisation enthalpies and elements with comparatively high negative value
of electron gain enthalpies.

Lattice enthalpy
The energy required to completely separate one mole of a solid ionic compound into
gaseous constituent ions.

COVALENT BONDING
Bonds which are formed by the sharing of an electron pair between two atoms are
known as covalent bonds.
The shared electrons belong to the outermost shells of both the atoms and thus both
the atoms attain octet configuration or stable noble gas configuration.
Covalently bonded molecules have strong bonds within the molecule but
intermolecular forces are weak. Therefore these compounds have low melting and
boiling points.
Electrons are shared between atoms, and charged particles are not formed. Hence
covalent compounds are generally poor conductors of electricity.
Covalent bonding in Oxygen molecule

Covalent bonding in Nitrogen molecule

Covalent bonding in Chlorine molecule

Covalent bonding in methane molecule

Covalent bonding in HCl molecule

Covalent bonding in Water molecule

Covalent bonding in Ammonia molecule

BOND PARAMETERS
Bond length
The equilibrium distance between the nuclei of two bonded atoms in a molecule.
Measured by spectroscopic, X-ray diffraction and electron diffraction techniques.
Bond angle
The angle between the orbitals containing bonding electron pairs around the central
atom in a molecule/complex ion.
Expressed in degree which can be experimentally determined by spectroscopic
methods.
Bond enthalpy
The amount of energy required to break one mole of bonds of a particular type
between two atoms in a gaseous state. Unit : KJmol-1
Bond order
The number of bonds between the two atoms in a molecule, in the Lewis description
of covalent bond.
Single bond between 2 atoms : Bond order = 1
Double bond between 2 atoms : Bond order = 2
Triple bond between 2 atoms : Bond order = 3

Isoelectronic molecules and ions have identical bond orders.

POLARITY OF BONDS
Covalent bond with partial ionic character
In heteronuclear molecule, when two dissimilar atoms are bonded, the shared electron
pair shifts towards the more electronegative atom. As a result the one of the molecule
having more electronegative atom acquires a partial negative charge while the other
end acquires partial positive charge. Thus positive and negative poles are developed
and this type of bond is called polar covalent bond (ie,covalent bond with partial ionic
character).
Ionic bond with partial covalent character
Fajan’s rule
When a cation approaches an anion, the electron cloud of the anion is attracted
towards the cation and hence get distorted. This is called polarisation of the anion. The
power of the cation to polarise the anion is called its polarising power. The tendency of
the anion to get polarised is called polarisability.
The greater the polarisation produced, more is the neutralisation of the charges, and
hence ionic character decreases and covalent character increases.
Factors favouring the formation of covalent bond(character):
(i) Small size of the cation
The smaller the size of the cation, greater is its polarising power. That is why
LiCl is more covalent than KCl.
(ii) Large size of the anion
Larger the anion, greater is its polarisability.
Thus covalent character of lithium halides is in the order,
LiI > LiBr > LiCl > LiF
(iii) Electronic configuration of the cation
If two cations have the same size and charge , the one with pseudo noble gas
configuration(18 electrons in the outermost shell) has greater polarisability
than the one with noble gas configuration (8 electrons in the outermost
shell).
Eg: CuCl is more covalent than NaCl

DIPOLE MOMENT
The product of the magnitude of the charge and the distance between the
centres of positive and negative charges. Designated by the symbol μ.

Dipole moment = charge (q) x distance of separation (r)

It is a vector quantity. Depicted by small arrow with tail at the positive

centre and head pointing towards the negative centre.
 Greater the electronegativity difference between the bonded atoms,
greater is the dipole moment.

In the case of polyatomic molecules, the dipole moment is the vector sum
of the dipole moments of various bonds.

In symmetrical molecules like BF3, CH4 and CCl4 , the molecular dipole moment is found
to be zero. This is because the individual dipole moments cancel out on account of the
symmetry of the molecule.

Resultant dipole moment

If all the bonds are not identical, the molecule may have a net dipole moment, eg:
CHCl3.
DIPOLE MOMENTS IN NH3 AND NF3
The net dipole moment of NH3 is greater than that of NF3. This is because in NH3, the
orbital dipole due to lone pair is in the same direction as the resultant dipole moment
of the N-H bonds, whereas in NF3, the orbital dipole is in the direction opposite to the
resultant dipole moment of the three N-F bonds.
The orbital dipole because of lone pair decreases the effect of the resultant N-F bond
moments, which results in the low dipole moment of NF 3.

VSEPR THEORY
VALENCE SHELL ELECTRON PAIR REPULSION THEORY.
 Proposed by Sidgwick and Powell in 1940
 Further developed and refined by Nyholm and Gillespie in 1957.
Postulates of VSEPR theory
 The shape of the molecule depends on the number of valence shell
electron pairs (bonded and nonbonded) around the central atom.
 Pairs of electrons in the valence shell repel one another since their
electron clouds are negatively charged.
 These pairs of electrons tend to occupy such positions in space that
minimise repulsion and thus maximise distance between them.
 The valence shell is taken as a sphere with the electron pairs localising
on the spherical surface at maximum distance from one another.
 A multiple bond is treated as a single electron pair and the two or three
electron pairs of a multiple bond are treated as a single super pair.
 If there are more structures that can represent a molecule, the VSEPR
model is applicable to any such structure.
 The repulsive interaction of electron pairs decreases in the order:
Lone pair - Lone pair > Lone pair – bond pair > bond pair - bond pair

SHAPES OF MOLECULES CONTAINING BOND PAIRS ONLY AND BOTH BOND

PAIRS AND LONE PAIRS.
PREDICTING THE SHAPES OF MOLECULES
(i) Total number of electron pairs around the central atom = ½( number of
valence electrons around the central atom + number of atoms linked to the
central atom by single bond)
 For –ve ions: Add the no. of electrons equal to the units of negative charge
on the ion to valence electrons of the central atom
For +ve ions: Subtract the no. of electrons equal to the units of positive charge
on the ion from the valence electrons of the central atom

(ii) No. of bond pairs(shared pairs) = number of atoms linked to the central atom
by single bond
(iii) No. of lone pairs = Total number of electron pairs - No. of bond pairs(shared
pairs)

Practice problems:
On the basis of VSEPR theory predict the shape of
(i) ClF3
(ii) BrF5
(iii) NH2-
(iv) H3O+

Limitations of VSEPR theory

 Unable to predict the shapes in many cases.
 Direction of electron pairs is not rational.

VALENCE BOND THEORY

 Put forward by Heitler and London in 1927
 Developed by Pauling and others.
Consider two hydrogen atoms A and B. When the two atoms are far apart from
each other, there is no interaction between them. When they come closer to
each other, the new forces come into operation.
(i) Force of attraction
Between Nucleus of A and electrons of B
Between Nucleus of B and electrons of A
(ii) Force of repulsion
Between electrons of the two atoms
Between the nuclei of the two atoms
In case of hydrogen the magnitude of the attractive forces is more than the repulsive
forces. As a result PE of the system decreases and the molecule is formed.
Since energy is released when the bond is formed between them, the hydrogen
molecule is more stable than the isolated hydrogen atoms. The energy so released is
called bond enthalpy.

Orbital overlap concept

According to this concept, lowering of energy takes place when atomic orbitals of the
approaching atoms partially interpenetrate into each other.
Thus, a covalent bond is formed between two atoms by the partial overlap of two half-
filled atomic orbitals containing electrons with opposite spin.
The strength of the bond depends on the extent of overlapping. Greater the
overlapping, stronger is the bond formed.

OVERLAPPING OF ATOMIC ORBITALS

When orbitals of two atoms come close to form a bond, their overlap may be positive,
negative or zero depending upon the sign (phase) and direction of orientation of
amplitude of orbital wave function in space.
Orbitals forming bond should have same sign (phase) and orientation in space, called
positive overlap.
TYPES OF BONDS
SIGMA AND Pi BONDS
SIGMA BONDS
 Formed by the head-on overlap or axial overlap or end-to-end overlap of the
combining atoms
 It can be between
o s and p orbitals
o p and p orbitals
 It is longer than pi bonds
 Since the extent of overlap is greater, it is effective and stronger and involves
less strain.
 Complete rotation of bonds is possible in sigma bonding.

Pi BONDS
 Formed by the sideways overlap of the orbitals of the combining atoms
 It can be between
o p and p orbitals
 It involves strain in the bonding
 Rotation is not possible around the bonds
 Less effective and weaker than sigma bonds.
 Since there is electron charge cloud above and below the orbitals, it is a reactive
site for the incoming electrophiles.
 A single bond will always be a sigma bond.
A double bond consists of one sigma bond and one pi bond.
A triple bond consist of one sigma bond and two pi bonds.

HYBRIDISATION
The process of intermixing of atomic orbitals of slightly different energies so as to
redistribute their energies, resulting in the formation of new set of orbitals of
equivalent energies and shape is called hybridisation.
Salient feaures of hybridisation
 The number of hybrid orbitals is equal to the number of atomic orbitals that get
hybridised.
 The hybridised orbitals are always equivalent in energy and shape.
 The hybrid orbitals are more effective in forming stable bonds than the pure
atomic orbitlas.
 These hybrid orbitals are directed in space in some preferred direction to have
mimimum repulsion between electron pairs and thus a stable arrangement.
Therefore the type of hybridisation indicates the geometry of the molecules.
Important conditions for hybridisation
 The orbitlas present in the valence shell of the atom are hybridised.
 The orbitals undergoing hybridisation should have almost equal energy.
 Promotion of electron is not essential condition prior to hybridisation.
 It is not necessary that only half filled orbitals participate in hybridisation. In
some cases, even filled orbitals of valence shell take part in hybridisation.
 TYPES OF HYBRIDISATION
(1) sp hybridisation or diagonal hybridisation.
 Invoves mixing of one s and one p orbital resulting in the formation of
two equivalent sp hybrid orbitals. (s and pz).
 Each sp hybrid orbitals have 50% s character and 50% p character.
 Has linear geometry.

Eg: BeCl2.

The ground state electronic configuration of Be

The excited state electronic configuration of Be

ACETLENE, C2H2
In the formation of ethyne molecule, both the carbon atoms undergo, sp hybridisation
having two unhybridised orbital, 2px and 2py.
o One sp hybrid orbital of one carbon atom overlaps axially with sp hybrid orbital
of the other carbon atom to form C-C sigma bond, while the other hybridised
orbital of each carbon atom overlaps axially with the half filled s orbital of
hydrogen atoms forming sigma bonds.
o Each of the two unhybridised p orbitals of both the carbon atoms overlap
sideways to form two pi bonds between the carbon atoms.

o So the triple bond between two carbon atoms is made up of one sigma bond
and two pi bonds.

(2) sp2 hybridisation or trigonal hybridisation

 Invoves mixing of one s and two p orbitals resulting in the formation of
three equivalent sp2 hybrid orbitals.
 Each sp2 hybrid orbitals have 33% s character and 67% p character.
 Has trigonal planar geometry with bond angle 1200.

Eg: BF3.
 HW: Explain the structures of BH3 and C2H4

(3) sp3 hybridisation or tetrahedral hybridisation

 Invoves mixing of one s and three p orbitals resulting in the formation
of four equivalent sp3 hybrid orbitals.
 Each sp3 hybrid orbitals have 25% s character and 75% p character.
 Has tetrahedral geometry with bond angle 109.50.

Eg: CH4.
AMMONIA : NH3

The force of repulsion between a lone pair and a bond pair is more than the the force
of repulsion between two bond pairs of electrons. The molecule thus gets distorted
and the bond angle gets reduced to 1070 from 109.50.
Thus the geometry of the molecule is pyramidal (trigonal pyramidal).
Hybridisation is sp3.
WATER : H2O

Hybridisation : sp3
Bond angle and geometry: The four sp3 hybrid orbitals acquire a tetrahedral geometry,
with two corners occupied by hydrogen atoms while the other two by the lone pairs.
The bond angle is thus reduced to 104.50 from 109.50 and the molecule acquires a
V- shape or bent shape.

(4) sp3d hybridisation

o In PCl5, the five sp3d hybrid orbitals of phosphorus overlap with the singly
occupied p orbitals of chlorine atoms to form five P-Cl sigma bonds.
o Three P-Cl bonds lie in one plane and make an angle of 1200 with each other.
These bonds are termed as equatorial bonds.
o The remaining two P-Cl bonds- one lying above and the other lying below the
equatorial plane, make an angle 900 with the plane. These bonds are called axial
bonds.
o As the axial bonds suffer more repulsive interaction from the equatorial bond
pairs, therefore axial bonds have been found to be slightly longer and weaker
than the equatorial bonds. As a result of which PCl5 molecule is more reactive.
 (5) sp3d2 hybridisation

In SF6 the central sulphur atom has the ground state configuration, 3s23p4 . One electron each
from 3s and 3p orbitals is promoted to 3d orbitals. These six orbitals get hybridised to form
six sp3d2 hybrid orbitals. Each of these sp3d2 hybrid orbitals overlaps with 2p orbital of
fluorine to form S−F bond. Thus, SF6 molecule has octahedral structure.
MOLECULAR ORBITAL THEORY
Developed by F Hund and RS Mulliken in 1932.
Salient features:
 The electrons in a molecule are present in the various molecular orbitals
as the electrons of atoms are present in the various atomic orbitals.
 The atomic orbitals of comparable energies and proper symmentry
combine to form molecular orbitals.
 While an electron in an atomic orbital is influenced by one nucleus
(monocentric), in a molecular orbital it is influenced by two or more nuclei
(polycentric) depending upon the number of atoms in the molecule.
 The number of molecular orbitals formed is equal to the number of
combining atomic orbitals.
o One is known as bonding molecular orbital
o The other is known as anti antibonding molecular orbital

 The electron probability distribution around a group of nuclei in a

molecule is given by a molecular orbital.
 The bonding molecular orbital has lower energy and hence greater
stability than the corresponding antibonding molecular orbital.
 The molecular orbitals are filled according to auf bau principle, Pauli’s
exclusion principle and Hund’s rule.

LINEAR COMBINATION OF ATOMIC ORBITALS

The formation of molecular orbitals may be described by linear combination of
atomic orbitals by addition and subtraction of wave functions of individual atomic
orbitals.

 The wave functions formed by the addition of atomic orbitals is called the
bonding molecular orbital.
 The wave functions formed by the subtraction of atomic orbitals is called the
antibonding molecular orbital.
 The bonding molecular orbital always possesses lower energy than either of the
atomic orbitals that have combined to form it.
  The energy of the antibonding molecular orbital is raised above the energy of
the parent atomic orbitals.

CONDITIONS FOR THE COMBINATION OF ATOMIC ORBITALS

1. The combining atomic orbitals must have the same energy or nearly same
energy.
2. The combining atomic orbitals must have the same symmetry about the
molecular axis.
3. The combining atomic orbitals must overlap to the maximum extent.

TYPES OF MOLECULAR ORBITALS.

Sigma, pi, delta, etc.

Molecular orbital elecrtonic configuration

For Li2, Be2, B2, C2, N2
σ1s < σ*1s < σ2s < σ*2s < (π2px = π2py) < σ2pz < (π*2px = π*2py) < σ*2pz

For O2 and F2
σ1s < σ*1s < σ2s < σ*2s < σ2pz < (π2px = π2py) < (π*2px = π*2py) < σ*2pz
ENERGY LEVEL DIAGRAM FOR MOLECULAR ORBITALS

ENERGY LEVEL DIAGRAM FOR N2 MOLECULE

ENERGY LEVEL DIAGRAM FOR O2 MOLECULE

ENERGY LEVEL DIAGRAM FOR O2+ MOLECULE

STABILITY OF MOLECULES
It is determined by bond order. Higher is the bond order greater is the stability of
molecule.

BOND ORDER (BO)

One half of the difference between the number of electrons present in the
bonding orbitals and the antibonding orbitals.

 Nb is the number of electrons in BMO and N a is the number of electrons in ABMO

o If Nb > Na, the molecule is stable
o If Nb < Na, the molecule is unstable
o If Nb = Na, the molecule is unstable

o +ve Bond order : Stable molecule

o -ve Bond order : Unstable molecule
o Zero Bond order : Unstable molecule

BO = 1 : Single bond
BO = 2 : Double bond
BO = 3 :Triple bond

BOND LENGTH

The bond length decreases as bond order increases.

MAGNETIC NATURE

Diamagnetic (repelled by magnetic field):

If all the molecular orbitals in a molecule are paired (doubly occupied).

Paramagnetic (attracted by magnetic field):

If one or more molecular orbitals in a molecule are unpaired (singly
occupied).
Q: Calculate the bond order of the following molecules.

H2:

Practice time
Q: Compare the relative stability of the following molecules and indicate their magnetic
properties.
a) O2, O2+, O2-, O22-
Q: Predict the magnetic property of the following molecules.
a) H2
b) Cl2
c) Be2
d) C2
e) N2
f) O2-
g) F2