Main postulates of VSEPR theory

 The shape of a molecule depends upon the number of valence shell electron
pairs (bonded or non-bonded) 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 the 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 if it is a single electron pair and the two or three
electron pairs of a multiple bond are treated as a single super pair.
 Where two or more resonance structures can represent a molecule, the VSEPR
model is applicable to any such structure.
Electron pair’s repulsive interactions decrease in the following order: Lone pair
(lp) – Lone pair (lp) > Lone pair (lp) – Bond pair (bp) > Bond pair (bp) – Bond
pair (bp)
Prediction of geometrical shapes using VSEPR theory
It is convenient to divide molecules into two groups when using VSEPR theory to predict
the geometrical shapes of molecules:
I. Molecules with no lone pairs in the central atom
II. Molecules with one or more lone pairs in the central atom

The shape and geometry of a molecule with two electron pairs

The shape and geometry of a molecule with three electron pairs

The shape and geometry of the molecules with four electron pairs
The shape and geometry of the molecules with five electron pairs
Limitation of VSEPR theory
 Isoelectronic species that are not explained by this idea (i.e. elements having
the same number of electrons). Despite having the same number of electrons,
the shapes of the species can differ.
 The VSEPR theory provides little insight into transition metal compounds. This
theory cannot accurately describe the structure of several such molecules. This
is due to the fact that the VSEPR theory hypothesis ignores the substituent
groups' associated sizes as well as the inactive lone pairs.

Postulates of Valence Bond Theory:

 The overlapping of two half filled valence orbitals of two different atoms result in
the formation of the covalent bond. Due to overlapping, the electron density
between two bonded atoms increases and this gives stability to the molecule.
 In case the atomic orbitals possess more than one unpaired electron, more than
one bond can be formed and electrons paired in the valence shell cannot take part
in such a bond formation.
 A covalent bond is directional and it is parallel to the region of overlapping atomic
orbitals.
 Based on the pattern of overlapping, there are two types of covalent bonds: sigma
bond and a pi bond. The covalent bond formed by sidewise overlapping of atomic
orbitals is known as pi bond whereas the bond formed by overlapping of atomic
orbital along the inter nucleus axis is known as a sigma bond.
Hybridisation : It is a phenomenon of intermixing of atomic orbitals of almost equal
energy which are present in the outer shells of the atom and their reshuffling or
redistribution into the same number of orbitals but with equal properties like energy and
shape.

Formation of BF3 molecule:

(1) 5 B has electronic configuration 1s2 2s2 2px1.

(2) The excited electronic configuration of 5B is 1s2 2s1 2px1 2py1 .

(3) As it forms three identical B-F bonds in BF3 .

(4) It is suggested that excited 'B' atom undergoes hybridisation.

(5) There is an intermixing of 2s, 2px , 2py orbitals and their redistribution into three
identical orbitals called sp2 hybrid orbitals.

(6) For three sp2 orbitals to get separated to have minimum repulsion the angle between
any two orbitals is 120° at the central atom and each sp2 orbital gets one electron.

Formation of an ammonia (NH3) molecule on the basis of sp3 hybridization :

i) Ammonia molecule (NH3) has one nitrogen atom and three hydrogen atoms.

ii. The ground state electronic configuration of nitrogen (Z = 7) is 1s2 2s2 2 p 1 x 2px1 2 p
1 y 2py1 2 p 1 z 2pz1 Electronic configuration of nitrogen :

iii. The ground state electronic configuration explains the observed valency of nitrogen in
NH3 which is three.

iv. The 2s, 2px, 2py and 2pz orbitals of nitrogen atom mix and recast to form four sp3
hybrid orbitals of equivalent energy. These orbitals are tetrahedrally oriented in space.
One of the sp3 hybrid orbital contains a lone pair of electrons.
v. Three half-filled sp3 hybrid orbitals of N atom overlap axially with half-filled 1s orbital
of three different hydrogen atoms to form three N-H (sp3 -s) sigma covalent bonds.

vi. Since, there is one lone pair of electrons in one of the sp3 hybrid orbitals of nitrogen,
there is repulsion between lone pair and bonding pair of electrons. As a result, The HN-H
bond angle is reduced from regular tetrahedral angle 109°28′ to 107°18′. Geometry of
NH3 molecule is pyramidal or distorted tetrahedral

Formation of water (H2O) molecule on the basis of sp3 hybridization :

i. Water molecule (H2O) has one oxygen atom and two hydrogen atoms.

ii. The ground state electronic configuration of oxygen (Z = 8) is 1s2 2s2 2 p 2 x 2px2 2 p
1 y 2py1 2 p 1 z 2pz1. Electronic configuration of oxygen

iii. The ground state electronic configuration explains the observed valency of oxygen in
H2O molecule which is 2.

iv. The 2s, 2px, 2py and 2pz orbitals of oxygen atom mix and recast to form four sp3
hybrid orbitals of equivalent energy. These orbitals are tetrahedrally oriented in space.
Two of the sp hybrid orbitals contain lone pair of electrons.

v. Two half-filled sp3 hybrid orbitals of O atom overlap axially with half-filled 1s orbitals
of two different hydrogen atoms to form two O-H (sp3 -s) sigma covalent bonds.

vi. Since, there are two lone pairs of electrons in two of the sp hybrid orbitals of oxygen,
there is repulsion between lone pair and bonding pair of electrons. As a result, the HO-H
bond angle is reduced from regular tetrahedral angle 109°28′ to 104°35′. The geometry
of H2O molecule is angular or V shaped.
BOND ANGLE: Bond angle can be defined as the angle formed between two covalent
bonds that originate from the same atom. An illustration detailing the bond angle in a
water molecule (104.5oC) is provided below.

The geometric angle between any two adjacent covalent bonds is called a bond angle.

Bond Length
Bond length is a measure of the distance between the nuclei of two chemically bonded
atoms in a molecule. It is approximately equal to the sum of the covalent radii of the two
bonded atoms. For covalent bonds, the bond length is inversely proportional to the bond
order – higher bond orders result in stronger bonds, which are accompanied by stronger
forces of attraction holding the atoms together. Short bonds are a consequence of these
strong forces of attraction.