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116 CHEMISTRY

Table 4.8 Shapes of Molecules containing Bond Pair and Lone Pair
Molecule No. of No. of Arrangement Shape Reason for the
type bonding lone of electrons shape acquired
pairs pairs

AB2E 4 1 Bent Theoretically the shape

should have been triangular
planar but actually it is found
to be bent or v-shaped. The

1
reason being the lone pair-
bond pair repulsion is much
-

B.A
-

0] more as compared to the

bond pair-bond pair repul-
sion. So the angle is reduced
to 119.5° from 120°.

AB3E 3 1 Trigonal Had there been a bp in place

pyramidal of lp the shape would have
been tetrahedral but one
lone pair is present and due
to the repulsion between
lp-bp (which is more than
bp-bp repulsion) the angle
between bond pairs is
reduced to 107° from 109.5°.

Bent The shape should have been

AB2E2 2 2 tetrahedral if there were all bp
but two lp are present so the
shape is distorted tetrahedral
or angular. The reason is
lp-lp repulsion is more than
lp-bp repulsion which is more
than bp-bp repulsion. Thus,
the angle is reduced to 104.5°
from 109.5°.

AB4E 4 1 See- In (a) the lp is present at axial

saw position so there are three
lp—bp repulsions at 90°. In(b)
the lp is in an equatorial
position, and there are two
lp—bp repulsions. Hence,
arrangement (b) is more
stable. The shape shown in (b)
is described as a distorted
tetrahedron, a folded square or
(More stable)
a see-saw.

2018-19
 CHEMICAL BONDING AND MOLECULAR STRUCTURE 117

Molecule No. of No. of Arrangement Shape Reason for the

type bonding lone of electrons shape acquired
pairs pairs

AB3E2 3 2 T-shape In (a) the lp are at

equatorial position so
there are less lp-bp
repulsions as
compared to others in
which the lp are at
axial positions. So
structure (a) is most
stable. (T -shaped).

4.5 VALENCE BOND THEORY knowledge of atomic orbitals, electronic

As we know that Lewis approach helps in configurations of elements (Units 2), the
overlap criteria of atomic orbitals, the
-

writing the structure of molecules but it fails

to explain the formation of chemical bond. It
also does not give any reason for the difference
* -in bond dissociation enthalpies and bond
µ lengths in molecules like H2 (435.8 kJ mol-1,
74 pm) and F 2 (155 kJ mol -1 , 144 pm),
hybridization of atomic orbitals and the
principles of variation and superposition. A
rigorous treatment of the VB theory in terms
of these aspects is beyond the scope of this
book. Therefore, for the sake of convenience,

÷ _¥÷
although in both the cases a single covalent
bond is formed by the sharing of an electron
valence bond theory has been discussed in
terms of qualitative and non-mathematical
s pair between the respective atoms. It also gives
-
.

treatment only. To start with, let us consider

e.
no idea about the shapes of polyatomic the formation of hydrogen molecule which is
molecules. the simplest of all molecules.

#
Similarly the VSEPR theory gives the Consider two hydrogen atoms A and B
geometry of simple molecules but approaching each other having nuclei NA and
theoretically, it does not explain them and also N B and electrons present in them are
it has limited applications. To overcome these represented by eA and eB. When the two atoms
limitations the two important theories based
are at large distance from each other, there is
on quantum mechanical principles are
no interaction between them. As these two
introduced. These are valence bond (VB) theory
atoms approach each other, new attractive and
and molecular orbital (MO) theory.
repulsive forces begin to operate.
Valence bond theory was introduced by
Attractive forces arise between:
Heitler and London (1927) and developed
further by Pauling and others. A discussion (i) nucleus of one atom and its own electron
of the valence bond theory is based on the that is NA – eA and NB– eB.
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