4.

etet rule: Atoms combine either by transfer of valence

electrons or by sharing electrons from one atom to aiiOuther
in order to have 8 electrons (octet) in their valence shell.
It is called octet rule.
5. Limitation of
octet rule:
H, He, Li" have 2 electrons in their outermost shell,
still these are stable.
BeF2, BF, AlCl,, BH,, BeCl,, BeH,, LiCl have
electrons less than octet.
These are electron deficient
compounds.
PCI, SF, IF, have 10, 12. 14 electrons aftersharing,
it is called super octet or
expanded octet.
. VSEPR Theory (Valence Shell Electron Pair Repulsion
Theory): According to this theory, the direction of the
bonds around an atom in a molecule depends upon
the total number of electron pairs (bonding as well as
non-bonding) in the valence shell of an atom. Since the
electron pairs repel each other, therefore, that geometrical
arrangement will be favoured in which repulsion is
minimum.
 The repulsive interactions between tuwo lone pairs (lp) are difjerent from those between
two bond pairs (bp) or those betuween a lone
pair and a bond pair. The repulsive
interactions between various electron pairs decrease in order a s :
Ip-lp> lp-bp > bp-bp
When l o n e nairs are also
present n addition to bond
interactions between the electron pairs pairs around the central atom,
the r e p u l s i

This causes distortion in around the central

unequal. T
geometrical atom become
lecule is said to have an irregular or
arrangement of electron pairs. Such a
distorted geometry. T

lt may be noted that for the purpose of applying VSEPR theory, a multiple bond is
treated as a single electron pair. For example in formaldehyde molecule (HCHO),
the bond pairs around carbon atom are counted as three (2 bp for two C-H bonds
and

1 bp for C O bond). Similarly two, C O bonds in CO, molecule are counted as two
=
=

shown below:
bond pairs. The shapes of HCHO and CO, are

180°

H 0-c>o
120 C=O
H 2 bond pairs
Linear
3 bond pairs
Trigonal planar
 Table 4.3.
4.3. Geon
Ta Geometry of
Molecules in which Central Atom has No Lone Pair of
Electrons (Here central atom is A Lone PAI
and Surrounding atoms Are D
Number of Molecular
electronp a i r s formula Arrangement of. electron pairs Examples

2 AB Linear 180°
B A B BeF, BeCl,, HgCl,
B
3 AB3 Trigonal planar 120°

BF, AIC
B. .

109°28'
4 AB Tetrahedral
8 CH, SIF NH,

5 AB Trigonad 90
bipyramidal B .--e_
/120
PFs, PCl SbCl5, AsF
--

In this
arrangement three of the bond pairs lie in
the same plane at an
angle of 120°. These are
marked ase and are called
other two bond pairs lie at equatorialtopairs.
The
right
of equatorial pairs. These are
angle the plane
called axial pairs
and are marked as a.
Axial pairs in this arrangement experience
relatively larger repulsive interactions. Hence
axial bonds are relatively
longer than equato-
rial bonds.
Any lone pair appearing in this arrangement
tend to occupy equatorial positions due to
relatively lower repulsive interactions.

90
6
AB Octahedral B 90 SF TeFs
.
 and Lone
one Pairs
366 c o n t a i n i n g
Bond
Pairs

Lone Pair)
Lis
M o l e c u l e s
atom,
Table 4.4. Geometry/Shapes of S u r r o u n d i n g

is
(Here A is Cer atom, B
Reason /other examples
Shape
Type No. of No. of | Arrangement of Example

bond lone electron pairs of

of mole
Mol pairs pairs (bp + lp)
cule
ecule (bp) p) The SOS angle around the
central atom decreases f
120° to 119.5 due to arger
Bent O 114.5
O Ip-bp repulsions. Otherez.
A
AB,L 2 B B SO, molecule
amples:O,,SnCl,,NO
Trigonal Planar

The HNH angle decreasen

from ideal angle 109°28 t
107 because of relativeh
Pyrami- N larger lp-bp repulsive inte
ABL 3 dal
B
H H 107H
ractions.

B NHg molecule Other examples PCL,NCL

Tetrahedral
PH, H,O

The larger lp-bp repulsive

Bent interactions push 0-H
2 2
AB,L bonds closer decreasing

B
H HOH angle from 109° 28 to
104.5° H
B 104.5
Tetrahedral H2O molecule
Other examples HS,NH,|

The lone pair preferably

oo

1 B
See- cupies equatorial position
4
ABL B
Saw because repulsive interac-

-B tions at equatorial posihon

than
B F. are less pronounced
Trigonal Bipyramidal
SF molecule those at axial position.

to
pairs prefer
The two lone
3 2
ABL2 B T-Shape Occupy equatorial positions
to each
at an angle of 120°
B
other.
BrE, ,
B Other examples:
CIF molecule
Trigonai Bipyramidal
the three
lone pairs o
ABL 2 3 Linear F All positionsa
equatorial
Cupy
an angle
of 120°
A
Br
examples:,
Other
Trigonal Bipyramidal XeF2 molecule
 BONDING AND MOLECULAR STRUCTURE
367
uEMICAL
1
B Other examples: BrF3
ABL 5 Square
B B Pyra F
B- -B midal F F
Octahedral IFs molecule
The two lonepairs tend to lie
Square
ABL 4 2
B B planar F
Xe.
opposite each other at angle
B F of 180 .
B-
Octahedral XeF molecule
l n nresent in addition to bond pairs around the central atom.
368 COMPREH
CHEMISTRY A
Species Lewis dot Electron pairs Arrangement of
structure around central
atom
electron pairs
Shape
bp p

F-Be-F
BeF2 F:Be:F 2 0
1800
Linear
CI

0
BClg Cl:B:CI 3 Trigonal
Cl CI - .
CI
120

109 28
F
Tetrahedral
SiF F:si:F
F

F
F Square
Pyramid
P.F
IF5 F''F

Pyramidal

2 H
H,O H:0:H
H H

Tetrahedra

BF4 F:B:F
F J