ACKNOWLEDGMENT

To my teachers : I owe an enormous debt of thanks to my teachers, especially to

Mr. Gurdev Bharadwaj & Dr Ram Kuntal Hazra who always blessed & supported
me during my entire student life.
To my family : I express special thanks to my parents, bhaiya bhabhi & my wife
who constantly motivated me to write this book & also to my sweet daughter
Parlika who smile has been a constant source of motivation for me.
I am indebted to Archana Grover for her help in doing editing and proof reading.
I would like to thank my publisher for his faith in me & for brilliant editing over
designing of this book. I would also mention sincere efforts of my computer operator
Mr. Sunil Kumar & wish a joyous time to all the readers of this book.

This book is dedicated to my mother who always

inspired me to go high butI couldn’t touch.

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(ii)
I wish to express my gratitude and indebtedness to all students and teachers who have
been using the earlier editions. The book has been improved a lot as a result of their
valuable suggestions and comments.

The present edition of this book has been thoroughly revised in accordance with the
latest competitive trends while retaining the salient features and strengths of the previous
editions.

In this edition, a new topic entitled 'Resonance' has been introduced. Errors in previous
editions have also been rectified. Requisite modifications in some chapters and addition
of problems in every chapter has been done keeping in mind the requirements of IIT-JEE
aspirants.

A separate section comprising of true-false exercises has also been introduced at the
end of the book with the primary aim of enabling the students to check their conceptual
base and strengthen it accordingly.

I shall feel highly obliged, if the students and their fellow teachers send their constructive
criticism and suggestions which we will be using in the publication of future editions.

I hope that the readers will enjoy and benefit from the experience of learning
'Chemical bonding' as is presented in this revised edition.

VAIBHAV TRIVEDI
M.Sc IIT-R, NET
[email protected]

(iii)
 Page No.

1. Some Basic Concepts of Atomic Structure & Periodicity Properties 1-6

2. Bonding 7-22

3. Valence Bond Theory & Resonance 23-34

4. Hybridization (VSEPR, Bent's & Drago's Rule) 35-66

5. Polarization, Dipole Moment & Hydration Energy 67-90

6. Molecular Orbital Theory & Metallic Bonding 91-112

7. Hydrogen Bond & Inter Molecular Force of Attractions 113-126

8. Miscellaneous Problems 127-152

(iii)
Chapter 1 : Some Basic Concepts of Atomic Structure & Periodicity Properties 1

1
Some Basic Concepts of Atomic
Structure & Periodicity Properties
It is necessary to understand atomic structure and periodic properties to know the concept of chemical bonding
fully.
Every atom has one nucleus inside it and orbits all around or we call them energy levels. These orbits further
have sub shell or sub energy levels and these sub energy levels contain orbitals . 1st, 2nd, 3rd …….shells are
called K, L, M …………etc. The sub shells are assigned with s, p, d, and f. If 'n' shows number of shell then it
must have 'n' sub shell and n 2 orbitals. Since each orbital has maximum capacity of 2 electrons thus, a shell can
not hold more than 2n 2 electrons.
s-sub shell One orbital (2e–)
p-sub shell Three orbitals (6e–)
d-sub shell Five orbitals (10e–)

f-sub shell Seven orbitals (14e–)

Finally we can say that in 1st energy level only one sub shell (s) is present, in 2 nd shell two sub shells (s & p) are
present similarly in 3rd & 4th shell three (s, p & d) & four (s, p, d & f) sub shells are present.

Maximum
No. of shell (n) Sub shells (n) Total number orbitals (n 2)
electrons 2n2
1s
1st (K) s 2
2s 2p
2nd (L) s&p 8
3s 3p 3d
3rd (M) s, p & d 18
4s
4th (N) s, p, d & f 4p 4d 32
4f
 2 Chemical Bonding

Ø1.1 Orbital and orbital wave function

"The region around the nucleus where probability of finding electron is maximum is called orbital and
the region where probability of finding electron is zero is called node"
In order to find out the probability of finding electron in a given space of volume within the nucleus, we
take help of wave function (y). Orbital wave function (y) can be written in the form of product of two
wave functions.
y = y (r) × y (q, f)
(Radial function) (Angular function)
The radial part of orbital wave function i.e y (r) gives the information about the size of orbital and
depends on quantum number 'n' & 'l'. On the other hand, the angular part of wave function gives the
information of shape of orbital and depends on quantum numbers 'l' & 'm'. The variation of the radial part
of the orbital wave function for 1s and 2s orbitals is given below

+
y (r) (1s) y (r)
–
+

r r

It is observed that the shape of 's' orbital does not depend on angular part of wave function but it only
depend upon radial part of wave function. Therefore, all's' orbitals are spherical because they have no
directional dependence.

y y
z z
+
+ + + +
x + + x
+ +
+

1s 2s

In this figure, +ve and –ve sign indicates that in particular region wave function is +ve and –ve. It has no
relation with +ve and –ve charge.
Probability density (y2): - Wave function ? only shows amplitude of electron wave whereas square of
wave function y2 shows the probability of finding electron in a definite region around the nucleus.
The graph between y2 and r (distance from nucleus) denotes probability density curve. Here probability
density curves for 1s & 2s orbitals are shown below
Chapter 1 : Some Basic Concepts of Atomic Structure & Periodicity Properties 3

1s 2s node

+ +
y2 y2
r r

+ node

1s 2s
The shapes of the orbitals can be represented quite accurately with the help of boundary surface
diagram. The boundary surface diagram for's' orbitals are spherical in shape. The size of's' orbital how-
ever increases with increase in number of shell. The boundary surface diagram of the three 2p orbitals is
not spherical. Each 'p' orbital consists of two lobes which are separated by a region of zero probability
(node).
In three 'p' orbitals lobes lie on px, py & pz axis respectively

y y y y
z z z z

x x x x

2px 2p 2p
1s y z

dum - bell shape

Shapes of d orbitals (double dumbell):-

z y y y y
y z
z z z

x x x x x

dz2 dx2 – y2 dxy dyz dzx

Out of five'd' orbitals, only two'd' orbitals d z 2 & d x2 - y 2 have their lobes on the axis, rest all'd' orbitals
have their lobes in between the axis.
 4 Chemical Bonding

Ø1.2 Aufbau principle and electronic configuration

The electrons are added progressively to the various orbitals in their order of increasing energies
starting with the orbital of lowest energy.
In order to remember the various orbitals in increasing order of energy, we take help of following diagram

1s

2s 2p

3s 3p 3d

4s 4p 4d 4f

5s 5p 5d 5f

6s 6p 6d

7s

1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s ………………..
Electronic configurations of some elements are given below
H (1e–) 1s1
He (2e–) 1s2
Li (3e–) 1s2, 2s1
C (6e–) 1s2, 2s2, 2p2
V (23e–) 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d3

Ø1.3 Hund's rule of maximum multiplicity

Pairing of electron in degenerate orbitals (orbitals with same energy) belonging to same sub shell does
not occur till each orbital of that sub shell is singly occupied with parallel spin.
N (7e–)
1s2 2s2 2p3
F (9e–)
1s2 2s2 2p5
Chapter 1 : Some Basic Concepts of Atomic Structure & Periodicity Properties 5
Ø1.4 Nuclear charge (Z) and effective nuclear charge (Z*) & Screening effect
Nuclear charge (Z) is defined as the number of protons, present in the nucleus, for example the nucleus
of H has one electron therefore, its Z = 1 similarly Z = 3 for lithium as it possesses three protons in its
nucleus.
The electron in the outermost shell is attracted by the protons present with in the nucleus but it is also
repelled by the electrons present in the inner shell as well as from the electrons present in its own shell.
The combined effect of this attractive and repulsive force acting on valence electron is that the valence
electron experience less attraction from the nucleus. This is called Shielding or Screening effect.
Therefore, the net charge with which valence electron feels attraction is called effective nuclear charge
(Z*)
Z* = z – s
Here s = screening constant.
The electrons present in different sub shell possess different capacity to shield or screen the nucleus.
The electrons present in 's' orbital shield the nucleus maximum as they are closer to nucleus, whereas
electrons in 'd' and 'f ' sub shells have poor screening effect as they are away from the nucleus. The
sequence of shielding capacity by the electron in different sub shell is given as:-

+ s p d f

s > p > d > f

(Good screening) (Poor screening)
Along with it, if all sub shells are completely filled with electrons, the order of screening will be:-
f > d > p > s
Effective nuclear charge increases while moving from left to right in a periodic table whereas it remains
constant on moving down in a group.

Ø1.5 Periodic properties and their variations

(a) Atomic radius: - It is the distance from the centre of the nucleus of the atom to the valence electron

Atomic radius
Decreases (along a period)

Increases (along a group)

(b) Ionic radius: - It is defined as the effective distance from the nucleus of the ion to the point up to
which it has an influence (or effect) in the ionic bond.

Ionic radius
Decreases (along a period)

Increases (along a group)

6 Chemical Bonding
The radius of cation is smaller than its parent atom because when atom releases an electron to
form cation, its effective nuclear charge (Z* = p/e theoretically) increases and valence electron
feels more attraction from the nucleus, consequently radius decreases. On the other hand the
radius of anion is more than its parent atom because when an atom gains electron to form anion its
effective nuclear charge (Z* = p/e) decreases and valence electron feels less attraction from the
nucleus resulting in small ionic radius.
(c) Ionization energy (I.E) or Ionization potential (I.P): - It is the amount of energy required to remove
an electron from an isolated gaseous atom to produce cation
(I.E.) (+)
M(g) M (g) + e–
In general I.E. decreases on moving down the group because on moving down the group atomic
size increases & valence electron feels less attraction from nucleus.
If an atom has exactly half filled or completely filled sub shells, then such an atom requires more
ionization energy than the atom with partially filled sub shell. For example first I.E. of nitrogen is
greater than oxygen.
N 1s2 2s2 2p3 O 1s2 2s2 2p4
half filled Partially filled
'p' sub shell 'p' sub shell

(d) Electron gain enthalpy of electron affinity (E.A):- It is the energy released when an electron is
added to a neutral gaseous atom to convert it in to an anion
(–)
X(g) + e– X (g) + E.A.
E.A. µ 1 / atomic size
E.A µ 1 / screening effect
(e) Electronegativity (E.N)
Electronegativity is a measure of the tendency of an element to attract electrons towards it self in a
covalently bonded molecules
EN
Increases (along a period)

Decreases (along a group)

There is no direct method to measure the value of electronegativity; however there are some scales
like Pauling scale, Mulliken scale & Allred - Rochow scale, to measure its value. In chemical
bonding, we often use Pauling scale Electronegativity of some elements on Pauling scale is given
below.
Li Be B C N O F
(1.0) (1.5) (2.0) (2.5) (3.0) (3.5) (4.0)
Na Cl
(0.9) (3.0)
K Br
(0.8) (2.8)
Rb I
(0.8) (2.5)
Cs
(0.7)
Chapter 2 : Bonding 7

2
Bonding
What is chemical bond?
If energy released by the attraction of two atoms is more than 42 KJ / mol then it is considered as chemical
bond.
A + B AB + Energy (more than 42 KJ / mol)
Or
The attractive force which holds together the atoms or groups of atoms in a chemical species is known as
chemical bond.
But the question arises that why elements combine with each other. Various facts have been put forward to
understand it; finally Kossel and Lewis successfully presented the fact in 1916. They made electronic
configuration as base and explained that atoms of inert gas possess least probability to combine with other
elements. It means that the electronic configuration of inert gases is more stable; therefore, they do not react
with other atoms (Except Xenon)
Outer most shell of all inert gas elements is completely filled. Except 'He' electronic configuration of all inert gas
atoms is ns2, np6, it means, there are 8e in their outermost shell. Except noble gas, no other elements possess 8e
in their outermost shell. Therefore, the other elements combine together or with other elements in order to
complete their octet. This gives birth to octet rule. According to octet rule:-
"Atoms combine together to complete their outermost shell and to attain the configuration of noble gas which
is a stable configuration."
Based on modes of combination chemical bonds are classified as:-
(a) Ionic bond (b) Covalent bond
(c) Coordinate bond (d) Metallic bond

Ø2.1 Ionic bond or Electrovalent bond

We all know that sodium reacts with chlorine readily to form NaCl. The outermost shell of Na has one
electron (2, 8, 1) whereas chlorine has 7- electrons in valence shell (2, 8, 7) so, 'Na' transfers its one
electron to 'Cl' and forms NaCl. This allows 'Na' and 'Cl' to complete their octet. These oppositely charged
ions (Na+ and Cl–) are held together by an electrostatic force of attraction called ionic bond or electrovalent
bond
 8 Chemical Bonding

Na
. Cl Na
(+)
Cl
. (–)

(2, 8, 1) (2, 8, 7) (2, 8) (2, 8, 8)

Thus, ionic bond can be defined as:-

"It is electrostatic force of attraction between two oppositely charged ions"

Conditions for formation of ionic compounds:-

(1) The electro negativity difference between combining atoms should be large
(2) The atom which makes cation should have greater size and low ionization energy so that it can
easily loose its outermost electron. Nearly all elements of s - block owing to their large sizes and low
ionization energies form ionic compounds. For e.g.
NaCl, KCl, CaCl2, and CsCl etc
(3) The atom which forms anion should have small size and more electron affinity. Non metals owing to
their small size and more electron affinity form ionic compounds with 's' block elements like Na2O,
MgO, CaSO4, CaCl2 …………….etc
(4) Ionic crystals have high lattice energy (discussed later)

General properties of ionic compounds

(1) Ionic compounds are soluble in polar solvents like water but insoluble in non polar solvents like
benzene.
(2) Due to the strong electrostatic forces of attractions between oppositely charged ions, ions are
tightly bound with each other and this result in high melting point and thermal stability.
(3) They exist in solid or liquid state at room temperature but not in gaseous state.
(4) Ionic solids are almost non conductor and conducts very small magnitude of current due to crystal
defect.
In solid state they do not conduct electricity because ions are not mobile whereas in molten state
ionic compounds conduct electricity because ions are mobile and can easily conduct current from
one place to another. The aqueous solution of these compounds are good conductor of electricity
because ions remain mobile in this form.
(5) They show isomorphism (see section 4.7 in chapter - 04)

Note: -All the physical properties of ionic compounds have been discussed in chapter - 05 with detailed
discussion & clear explanation.

Ø2.2 Lattice energy

Ionic compound not only forms by the combination of cation and anion but ionic compound requires
considerable electrostatic forces of attractions between cation and anion.
Chapter 2 : Bonding 9
When these cations and anions in large number and in equal number come closer, they arrange themselves
in regular pattern and attain a closed packed structure; during this arrangement energy is released to
stabilize the system. This released energy is called lattice energy.
(+) (–) (+) (–)
Na + Cl Na Cl + lattice energy
crystal lattice

Structure of NaCl crystal is shown below

. .
.
. .
.
(–) .
Cl .
(+) .
Na
.
.
. .
(Closed packed structure)

Thus, lattice energy can be defined as:-

"Energy released when 1 mol of an ionic compound is formed by its constituent ions in gaseous state"
Or
"Energy required to break 1 mol of an ionic compound in to its constituent ions in gaseous state"

Na (+) + Cl (–) NaCl + 185.2 Kcal / mol

(g) (g)

It means that if 1 mol NaCl is to be broken in gaseous ions Na(+) & Cl(–) then 185.2 Kcal energy is
required.
Ø Determination of lattice energy: - There are two methods to determine lattice energy.
(a) Born Haber cycle (indirect method )
(b) Kapustunskii equation (direct method)
(a) Born Haber cycle: - This method is based on Hess law. For example NaCl is formed by two methods
Path - I Na + 1/2Cl2 NaCl + DHf ( heat of formation)
(s) (g)

H sublimation
Path - II Na Na
(s) (g)

Na I.E. Na+ + e– I.E = Ionisation energy

(g) (g)

H dissociation
1/2Cl2 Cl
(molecule) (atom)
 10 Chemical Bonding

Cl + e (–) E.A. Cl(–) EA = Electron affinity

(g) (g)

E.A.
Na (+) + Cl (–) NaCl + lattice energy
(g) (g)

By Hess law (the law of conservation of energy) the total heat change from path I & path II will be
same
DHf = D H (sublimation) + I.E + DH (dissociation) + E.A. + lattice energy ……….(1)
If we know the values of DHf, I.E, E.A, sublimation & dissociation energy, we can calculate lattice
energy by the help of equation (1)
(b) Kapustunskii equation

120200 g Z + Z –
L.E. = 1 – 34.5 KJ / mol
r r

g = No. of ions per mol for example for Na 2SO4 g = 3 for BaSO4 g = 2, Z+ & Z– are the charges
present on cation and anion respectively.
r = Inter ionic distance = radius of cation (r+) + radius of anion (r –) (in pm)

Ø Factor affecting lattice energy :-

From Kapustunskii relation we have
L.E. µ | Z+ | | Z– | or q1 q2
L.E. µ 1 / (r + + r–)
For example

NaCl KCl RbCl CsCl

Increasing lattice energy
MgCl2 MgO Mg3N2
q1q2 = 2 ×1 2 ×2 2 ×3
Increasing lattice energy

Ø2.3 Covalent bond

According to Lewis, "Covalent bond is formed from the sharing of same number of electron between two
atoms"
The atoms which take part in sharing complete their octet by sharing one two or three electrons. If one
electron is shared between two atoms then it forms single bond. Similarly double & triple bonds are
formed by the sharing of two and three electrons. For example:-
Chapter 2 : Bonding 11

H2 H .. H H –H single bond

.. .. .. ..
O2 O O O = O double bond

..
..
....
.. ..

.. .. .. ..
...

N N N N triple bond
...
N2

Ø Only the electrons of valence shell take part in sharing. The electrons of valence shell which do not
take part in chemical bonding are called lone pair or non bonding electrons. For example in O2 six
valence electrons of oxygen atom (2, 6) can take part in bonding. Out of six electrons two electrons
are shared by one oxygen atoms thus after bond formation each oxygen possesses four electrons
(or two lone pairs)

.. .. lone pair .. ..
O = O N N
..

..

Ø Bond length :- It is defined as the inter nuclear distance between two covalently bonded atoms

A B

+ +

d = bond length

1 1
Bond length µ µ
Bond order Stability

Ø Bond order (B.O.) :- The number of bonds present between two covalently bonded atoms is called
bond order
F–F B.O. = 1, O=O B.O. = 2

1
Bond order µ Stability µ
Bond length

If the number of bonds is more between two atoms, more energy is required to break those bonds,
thus, it increases the stability
CH = CH CH2 = CH2 CH3 – CH3
Increasing B.O & bond dissociation energy
 12 Chemical Bonding
This clears the concept why N2 behaves like inert gas at room temperature. The reason is that in N 2,
nitrogen atoms are joined with each other by the help of triple bond which is difficult to break at
room temperature.
Due to increase in number of bonds (B.O), bonding atoms come close to each other and bond
length decreases

CH = CH CH2 = CH 2 CH3 – CH3

Increasing bond length

Ø2.4 Lewis structure drawing

For this we have to follow following rules
Rules - 1 :-
Calculate n1 = Total number of valence shell electron + ( negative charges) – (positive charges)
Calculate n2 = 2 (number of H – atoms) + 8 (number of other atoms)
Calculate n3 = (n 2 – n1)
Number of bonded electrons i.e. number of bond pair = n 3 / 2
Calculate n4 = (n 1 – n3)
Number of lone pair of electrons = n 4 / 2
Rules - 2 :-
Find out central atom either more electro positive or least in number for example in H2SO4, 'S' is considered
as central atom similarly P is considered as central atom in PCl5 & H3PO4
Rules - 3:-
Arrange the surrounding atoms around central atom and join them with the help of bond pair calculated
(n3 / 2) verify octet of each atom. If octet is not found to be completed then utilize the lone pair to fulfill
the octet.
Rules - 4:-
To understand the bonding properly we shall calculate formal charge for each atom (discussed later)
Let us consider some examples
1. H – CN n1 = 1+4+5 = 10
n2 = 2× 1+8×2 = 18
n3 = n2 – n1 = 18 – 10 = 8
Bond pair = 8/2 = 4
••
Lone pair = 10 – 8 / 2 = 1, i.e H–C º N

..
H C N
...
...

..
Chapter 2 : Bonding 13
2. CO2 n1 = 4 + 6 + 6 = 16
n2 = 3 × 8 = 24
n3 = 24 – 16 = 8
bond pair = 8 / 2 = 4
n4 = n1 – n3 = 16 – 8 = 8
.. ..
lone pair = n4 / 2 = 8/2 =4 i.e O
.. = C = O..
.. ..
..
O .. C O
..
..
..
..
Calculation of formal charge (F.C)
F.C = (valence shell electrons of atom) –(number of bonds associated with that atom) –(number of
unshared electrons by it)
3. NO3– n1 = 5 + (6 × 3) + 1 = 24
n2 = 8 × 4 = 32
n3 = 32 – 24 = 8, bond pair = 8 / 2 = 4
n4 = n1 – n3, = 24 – 8 = 16
lone pair = 16 / 2 = 8

.. (2) ..
(1) O
.. N = O (3) Now formal charges on 1, 2, 3 & 4
..
..

can be calculate as
O
.. (4)
..
..

1st atom: - F. C = 6 – 1 – 6 = –1
2nd atom: - F. C = 5 – 4 – 0 = +1
3rd atom: - F. C = 6 – 2 – 4 = 0
4th atom: - F. C = 6 – 1 – 6 = –1

.. (+) ..
Hence NO3– can be represented as:- (–) O
.. N = O
..

..

O
..
..
..

(–)

Lewis dot structures of some species are given below:-

H2O2 .. .. . . .. ..
H O
.. H or H ..
O O
.. H

PH3 H . . .. . .
P. H or H
..
P H
.
H H
.. (–)
O..
..
..

O
.. ..
..

.. . . ..
CO32–
.. .. ..
O O O or O = C O
..
..
..

..
..

..
..

(–)
 14 Chemical Bonding

+
(+)
. . O. . .
..
H H or H O H
O+ .

..
H3
H H

.. .. .. (+) ..
HNO3 O N O H or O = N O H
.. ..
..

..
..
..

..
..
..
O O

..
..
..
..
..

.. (–)

H
.. H
O
..
..
..

.. O

..
..
.. .. .. ..
H ..
O P O H or H O P O
.. H
.. ..
..

..
.. . . ..
H3PO4
.. O..

..
O
..
..
..

–2
.. –2
.. O
..
..
O
..
..

.. .. . . .. .. ..
O S
.. O or O
.. S O
..
..

..

..

..
SO4–2
.. . .
O
..
..

.. ..
O
..
..

Ø2.5 Limitations of the octet rule

It is useful for understanding the structures of most of the organic compounds and it applies mainly to
the second period elements of the periodic table. There are three types of exceptions to the octet rule.
(a) The expanded octet or super octet (Hypervalent compounds):-
There are many stable molecules in which central atom have more than 8e– in its valence shell for
e.g. IF7 (14e– in valence shell), PCl5 (10e–), SF6(12e–)

.. .. ..
F Cl F
..
..
..
..
..

..

.. .. .. ..
..F ..F
..
..

F
..

..F
..

..

Cl
..

.. .. .. ..
..
F I Cl
.. P S
..

..

..
Cl
..
..

..
F
..

..

.. .. ..
..
F ..F F
..
..
..
..

F
.. ..F
..
..
..
..

Cl
..
..
..

For such kind of molecules central atom should have'd' orbitals for bonding
(b) The incomplete octet of central atom (Hypovalent compounds):-
In some compounds, the number of electrons surrounding the central atom is less than 8. This is
specially the case with elements having less than four valence electrons.
For e.g. BeCl2, BCl3, LiCl
Chapter 2 : Bonding 15

..
Cl
..

..
.. .. ..
Cl
.. Be Cl
.. B Cl
..

..
..

..
..
Cl
..

..
(4 valence e–) (6 valence e–)

(c) Odd electrons molecules : There are some species which have odd number of electrons, like KO2,
RbO2, NO, NO2 and CsO2. In these cases, octet rule is not obeyed by all the elements of species
(+) (–)
. O.
.. ... .. .. ..
N ..
O = N O
..

..
..
(Nitric oxide)

These species are coloured and paramagnetic in nature because of presence of unpaired electron.
Apart from these, octet rule does not give any information about the shape of species as well as it
can not explain that why Xe (inert gas elements) forms variety of compounds like XeF6, XeOF2 &
XeF4 etc.

Ø2.6 Polar and non polar covalent molecules

If the two bonded atoms have equal values of electronegativites, the bonded pair of electrons is equally
shared between them, i.e. shared pair of electrons remains in the middle (just in between the atoms). Such
a bond is called non polar covalent bond.
For example H — H, O = O, N º N , C — C, F — F …………..etc bonds. However, if the bonded atoms
differ in their elecronegativities, the bonded pair of electrons is attracted more towards at atom with the
larger electronegativity, resulting in the development of partial negative charge over this atom and equal
but opposite charge over the other bonded atom. Such a covalent bond is called polar covalent bond.
For e.g. I — Cl, C — Cl, C = O, H — F
s+ s–
H H H F
(non polar molecule) (polar molecule)

Extent of polarity in a bond is measured in terms of dipole moment (discussed later in chapter - 05)

Ø2.7 General properties of covalent molecules

Ø Solubility : These compounds are usually insoluble or less soluble in water and in other polar solvents.
Polar covalent molecules are more soluble in water in comparison to that of non polar covalent molecules.
Ø Low melting point and boiling point: - The intermolecular forces of attractions between the molecules
of covalent compounds are generally weak. As a result, lesser amount of energy is needed to
overcome these intermolecular forces. Thus, these compounds usually have low melting point and
boiling point than ionic compounds.
Ø Conducting nature: - These are generally poor conductors of electricity in the fused or dissolved
state due to non existence of ions.
 16 Chemical Bonding
Ø Molecular reactions:- These compounds generally do not produce ions in aqueous medium. There
fore, their reactions are not ionic in nature. These reactions involve the breaking of covalent bonds
in reaction molecules and forming new bonds to give molecules of the products. Therefore, these
reactions are quite slow because energy is required to break covalent bonds.
Ø State of existence: - There are weak intermolecular forces between the molecules and hence, they
exist as liquids or gases at room temperature. However, a few covalent compounds also exist in the
solid state for e.g. glucose, urea, thiourea & sugar etc.

Ø2.8 Coordinate bond (Dative bond)

In this type of bonding, one atom donates its electron pair to the other. In other words electron sharing
takes place between two atoms but sharing involves one atom only. The atom which receives electron
pair is known as receiver whereas the one which donates electron pair is known as donor atom.

.. (+) (–)
NH3 + BF3 NH3 BF3
(donor) (receiver)

.. .. .. .. ..
O
.. = O.. + O
.. O = O(+)
..

..

.. (–)
O
..
..

donor receiver
The nature of coordinate bond is semi ionic or semi covalent. This is explained as:-
There are two steps involved in the formation of coordinate bond between A and B.
Step - I: - Firstly, atom A gives its electron to atom B

–
A+
.. . .
A + B B
Step - II: - Now both A + and B- share one electron with each other
+ . – . + –
A + B A B
..

Thus, coordinate bond has semi ionic nature. Therefore physical properties of these compounds like
solubility, melting point, boiling point and electrical conductance lies between covalent and ionic
compounds (For more discussion see chapter - 05)
Chapter 2 : Bonding 17

Q.1 Draw Lewis dot structures for the following species:-

CO32–, HCO3(–), SO2, SO3, Na2CO3, N2O4
Q.2 Calculate formal charges on bold elements

O H H
..
..

(a) (b)
.. .. H — N — CH2— O—H
..
.. — C — O.. —H
H— N
H

.. .. H
(c) H2C — NH — S
H
Q.3 Arrange the following in decreasing order of electrical conductance.
(a) NaCl(l) MgCl2(l) K2SO4(l) (b) NaCl(l) MgCl2(l) NaCl(s)
(c) MgCl2(s) NaCl(l) MgCl2(l)
Q.4 NaCl is soluble in water but not in benzene explain.
Q.5 Use Lewis symbols to show electron transfer between the following atoms to form cations & anions
(a) K and O (b) Ca & S
Q.6 Predict the nature of bond in each case formed between atoms
(a) P & H (b) N & Cl
(c) Mg & O (d) K & O
(e) Sr & F
Q.7 Draw Lewis dot structure of the molecule in which three 'C' atoms are present, total atoms are 5 and total
double bonds are '4'
Q.8 Calculate number of double bonds in following species
(a) HCOOH (b) COOH – COOH
(c) N2H4 (d) CH3COCOOH
Q.9 Calculate L.E. of CaF2 by using following data DH sublimation (Ca) = 48 K Cal / mol
(I.E.)1 = 141 K Cal / mol
(I.E.)2 = 274 K Cal / mol
DH dissociation (F2) = 34 K Cal / mol
E.A. = – 83 K Cal / mol
D H°f (CaF2) = –296 K Cal / mol (Ans = –627 K Cal / mol)
Q.10 Write partial positive and negative charges on each atom in following molecules
(a) H2O (b) F2O (c) NH3 (d) NF3
 18 Chemical Bonding

Q.1 Which among the following possesses ionic as well as covalent bonds?
(a) MgCO3 (b) NH4Cl
(c) HBF4 (d) All of these
Q.2 The type of bond present in N2O4
(a) Only covalent (b) Only ionic
(c) Ionic and covalent (d) Covalent & Coordinate
Q.3 Which of the following does not contain coordinate bond?
(a) SO3 (b) H2SO4
(c) H3O(+) (d) All of these contains coordinate bond
Q.4 Which of the following is an example of super octet rule?
(a) CO2 (b) PCl3
(c) ClF3 (d) NF3
Q.5 Which of the following is an example of super octet rule?
(a) XeF6 (b) IF7
(c) SF6 (d) All of these
Q.6 One mol of phosphate ion reacts with two moles of H(+) ion to produce 'X'. The formula of compound
formed by Na(+) & X is
(a) Na2X (b) NaX
(c) Na3X (d) Na3X2
Q.7 How many double bonds are present in C3O2:-
(a) 1 (b) 2
(c) 3 (d) 4
Q.8 Highest electrical conductance will be found in:-
(a) LiCl(l) (b) NaCl(l)
(c) KCl(l) (d) RbCl(l)
Q.9 Highest electrical conductance will be found in:-
(a) Na3AlF6(l) (b) MgCl2((l)
(c) MgSO4(l) (d) KNO3(l)
Chapter 2 : Bonding 19
Q.10 Column - I Column - II
(A) Na3AlF6 (1) Contains '4'double bonds
(B) AgCl (2) Contains Coordinate bond
(C) Na2SO4 (3) Least electrical conductance in molten state
(D) C3S2 (4) Produce 4 ions when dissolve in water
Correct matching code is:-
(a) A ® 4, B ® 2, C ® 3, D ® 1
(b) A ® 4, B ®3, C ®2, D ® 1
(c) A ® 3, B ® 2, C ® 4, D ® 1
(d) A ® 1, B ® 2, C® 3, D ® 4
Q.11 Which will not produce ions in aqueous medium
(a) MgCl2 (b) BeCl2
(c) NaCl (d) CsCl
Q.12 In NO3(–) ion, number of bond pair and lone pair of electron on nitrogen atom are?
(a) 2, 2 (b) 3, 1
(c) 1, 3 (d) 4, 0
Q.13 Which of the following is the electron deficient molecule?
(a) C2H6 (b) B2H6
(c) SiH4 (d) PH3
Q.14 Which of the following types of bonds are present in CuSO4.5H2O?
(1) electrovalent (2) covalent (3) coordinate
Select the correct answer using the code given below.
(a) 1 and 2 only (b) 1 and 3 only
(c) 1, 2 and 3 (d) 2 and 3 only
Q.15 Lattice energy of an ionic compound depends upon
(a) packing of ions only (b) size of the ion only
(c) charge on the ion and size of the ion (d) charge on the ion only
Q.16 In OF2, number of bond pairs and lone pairs of electrons are respectively
(a) 2, 6 (b) 2, 8
(c) 2, 10 (d) 2, 9
Q.17 The ion which is ioselectronic with CO is
(a) CN(–) (b) O2 (–)
(c) N2 (+) (d) O2 (+)
 20 Chemical Bonding
Q.18 The octet rule is not valid for which of the following molecule?
(a) CO2 (b) H2O
(c) O2 (d) CO
Q.19 Out of the following pair of species which one is most likely to combine by co-ordinate bond?
(a) H2 + I2 (b) Mg + 1/2O2
(c) Cl (g) + Cl (g) (d) H(+) and H2O
Q.20 The most polar bond is:-
(a) Cl – F (b) Br – F
(c) I – F (d) F – F
Q.21 In an ionic compound X(+)Y(–) the degree of covalent bonding will be maximum when
(a) Both cation & anion are small
(b) cation is small & anion is large
(c) Both cation & anion are of approximately same size
(d) anion is small & cation is large
Q.22 The formal charge on the nitrogen atom of nitrite ion is
(a) + 1 (b) – 1
(c) 0 (d) + 3
Q.23 The total number of electrons involved in double bonds in 0.5 mol of nitrate ions (according to its Lewis
structure) is:
(a) 4NA (b) 2NA
(c) NA (d) 3NA
Q.24 The number of pi electrons present in 2.6 g of ethyne is
(a) 2.408 × 1024 (b) 2.408 × 1025
(c) 2.408 × 10 23 (d) 1.204 × 1023
Q.25 Which is the correct Lewis arrangement of S22– ion?
2– 2–
(a) S S (b) S =S

(c) 2– (d) None of these

S =S
Q.26 Electronic structure of four elements is X, Y, Z, W are given below
X : 2s2 ; Y : 1s22s22p2
Z : 1s22s22p5 ; W : 1s22s22p6
The tendency to form covalent bond is maximum in
(a) W (b) Y
(c) Z (d) X
Q.27 Which of the following bond is most ionic?
(a) Cs – Cl (b) Al – Cl
(c) I – Cl (d) H – Cl
Q.28 Ionic reaction take place mainly in:–
(a) Liquid state (b) Solution in benzene
(c) aq. solution (d) Gaseous State
Chapter 2 : Bonding 21
Q.29 Of the following solvents, the one most likely to dissolve ionic compound is:-
(a) Carbon tetrachloride (b) Methanol
(c) Liquid NH3 (d) Dibutyl ether
Q.30 Odd electron bonds are present in:-
(a) NO (b) NO2
(c) ClO2 (d) All the above
Q.31 Which compounds do not have all three types of bonds?
(a) Na2S2O3 (b) BF4(–)
(c) NH4CN (d) Al2Cl6
Q.32 Dative bond is present in:-
(a) N2 H5(+) (b) H3O(+)
(c) CO (d) All of these
Q.33 The compound with highest lattice energy is:-
(a) LiI (b) NaF
(c) MgO (d) Na2O
Q.34 The bonds present in N2O5 are:-
(a) Ionic (b) Covalent and co-ordinate
(c) Covalent (d) Ionic and covalent
Q.35 Octet rule is not valid for the molecule:-
(a) HCN (b) PCl3
(c) N2 (d) HNC
Q.36 Which combination is best explained by the co-ordinate covalent bond?
(a) H2 + I2 (b) Ca + S
(c) F + F (d) H(+) + H2O
Q.37 The internuclear distance in H2 and Cl2 molecules are 74 and 198 pm respectively the bond length of HCl
may be:-
(a) 272 pm (b) 70 pm
(c) 136 pm (d) 248 pm
Q.38 Which of the following is not isoelectronic:-
(a) NO(–) (b) CN(–)

(c) N2 (d) O 2(+)

2

Q.39 Hypervalent compound is:-

(a) MgSO4 (b) NH3
(c) BeCl2 (d) MgCO3
Q.40 Which of the following does not contain co-ordinate bond?
(a) BH4 (–) (b) NH2 (–)

(c) CO32(–) (d) O3

Q.41 Br2 has lesser boiling point than ICl. This is because of:-
(a) Radius of I is greater than Br (b) I. E. of I is lesser than Br
(c) ICl is polar while Br2 is non polar (d) ICl has large size in comparison to Br 2
 22 Chemical Bonding

SUBJECTIVE EXERCISE
2. (a) –1, 0, 0 (b) +1, +1 (c) –1, +1
3. (a) MgCl2 > K2SO4 > NaCl (b) MgCl2(l) > NaCl(l) > NaCl (s)
(c) MgCl2(l) > NaCl (l) > MgCl2(s)
4. NaCl is an ionic compound & hence it will not dissolve in benzene as benzene is a non polar solvent (like
dissolves like)
6. (a) Covalent (b) Covalent (c) ionic (d) ionic (e) ionic
7. O=C=C=C=O i.e. C3O2
8. (a) 1 (b) 2 (c) 0 (d) 2
s+ s– s+ s– s+ s–
10. H –O –H F –O –F
s– s+ s+ s–
s–
s+H –N –H F –N –F

H s+ F s–

OBJECTIVE EXERCISE
1. (d) 2. (d) 3. (d)
4. (c) There are 10 e in valence shell of chlorine atom
5. (d)
Na +
6. (b) PO 3– +
® H 2 PO 4– ¾¾¾
4 + 2H ¾¾ ® NaH 2 PO 4 (NaX)
7. (d)
8. (a) small size of Li+ provides lithium ion more velocity and more electrical conductance.
9. (a) It gives four ions 10. (b) 11. (b) 12. (b) 13. (b)
14. (c) 15. (c) 16. (b) 17. (a)
18. (d) Carbon has incomplete octet & it completes its octet by receiving electrons with oxygen by the help
of coordinate bond.
19. (d) 20. (c) 21. (b) 22. (a)
23. (b) 24. (c) 25. (b) 26. (b) 27. (a)
28. (c) in ionic compound ions are bonded by strong electrostatic forces of attractions, thus, to break
these forces a polar medium is required thus ions react with one another in polar medium like water
& not in benzene.
29. (c) 30. (d) 31. (d) 32. (d) 33. (c)
34. (b) 35. (b) 36. (c) 37. (c) 38. (a)
O –2
+2
39. (a) Mg O S O 40. (c) 41. (c)
O
Chapter 3 : Valence Bond Theory & Resonance 23

3
Valence Bond Theory
& Resonance
Ø3.1 Valence bond theory (V.B.T)
In order to explain the nature of covalent bond, Heitler and London proposed a theory in 1927 which is known
as valence bond approach, later extended by Pauling and Slater in 1931. According to this theory:-
(a) Covalent bond between two atoms is formed by the partial overlap of atomic orbitals.
(b) Each overlapping orbital should have one electron with opposite spin for the formation of covalent
bond or one overlapping orbital should have a pair of electron & other overlapping orbital should
be empty.

(Covalent bond)

(Coordinate bond)

(c) Covalent bonds are of two type viz. Sigma bond & Pi bond
(d) Sigma bond (s bond):- It is the bond formed by the head on overlapping of orbitals i.e. overlapping
orbitals along molecular axis or internuclear axis. Suppose 'z' is molecular or internuclear axis then
various sigma bonds can be formed as:-
(i) s - s sigma bond :- (For e.g. H2, Li2)

z z z (s - s s bond)

(ii) s- p sigma bond :- (For e.g. HF, H2O)

z z z (s - p s bond)

(iii) p - p sigma bond :- (For e.g. F2, N2, O2………etc)

z z z z

p - p s bond
24 Chemical Bonding
(e) Pi bond (p bond):- The bond formed by the lateral overlapping of atomic orbitals is called Pi bond.
This overlapping takes place on the axis perpendicular to molecular axis. If 'z' is molecular axis then
p bond forms either on 'y' axis or on 'x' axis. Various types of pi bonds are shown below.

z or

px – px or pz – pz

This kind of pi bond is called pp - pp bond, 'd' orbitals can also form p bonds with 'd' & 'p' orbitals.

Ø z (pp – dp bond)

z or (dp-dp bond with two

z
Ø lobes interaction)

z
Ø (dp - pp bond with four lobes interaction)

pp - pp bond with four lobe interaction is called delta bond (d - bond).

(f) Sigma bond is stronger bond than pi because in sigma bond overlapping area of orbitals is large in
comparison to pi bond.

(overlapping area)

(large overlapping area) (small overlapping area)

Chapter 3 : Valence Bond Theory & Resonance 25
(g) Following overlappings of atomic orbitals are not allowed:-
Ø If the wave function of two overlapping atomic orbitals is different then bond formation is not
possible.

+ –
no bond formation
– +

+ + + +
z p bond
– –

– + z + z no bond formation

+ + – z – + – s bond
z –
Ø It is not possible to form bond with 'p' orbitals having their lobes on different axis

no bond formation

p p
z x
Ø 's' orbital does not form p bond.
+
+ (not possible)
–
(h) Strength of s bonds: - Higher is the extent of overlap, higher will be the strength
p - p > s - p > s - s (descending order of strength)
F2 can be supposed to be formed by two ways
(A) (B)
F (ground state) F (ground state)

2s2 2p5 2s2 2p5

Excited state
F F

2p 2p
F F

i.e. F F (s - s s bond)
F F ( p - p s bond)
2s 2s
Out of A & B, former has more probability than later because in (A) p – p s bond formation occurs
which is stable than s – s s bond of (B)
26 Chemical Bonding
Strength of p - bond: - Strength of p bond depends on the closeness of overlapping orbitals
Stability of p bond µ 1 / distance between overlapping orbitals
2pp - pp > 3pp - pp
(More stable) (Less stable)

R>r

r R

3pp - 2pp < 3dp - 2pp

(Less stable) (More stable)

R>r

R r
This is the reason that compounds with 2pp – 2pp bonds are much abundant while compounds with
3pp – 2pp bonds are rare

C=C Si = Si
(Many compounds) (Rare)

Let us discuss the structures of some molecules by the help of V.B.T

O2

2s 2p O O

s
i.e O = O
p
2p 2p

N2

2s 2p N N

s
i.e N N
2p
Chapter 3 : Valence Bond Theory & Resonance 27
From these two examples it is evident that in between two atoms s bond forms only one time, rest
all bonds are p bonds.
B.O. = 1 (one sigma bond)
B.O. = 2 (one sigma + one pi bond)
B.O. = 3 (one sigma + two pi bonds)
The valence bond theory introduced an idea about the directional property of covalent bond
For e.g. In H2O oxygen contains two lone pair, out of which one is present in 2s orbital and second lone
pair is present in 2p orbital. Rest two p orbitals possess one unpaired electron which can form two s
bonds with two 'H' atoms. Since all the 'p' orbitals are mutually perpendicular to one another hence the
two s bonds (O — H bonds) in water should be perpendicular to each other.

H2O 2s2 2p4

lone pairs can form s-p- sbond with two hydrogen

atoms.

s orbital

H
O – H bond pairs are at 90° O
..
..

H
H H
p orbital
(angular shape)

NH3 2s2 2p3

lone pair can form s - p s bonds with three

hydrogen atoms.

H ..
N– H bond pairs are at 90° N
H

H H H (Pyramidal shape)
H
 28 Chemical Bonding
Ø3.2 Limitations of V.B.T

In CH4, carbon forms 4 sigma bonds

C 2s2 2p2
(Ground state)

(Excited state)
Carbon can form three sigma bonds with three hydrogen atoms by s-p overlapping. These three bonds
are mutually perpendicular to one another but there is no certainty of position of 4th C – H bond which
is formed by s – s overlapping because infinite direction of approaches are there in s – s overlapping.

H
C - H bonds formed by s - p overlapping
H

Since s – p bond is stronger than s – s s bonds hence in CH4 three sigma bonds should be stronger than
fourth sigma bond but in actual practice it is found that all C – H bonds are identical. They have equal
bond lengths & same bond energies. Also in CH4 all the H – C – H bond angles are 109° 28'. Thus, in
order to explain these facts phenomenon of hybridization of atomic orbitals has been proposed (discussed
in chapter - 04)

Ø3.3 Resonance (Modification of V.B.T)

In V.B.T it is assumed that bonded atoms share electron pair equally in covalent bonding. The number of
bonds formed between bonded atoms must be integral always.
F—F B.O. = 1 (Single bond)
O=O B.O. = 2 (Double bond)
NºN B.O. = 3 (Triple bond)
Whereas experimental studies revealed that bond order is fractional in some species.
For e.g. in CO32–, bond order is 1.33 between C & O, on the contrary in PO 43–, bond order is 1.25.
The V.B.T does not provide any direct method for treating such species. In other words, it is not possible
to represent structure that would correctly account for the properties of the species concerned. It is
possible, however, to explain properly the properties of many species in terms of a combination hybrid
of two or more valence bond structures. In such cases we can say that species is a resonance hybrid of
two or more valence bond structures. These structures are called resonating structures for e.g. CO 32–
can be represented by three resonating structures as follows :

(–) (–)
O O O
(–) (–) (–) (–)
O –C –O O = C –O O –C = O
(1) (2) (3)
Chapter 3 : Valence Bond Theory & Resonance 29
These three are resonating structures. It reveals that double bond and negative charge has no fixed
location. Therefore, in order to explain actual structure of this carbonate ion, a hybrid is shown (formed)
with the help of these resonating structures. This hybrid is called resonance hybrid.

Os–
Fractional bond order
C
s–O O s–

Similarly in phosphate ion four resonating structures are possible

(–) (–) O s–
(–)
O
(–)
O O (–)
(–) (–) O (–)
(–) s– s–
O –P O O=P O O P=O O P=O = O P O
O(–) O(–) O O(–) O s–
(Resonance hybrid)

Fractional bond order can be calculated by the formula

B.O. = No. of bonds taking part in resonance / No. of resonating structures
For e.g. in CO32– four bonds are participating in resonance & it has '3' resonating structures, there fore,
B.O. = 4 / 3 = 1.33
Similarly in phosphate ion B.O. = 5 / 4 = 1.25
Conditions for resonance: - A molecule or an ion undergoes resonance when it shows the following
conditions:-
(i) Identical arrangement of atoms in various resonating (or canonical) forms.
(ii) Each resonating structure must have same number of unpaired electrons.
(iii) Each resonating structure must have nearly same energy content.
(iv) The species must have planar structure.
(v) It usually involves delocalization of p - electrons.
Characteristics of resonance:-
(i) Due to resonance bond order & bond length of species get changed. Resonance gives rise to
identical bond lengths in molecule.

e.g., All the three bonds in CO32(–) are of same length with bond order 1.33

(ii) Resonance give rise to extra stability to a molecule. The resonance hybrid possesses less energy in
comparison to canonical forms and thus gains extra stability.
Resonance energy = Experimental heat of formation of molecule
– Theoritical heat of formation of molecule
R.E. of C6H6 = –1039 – (– 999) = – 40 kcal.
and R.E. of CO2 = – 336 – (– 300) = – 36 kcal.
(iii) Greater the resonance energy of the molecule more is its stability.
(iv) More is the number of covalent bonds is canonical forms, more is its stability.
 30 Chemical Bonding

Q.1 Explain why compounds with Si = Si linkages are rare.

Q.2 CO2 has discrete unit while SiO2 has long chain structure.
Q.3 Phosphorous exists as P4 while nitrogen exist as N2
Q.4 H2 is more reactive than F2 explain.
Q.5 Arrange p – p, s – s & s – p covalent bonds in order of extent of overlapping.
Q.6 (CH3)2 C (OH)2 is unstable & produce water along with CH3COCH3 but (CH3)2Si (OH)2 does not loose
water to produce CH3SiOCH3. Explain.
Q.7 Out of CH2 = CH – S(–) & CH2 = CH – O(–) former is less stabilized by resonance in comparison to later.
Q.8 Calculate bond order of C — O bond in carbonate ion.
Q.9 In sulphate ion, all S — O bonds are identical explain.
Q.10 Explain why a = b = g
O
g a
C
(–) (–)
O b O

Q.1 Correct order of stability is:-

(a) HF > H2 > F2 (b) H2 > F2 > HF
(c) F2 > H2 > HF (d) F2 > HF > H2
Q.2 Which of the following gives rise to formation of bond?

– +
+

+ –
(a) (b) –
– – +

+
+
(c) (d) None of these
–
Chapter 3 : Valence Bond Theory & Resonance 31
Q.3 Least stable ion is:-
(a) SO42– (b) PO43–
(c) CO32– (d) HCO3(–)
Q.4 Highest bond order will be present in:-
(a) CO32– (b) SO42–
(c) PO43– (d) All have same bond order
Q.5 In which case 1st overlap is more effective than 2nd one:-
(a) 3dp – 2pp, 3pp – 2pp (b) 3pp – pp, 2pp – 2pp
(c) s – p s bond, p – p s bond (d) p – bond, sigma bond
Q.6 According to V.B.T which is correct about CH4
(a) All the four C – H bonds are different
(b) All the four C – H bonds are identical
(c) Two C – H bonds are different from the other two C – H bonds
(d) One C – H bond is different than rest of the three C – H bonds
Q.7 Weakest bond is:-
(a) H – F (b) H – Cl
(c) H – Br (d) H– I
Q.8 In which case p bond will form if x is bonding axis.
(a) px–py (b) py–py
(c) px–px (d) px–pz
Q.9 In which of the following case s bond will form:-
(a) s – px (b) py – py (bonding axis 'x')
(c) py – pz (bonding axis 'z') (d) pz – pz (bonding axis 'y')
Q.10 In which case s bond will form
(a) px – py (bonding axis z) (b) py – py (bonding axis y)
(c) py – pz (bonding axis y) (d) pz – pz (bonding axis x)
Q.11 Which among the following diatomic molecule will require least bond dissociation energy?
(a) B2 (b) Cl2
(d) N2 (d) O2
Q.12 Which combination will not lead to the formation of sigma bond?

(a) (b)

(c) (d)
 32 Chemical Bonding
1 2 3
Q.13 In CH2 = C = C = CH 2 double bonds are numbered as 1, 2 & 3, pick out the correct statement

(a) 1, 2 & 3 are in same plane

(b) 1, 2 & 3 are in different plane
(c) 1 & 3 are in same plane and perpendicular to 2nd double bond
(d) 1 & 2 are in same plane and perpendicular to 3rd double bond
1 2 3 4
Q.14 In CH2 = C = C = C = CH 2 double bonds are numbered as 1, 2, 3 & 4 pick out the correct statement

(a) 1, 2 are in same plane and perpendicular to the plane in which 3 & 4 are present
(b) 1 & 3 are in same plane and perpendicular to the plane in which 2 & 4 are present
(c) 1, 2, 3 & 4 all are present in same plane
(d) 1, 2, 3 & 4 all are present in different plane
Q.15 In which of the following case both the bonds have same strength assuming that 'y' is bonding axis.
(a) s – py, px – px (b) px – px, py – py
(c) px – px, pz –pz (d) s – py , py – py
Q.16 In which of the following case 1st bond is stronger than 2nd one.
(a) s – s , px – px (x is bonding axis) (b) py – py, px – px (z is bonding axis)
(c) py – py, pz – pz (z is bonding axis) (d) py – py, pz – pz (y is bonding axis)
Q.17 Among the following ions the pp – dp overlap could be present in
(a) NO2(–) (b) NO(–)
(c) PO42– (d) CO32–
Q.18 Which of the following has pp – dp bonding?
(a) NO3(–) (b) SO32–
(c) BO33– (d) HCO3(–)
Q.19 What is the number of sigma and pi bonds present in a molecule of sulphuric acid?
(a) 6s, 2p (b) 6s, 0p
(c) 2s, 4p (d) 2s, 2p
Q.20 In which of the following species the bonds are non-directional?
(a) NCl3 (b) RbCl
(c) BeCl2 (d) BCl3
Q.21 The number of sigma (s) and pi (p) bonds present in tetracyanoethylene [(CN)2C = C(CN)2] molecule are
respectively
(a) 5 s and 9 p (b) 5 s and 8 p
(c) 9 s and 9 p (d) 9 s and 7 p
Chapter 3 : Valence Bond Theory & Resonance 33

Q.22 Which of the following resonating structure is not correct for CO2?
(–) (+)
(–) ..
(a) (b) O
.. C = O

..

..
(+) (–)
.. ..
(c) O (d) O=C=O
.. C = O

..
..

..
..
..

Q.23 How many resonating forms can be written for nitrate and chlorate ions respectively?
(a) 3, 2 (b) 2, 3
(c) 3, 3 (d) 2, 4
Q.24 Which of the following formula does not correctly represent the bonding capacities of the atoms involved?

(+)
H
F F
(a) H P H (b)
H
O

O O
(c) O N–O–H (d) H–C=C–O–H
Q.25 Among the following the bond with highest bond dissociation energy is:-
(a) Se – Se (b) Te – Te
(c) S – S (d) O–O
Q.26 In the lewis formula of O3, there are
(a) 2s, 1p bond, 4 lone pairs (b) 1s, 2p bonds, 1 lone pairs
(c) 2s, 2p bonds, 3 lone pairs (d) 2s, 1p bond and 6 lone pairs
Q.27 Select the correct statement
(a) According to V.B.T. bond angles in NH3 & H2O are same
(b) H2O is more acidic than H2S
(c) PH3 is less acidic than NH3
(d) According to V.B.T. bond angle is PH3 is lesser than NH3
Q.28 V.B.T. fails to explain the bonding in:-
(a) PCl5 (b) PH3
(c) PCl3 (d) N2
Q29 Among HF, HCl, HBr & HI strongest acid is:-
(a) HF (b) HCl
(c) HBr (d) HI
Q.30 Resonance is possible in:-
(a) BF4(–) (b) H3O(+)
(c) N2 H5(+) (d) None of these
 34 Chemical Bonding

SUBJECTIVE EXERCISE
1. 3pp – 3pp bond is weak due to more inter nuclear distance (see text)
2. Carbon can form multiple bonds with oxygen (2pp – 2pp bond) but silicon can not form multiple bonds -
with oxygen as 2pp – 2pp bond is stable then that of 3pp - 2pp bond

Si O Si
O C O O O
Si O Si
(CO2)
(SiO2)
6. Carbon can form stable 2pp - 2pp bond with oxygen while silicon can not form less stable 2pp – 3pp bond
O 2p p – 2pp
(CH3)2C(OH)2 H2O + CH3– C – CH3
O 2p p – 3pp bond
(CH3)2Si(OH)2 H2O + CH3– Si – CH3
(not possible)
(–) (–) (–) (–)
7. CH2 = CH – S CH2 – CH = S , CH2 = CH – O CH2 – CH = O

less stable 2pp – 3pp bond more stable 2p p – 2pp bond

In 1st case chances of resonance are least due to the formation of less stable 2pp – 3pp bond hence -ve
charge is less delocalized and more available for reaction with H(+) (acid)
8. Resonance takes place O
s–

9. Resonance makes all the bonds identical C

s– s–
O O
OBJECTIVE EXERCISE
1. (d) p - p > p - s > s - p 2. (d)
3. (d) Less chances of resonance
4. (b) 5. (a) 6. (d)
7. (d) More bond length due to large size of iodine hence less stability
8. (b) 9. (a) 10. (b) 11. (b) 12. (d)
H H
13. (c) C = C = C = C 14. (b) 15. (c) 16. (d)
H H
1 2 3
17. (c) 'P' belongs to third period & hence can form pp – dp bond
18. (b) 19. (a)
20. (b) Except RbCl rest all are covalent compounds while RbCl is ionic
21. (c) 22. (a) 23. (c)
24. (d) Carbon can not form five bonds
25. (c) 26. (d) 27. (a)
28. (a) V.B.T. fails to explain the bonding of hypervalent compounds
29. (d) 30. (d)
Chapter 4 : Hybridization (VSEPR, Bent’s & Drago’s Rule) 35

4
Hybridization
(VSEPR, Bent’s & Drago’s Rule)
Ø4.1 Hybridization
Ø In hybridization two or more than two atomic orbits having same energies or nearly same energies
combine to form two or more than two hybridized orbitals with same energy, same size and identical
shape.
Ø 1s, 2s, can not mix
2s, 2p can mix
3s, 4d, 5s can not mix
Ø On the basis of participation of atomic orbitals in hybridization, hybridized orbitals get their names.
For e.g. If one s & one p orbitals undergo hybridization they form two hybridized orbitals with the
name 'sp'. Similarly if one s and two p orbitals undergo hybridization then they form three hybridized
orbitals with the name 'sp2'
Atomic orbitals participating in No. of hybridized orbitals
Shape of hybridized orbitals
hybridization produced

or
One ‘s’ + one ‘p’ Two
sp

sp2

One ‘s’ + two ‘p’ Three

sp2

sp3

One’s + three ‘p’ Four

sp3
 36 Chemical Bonding
Ø All hybridized orbitals have same energy with equal % of s, % of p & % of d character
sp hybridization 50 % 's' character, 50% 'p' character
sp2 hybridization 33.33% 's' character, 66.66% 'p' character
sp3 hybridization 25% 's' character, 75% 'p' character
Note: -% s character µ Electro negativity
With the increase in % s character the bulkiness of hybridized orbital increases where as with increase
in % p character it attains longitivity and thinness
%'s' character µ bulkiness of orbitals
% 'p' character µ longitivity & thinness

sp hybridised orbital sp2 hybridised orbital sp3 hybridised orbital

As the shape of 's' orbital is spherical therefore, with increase in % 's' character bulkiness of hybridized
orbital also increases, where as, due to the increase in % 'p' character the longitivity and thinness in
hybridized orbital begins to develop because of thin and long shape of 'p' orbital.
In sp hybridization %'s' character is more therefore, its size is big in comparative to sp2 and sp3 hybridized
orbitals. Hence sp hybridized orbitals experience more repulsion from each other and due to this bond
angle between two 'sp' hybridized orbitals is found to be maximum (180°)
Consider the following examples -
BeCl2 Be 1s2 2s2 2po

Ground state

For the formation of two sigma bonds Be should have two unpaired electrons

Excited state

sp hybridization
Cl Cl
Cl atoms form two s bonds by overlapping with these hybridized orbitals

Cl Cl
Be

or 180°
Cl Be Cl 'Linear'
Here Be – Cl bond is sp – p sigma bond
Chapter 4 : Hybridization (VSEPR, Bent’s & Drago’s Rule) 37
BF3 B 1s2 2s2 2p1

Ground state

Excited state

sp2 hybridization
F F F
F atoms form three s bonds by overlapping with these sp2 hybridized orbitals

B or B 120°

F F F
F

'Triangular planar'

Here B – F bonds are sp2 – p sigma bonds

CH4 C 1s2 2s2 2p2

Ground state

Excited state

sp3 hybridization
H H H H

H
H
109° 28'
C or C
H H
H H
H
H 'Tetrahedral
Here, all C – H bonds are sp3 – s s bonds
38 Chemical Bonding
The concept of hybridization reduces the drawbacks of V.B.T. because it gives us the idea about
bond angle and shape. It gives the clear explanation why all C – H bonds of CH4 are identical.
In the same manner we can understand the geometries of PCl 5, SF6 & IF7
PCl5 Phosphorous wants to make 5 s bonds with 5 'Cl' atoms, so it needs five hybridized orbitals.
Thus, it involves mixing of five orbitals viz. one s, three p and one d orbital.
P 3s2 3p3 3d°

Ground state

Excited state

sp3d hybridization
Cl Cl Cl Cl Cl

Cl

Cl
90°
Cl P 120° Trigonal bipyramidal
Cl

Cl

SF6 For the formation of six s bonds with six F atoms sulphur needs six hybridized orbitals thus, it
involves mixing of one s, three p and two d orbitals
S 3s2 3p4 3d°

Ground state

Excited state

sp3d2 hybridization
F F F F F F
Chapter 4 : Hybridization (VSEPR, Bent’s & Drago’s Rule) 39
F

F F
90°
90° S

F 'Square bipyramidal'
F
or
'Octahedral'
F
IF7 I 5s2 5p5 5d°
Ground state
Excited state

sp3d3 hybridisation

F F F F F F F
F
F
90° F
F I 72°
F
F
'Pentagonal bipyramidal'
F

Bond Orbitals involved in

pairs or Geometry Examples
steric number angle hybridization
2 Linear sp 180° BeCl2 s + any ‘p’ orbital
Triangular
3 sp2 120° BCl3, BF3 s + any two p orbitals
planar
CH4, CCl4
4 Tetrahedral sp3 109°.28’ s +p+p+p
x y z
SiCl4
Trigonal
5 sp3d 90°, 120° PCl5 s + p + p + p + d z2
x y z
bipyramidal

s + all three p orbitals +

6 Octahedral sp3d2 90° SF6 d z2 + d x2- y2

Pentagonal s + all three p orbitals +

7 sp3d3 90°, 72° IF7 d z2 + d x2- y2 + d xy
bipyramidal
40 Chemical Bonding
Evaluation of hybridization:- To find hybridization of central atom either of the two ways can be
used.
Ist Method:-
(s bond pair) + (lone pair) + (–ve charge) = Hybridization
..
Cl — P — Cl s bp = 3
For e.g.
Cl lp = 1 sum = 3 + 1 = 4 (sp3)

(–)
H— C— H s bp = 3 – ve charge = 1
H sum = 3 + 1 = 4 (sp 3)
s s s bp = 2 (sp)
O = C = O
..
F — S —F s bp = 4 lp = 1
F F sum = 4 + 1 = 5 (sp3 d)
Here bp & lp are bond pair & lone pair of electrons respectively
2nd Method: -Firstly, valence electrons of all atoms should be counted in the species. If the sum of these
valence electrons varies between 2 to 8 then it should be divided by 2 and if sum varies from 9 to 56 then
it should be divided by 8 and if sum is found to be greater than 56 it should be divided by 18.

Sum of total valence electrons

2 to 8 9 to 56 57 onwards
(divide by 2) (divide by 8) (divide by 18)
The quotient so obtained is called steric number
For e.g.
• PCl5 Total valence electrons
= 5 + 7 × 5 = 40
= 40 / 5 = 5 i.e. 5 (sp3d)
• XeF4 Total valence electrons = 8 + 7 × 4 = 36

8 36 4
32
2 4 2
4
X

i.e. 4 + 2 = 6 sp3d2
• IF7 Total Valence electrons = 7 + 7 × 7 = 56
= 56/8 = 7 i.e 7 sp3d3
By using both the methods (1st and 2nd) we can evaluate hybridization as well as lone pair of
electrons of central atom.
Chapter 4 : Hybridization (VSEPR, Bent’s & Drago’s Rule) 41
For eg. PCl3 Total valence electrons
= 5 + 7 × 3 = 26

8 26 3
24
2 2 1
2
X

i.e. 3 + 1 = 4 (sp3 )
In PCl3, P can form 3 s bonds with three chlorine atoms
s bp + lp + (–ve charge) = hybridization
3 + lp + 0 = 4
lp = 1
Thus, in PCl3, phosphorous possesses one lp of electrons.
Similarly in XeF2 Total valence electrons = 8 + 7 × 2 = 22

8 22 2
16
2 6 3
6
X

i.e. 2 + 3 = 5 (sp3d)
Xenon can form only two s bonds with two 'F' atoms thus, in XeF2; Xenon contains three lone pair
of electrons.
s bp + lp + –ve charge = Hybridization
2 + lp + 0 = 5
lp = 3
Ø4.2 Shapes of molecules / ions when central atom contains lone pair of electrons
(1) While observing the shape of species, lone pair should not be considered, however, the presence
of lone pair may or may not influence the geometry of species (See VSEPR theory) but lone pair is
not the part of geometry.
For e.g. If central atom does not have lone pair in sp 2 hybridization, its shape is always triangular planar
but when central atom possesses one lone pair it attains bent shape
Trigonal planar Bent Linear

X X
..
X A A X A
..
X X

bp = 3 bp = 2 bp = 1
lp = 0 lp = 1 lp = 2
42 Chemical Bonding
Similarly, if central atom of sp2 hybridization has two lp then it possesses linear shape.

lp = 0, bp = 3 (Triangular planar)

sp2 lp = 1, bp = 2 (Bent shape)

lp = 2, bp = 1 (Linear)

x
A
lp = 0, bp = 4 (Tetrahedral) x x x
..
sp 3 lp = 1, bp = 3 (Pyramidal) A
x x x

..
..
lp = 2, bp = 2 (Bent) A
x x
lp = 3, bp = 1 (linear) ..
..A x

..
(2) Sp3d hybridization holds trigonal bi pyramidal shape (TBP). It has two types of bond, axial and
equatorial as shown in figure.

axial (a) Cl (a)

(e) Cl
900 (e)
equatorial (e) Cl P 120 0
(e) (e)
Cl
(e)
Trigonal bipyramidal Cl (a)
axial (a)

Axial and equatorial bonds have different characteristics (See Bent's rule). Axial bonds are longer
and weaker than equatorial bonds. Due to this reason both axial bonds in PCl5 break while heating.

PCl5 D
¾¾® PCl3 + Cl2
If lone pair is present in TBP geometry, then on the basis of repulsions in lp & bp, structure of the
species is decided.
Descending order of repulsion is :-
lp – lp > lp – bp > bp – bp
(more strong) (strong) (weak)
Only those repulsions are considered in which angle between electron pairs is less than or equal to
90° rest of the repulsions are ignored. For e.g. three geometries of ClF3 are possible
Chapter 4 : Hybridization (VSEPR, Bent’s & Drago’s Rule) 43

F
.. ..

F .. ..
F Cl F Cl F Cl
F F ..
.. F F

(1) (2) (3)

Repulsions
lp – lp = 0 lp – lp = 1 (more strong) lp – lp = 0
lp – bp = 6 (strong) lp – bp = 3 (strong) lp – bp = 4 (strong)
bp – bp = 0 bp – bp = 2 (weak) bp –bp = 2 (weak)
Among 1, 2 & 3, 3rd has minimum repulsions therefore 3rd shows the correct geometry of ClF3.
Similarly for SF4

F F

F F
F S S
..

F F
.. F
(wrong) (correct)

Repulsions
lp – lp = 0 lp – lp = 0
lp – bp = 3 (strong) lp – bp = 2 (strong)
bp – bp = 3 (weak) bp – bp = 4 (weak)
(3) Bent's rule (For sp3d hybridization)
This rule is applicable to understand TBP geometry According to this rule.
"More electronegative element prefers to stay at axial position whereas lone pair prefers to stay at
equatorial location. For e.g.

Fa ..
.. e Fe
.. a = axial
Cl F Cl
e e e = equitorial
F F
e e
F ..
a (correct) (wrong)
44 Chemical Bonding

Fa Cl
a
Cle Fe
Cl P Cl P
e e
Cl F
e e
F (correct) Cl (wrong)
a a

Explanation: - We can split sp3d hybridized orbital in the following manner.

sp3d = sp2 + pd
equatorial axial

pd

sp2
sp2

sp2

pd

In TBP geometry two 'pd' orbitals are present on axial position; therefore % s character on axial
position is zero. This is why central atom has minimum electro negativity at axial position. With the
same reason electronegative element prefers to stay at axial location so that the element attracts
electrons of bond pair towards it.
Lone pair of electrons is always attracted towards the nucleus of one atom; therefore, they like to
stay where they feel close to nucleus. Since's' orbital is closest to the nucleus, so lone pair prefer to
stay with those orbital which have more % s character. This allows lone pair of electrons to sit on
equatorial location because at equatorial location (sp2) 33.33%'s' character is present while at axial
position % s character is zero.

F
(zero % s character)

Cl F F
F Cl
sp2 (more % s F
F
character)

(Correct) (Wrong)
Chapter 4 : Hybridization (VSEPR, Bent’s & Drago’s Rule) 45
Since axial bonds have more % p character comparative to equatorial bonds, therefore, axial bonds
are longer & less stable than equatorial bonds.
% p character µ longitivity & thinness
By using Bent's rule various geometries in sp3d hybridization can be predicted.
X
X
lp = 0 bp = 5 X A TBP
X
X
X
X
lp = 1 bp = 4 .. A Sea - Saw
X
X
X
..
lp = 2 bp = 3 X A .. T - Shape
X
X
..
lp = 3 bp = 2
.. A .. Linear
X
Example: - Discuss the shape of the following
(a) XeOF2 (b) SF4 (c) ICl2+
Solution: - (a) XeOF2 Total valence electrons
= 8 + 6 + 14 = 28

8 28 3
24
2 4 2
4
X

i.e. 3 + 2 = 5 (sp3d)
'Xe' forms three s bonds, two with 'F' & one with 'O'
s bp + lp + (–ve charge) = Hybridization
3 + lp + 0 = 5, lp = 2
In TBP geometry lp prefers to stay at equatorial position hence XeOF2 has T shape

F
..
O Xe
..
F
 46 Chemical Bonding
Since in TBP geometry more electronegative element prefers to stay at axial position, thus, F is
placed at axial position while oxygen which is less electronegative than F, is placed at equatorial
position.
(b) SF4:- Total valence electrons = 6 + 7 × 4 = 34

8 34 4
32
2 2 1
2
X

i.e. 4 + 1 = 5 (sp3 d)
s bp + lp + (–ve charge) = Hybridization
4 + lp = 5, lp = 1

F
F
.. S
Sea - Saw
F
F

(c) ICl2+:- Total valence electrons = 7 + 7 × 2 – 1 (+ve charge) = 20

8 20 2
16
2 4 2
4
X

i.e. 2 + 2 = 4 (sp3 )
s bp + lp + (–ve charge) = Hybridization
2 + lp + 0 = 4, lp = 2

.. .. (+)

I
Bent or V Shape
Cl Cl

Ø4.3 Modified Bent's rule

(–)
XeF5 is the only species which exhibit pentagonal planar shape.

Total valence electrons = 8 + 7 × 5 + 1 = 44

Chapter 4 : Hybridization (VSEPR, Bent’s & Drago’s Rule) 47

8 44 5
40
2 4 2
4
X

i.e. 5+2=7 (sp3 d3 )

s bp + lp + (–ve charge) = Hybridization
5 + lp + 1 = 7, lp = 2

(–)
F
F
F Xe
F
F
..

Experimentally it has been observed that XeF5(–) has pentagonal planar shape. This geometry of
XeF5(–) can not be explained by Bent's rule. To understand above concepts Bent's rule is presented as
follows
"The orbital occupying more space with respect to the central atom will have more % s - character"
In means lone pair and negative charge prefers to stay in the orbital where % s character is more. Such
orbitals are big in size because % s character increases the bulkiness of hybridized orbitals. Hence these
orbitals require more space and like to stay where bond angle is more.
In TBP geometry bond angle between equatorial and axial bonds is 90° which is lesser than the angle
between two equatorial bonds i.e. 120°. Thus, lone pair stays with equatorial bonds because here more
space is available.

a
F
e
90° F
120° e S
F
more space e
F
a

Similarly, in pentagonal bi pyramidal (sp3d3) geometry the bond angle between axial and equatorial
bonds is 90° whereas it is only 72° in between equatorial - equatorial bonds.
 48 Chemical Bonding
Thus, the bond angle between axial and equatorial bonds is more so lone pair and negative charge stays
at axial location as here more space is available.
a (–)
more space
e F
90° e F
e F Xe
72°
e
less space F
e F
a

Note: - (a) In sp3d2 hybridization lone pair can be placed anywhere because in octahedral geometry all bond
angles are 90°.

lp = 0 bp = 6 octahedral
90°
A 90° lp = 1 bp = 5 square pyramidal

lp = 2 bp = 4 square planar

X X ..
X X X X X X

A A A

X X X X X
X

X .. ..
Octahedral Square pyramidal Square planar
..
AX6 AX5 AX4
..

..

(b) XeF6 is the only exception of Bent's rule. Its shape is distorted octahedral
F
1
F F

Xe Bond length of Xe – F1 > Xe – F2

F F

2F
This can not be explained with the help of Bent's rule. The bond length of both axial Xe–F bonds is
different due to lp–bp repulsion. The upper Xe–F bond is long where as the lower Xe–F bond is
comparatively short.
Chapter 4 : Hybridization (VSEPR, Bent’s & Drago’s Rule) 49

Ø4.4 Recent amendments in Bent's rule

The more electronegative element not only prefers to stay in the orbital having more p - character but it
can also increases the p - character in its attached orbital of the central atom depending upon the
circumstances.
This can be applicable only if all the substituents of central atom are not same
For e.g. In CH4 or CF4, this rule is not applicable but in CH2F2, CH2Cl2 and CHCl3 this principle can be
applied.
In CH2F2, the % p character of C – F is more because F is an electronegative element therefore, it
possibly reduces % s character & increases % p character in C – F bonds.

more repulsion
H H
H a H

C C a> b > g
b

F g F
F
F
less repulsion

Due to more % p – character in C – F bonds, these orbitals are long and thin, and shows least repulsion
while, on the other hand due to more % s character in C – H bonds, these orbitals are bulky and shows
maximum repulsion. This clears the concept that bond angle of HCH bond is more than 109° 28' whereas
bond angle of FCF bond is less than 109° 28'.
Since C – F bond has more % p character therefore it is longer as compared to C – H bond
(% p character µ longitivity)
Example: - Compare C – Cl bond length in CF3Cl and CH3Cl

Solution:- more % 's' character more % 'p' character

F H
F C Cl H C Cl
F H
more % 'p' character more % 's' character

Due to more % p character C — Cl bond of CH3Cl is longer than C — Cl bond of CF3Cl

Example: - Discuss the shape of XeO2F2 by the help of hybridization. How many pp - dp bonds are
present in it.
 50 Chemical Bonding
Solution: - Total valence electrons = 8 + 12 + 14 = 34

8 34 4
32
2 2 1
2
X
i.e. 4 + 1 = 5 (sp3d)
s bp + lp + (–ve charge) = Hybridization
4 + lp + 0 = 5,
lp = 1
According to Bent's rule it should have Sea - Saw geometry.
F

Xe ..

O
F
Since 'O' is less electronegative than F hence, F is placed at axial position.
Xe 5s2 5p6 5d°
Ground state

Excited state
sp3d hybridisation

dp
s s s
s Pp -
F F O dp
O Pp -
Hence in XeO2F2 two pp - dp bonds are present.
Ø4.5 Calculation of % s & % p character
The % s character and % p character can be calculated by using the following formula
Cos q = s / (s – 1) & Cos q = (p – 1) / p
Let us calculate % s character of axial bond is TBP geometry
a
q = 90°
e 90° Cos 90° = s / (s –1)
120° e
0 = s / (s –1)
e
thus, s = 0 i.e 0% s character
a
Chapter 4 : Hybridization (VSEPR, Bent’s & Drago’s Rule) 51
Similarly for equatorial bonds
q = 120°
Cos120° = s / s – 1, = s = 0.33, i.e. 33%
Example: - Calculate % s character in sp2 hybridized orbitals
Solution:-

q = 120°

120° Cos 120° = s / (s –1)

s = 0.33 i.e. 33%

Ø4.6 VSEPR Theory (Valence Shell electron pair repulsion)

Rule - 1 Presence of lone pair on central atom may or may not affect the angle as well as shape of the
molecule
Order or repulsion lp – lp > lp – bp > bp – bp

.. ..
lp –bp lp – bp repulsion HNH = 107°
N N

H H
H
H H H

..
.. ..
lp –bp lp –lp repulsion
O O
HOH = 104.5°
..
H H H
H
lp – bp

The Structure of SF4 is not a perfect Sea - Saw because lp – bp repulsion is present in it

F F
lp – bp repulsion
F F

S .. S ..

F lp – bp F
F
F
52 Chemical Bonding
Similarly, ClF3 does not show perfect 'T' due to the presence of lp – bp & lp – lp repulsions repulsions.

F lp – bp F
.. ..
lp – bp repulsion
F Cl F Cl
.. ..
lp – bp
F
F

While bond angles are not affected in XeF4 and XeF2 due to the presence of lone pair

F ..
..
F F
FXeF = 180° FXeF = 90°
.. Xe Xe

F
..
F
F ..

Rule - 2 A double bond needs more space than single bond. Descending order of repulsion is:-
db – db > db – sb > sb –sb
Here db = double bond & sb = single bond
For example in HCHO, carbon is sp2 hybridized but all bond angles are not exactly equal to 120°.

O
sb – db repulsion
C a
b a > b
H H
sb – sb repulsion

In CO32– ion, 'C' is sp2 hybridized but resonance makes all the bond angles equal

(–) –
Od
(–)
O O O
a
C C C = C
(–) (–) –
O b (–)
O O
(–)
O O – d
O O O
d
Here a = b
Chapter 4 : Hybridization (VSEPR, Bent’s & Drago’s Rule) 53
Rule - 3 : If central atom & number of lone pair present on central atom are same then as the electro
negativity of surrounding atom increases, bond angle reduces.
.. ..
N N
H F
H F
H F
HNH = 107° FNF = 102°

It is noted that this rule is applicable if and only if lone pair is present on central atom. This rule is not
valid for CH4 , CF4 & CCl4 like molecules.
Rule - 4 Back bonding : If two atoms are joined with each other by sigma bond then either of the two can
donate its lone pair or negative charge to the other atom when the other has vacant 'p' or 'd' orbital.

(–) (–)
H C H H C Cl

H H
(no back bonding) (back bonding is possible as Cl has vacant 'd' orbital)

For back bonding one of the two atoms must be from IInd period and other atom should be from IInd or
IIIrd period. The back bonding reduces lone pair bond pair repulsions, this increases bond angle.

.. ..
back bonding lp – bp repulsion
N N
Cl F
Cl F
Cl F
ClNCl > FNF

If we arrange NH3, NCl3 and NF3 on the basis of decreasing order of bond angle, we get the following
sequence
NCl3 > NH3 > NF3
NCl3 shows largest bond angle because Cl receives the lone pair of nitrogen by back donation which
reduces the lp – bp repulsion and increases the bond angle (Rule-4) we know that back donation is not
possible in NH3 & NF3 therefore, NF3 has small bond angle comparative to NH3 (Rule-3)
Similarly
..

..
..
..

O O O
..
..

H q1 H F q2 F Cl q3 Cl
(back bonding)
q3 > q1 > q2
 54 Chemical Bonding
Rule - 5 Keeping the surrounding atom same if the electronegativity of the central atom (having
lone pair) decreases then bond angle decreases

Molecules NH3 PH3 AsH3 SbH3

Bond angles 107° 94° 93° 92°

On moving from NH3 to SbH3, electro negativity of central atom reduces and thus, bond angle also
reduces. This decrease in bond angle is maximum in between NH3 & PH3. VSEPR can not explain this
sudden change in bond angle. Similarly when we move from H2O to H2Te, maximum reduction in bond
angle is found in between H2O & H2S
H2O H2S H2Se H2Te
104.5° 92° 91° 90.5°
This rapid change in bond angle can be explained by the help of Drago's rule.

Ø4.7 Drago's rule

If central atom belongs to 3rd period or onwards and electronegativity of surrounding atom is 2.5 or less,
then hybridization is not possible on central atom.

NH3 PH3 AsH3 SbH3 According to Drago’s rule,

H2O H2S H2Se H2Te central atom has no hybridization

Shows hybridization

In PH3, P does not show sp3 hybridization, therefore, three hydrogen overlap with half filled 'p' oribitals
and form PH3.

lone pair ..
H P H

P
3s2 3p3
H

All three 'p' orbitals are perpendicular to one another, there fore bond angle in PH3 is 94°.
If we compare the basic character of NH3 and PH3, then we find that NH3 is more basic than PH3, this is
because in NH3 lone pair is present in sp3 hybridized orbital whereas in PH3 lone pair is present in pure
's' orbital. Thus, lone pair of PH3 is more close to the nucleus and less available for the reaction with acid
or H(+)
For example: - Formation of PH4+ is difficult in comparison to NH4+
(+) (–)
NH3 (dil) + HCl NH4 + Cl
(+) (–)
PH3 (concn) + HCl PH4 + Cl
Chapter 4 : Hybridization (VSEPR, Bent’s & Drago’s Rule) 55
• Solubility of NH3 is much higher compared to PH3 in water
(+) (–)
NH3 + H2O NH4 + OH

PH3 + H 2 O (no reaction)

• NH3 forms large number of complexes while PH3 hardly forms complexes
Explanation of Drago's rule
According to Drago's rule, 'P' does not show hybridization in PH3. This fact can be explained on the
basis of calculation of % s character.

s
P q = 94º Cos q =
s–1
94º H s
H Cos 94 = s–1
H
s = 0.02
i.e 2%

This % s character is of a single 'P – H' bond. The % s character for three P – H bonds will be 6 %, thus,
% s character of the orbital containing lone pair will be 94%

94 % s character

P
H
H
H

Among sp (50%), sp2 (33.33%) and sp3 (25%) hybridized orbitals no one has 94% s character. This
shows that lone pair of electrons are present in almost pure's' orbital (94 % s character)

Ø4.8 Hybridization in odd electron species

The presence of odd electrons in an orbital increases its energy and this restricts its involvement in
hybridization. But if surrounding atom is more electronegative, partial positive charge is developed on
central atom. This positive charge attracts the orbital containing odd electron towards central atom &
hence it participates in hybridization. For example

sp2 sp3

C C

H H F F
H F
 56 Chemical Bonding

Ø4.9 Hybridization of some covalent compounds in solid state

Some covalent compounds dimerise in their solid state. They present in the form of cation and anion in
solid state. For e.g. PCl5 found in the form of dimer in solid state

2PCl5 [PCl4](+) [PCl 6](–)

solid sp3 sp3d2
But this dimerisation is not possible in PBr5 because the size of Br is large and P can not adjust more than
5 Br in its surrounding

2PBr5 [PBr 4](+) [PBr6](–) (not possible)

(s)

PBr5 [PBr4](+) Br(–)

solid sp3
In the same way:-

N2O4 NO(+) NO3(–)

solid sp sp2

Cl2O6 [ClO2]2+ [ClO4]2–

solid sp sp3

Ø4.10 Isomorphism
(1) The property of showing same crystal structure by two ionic compounds is called isomorphism For
e.g. FeSO4.7H2O & MgSO4.7H2O
(2) Conditions for isomorphism
Ø These compounds have same formula type
Ø The crystal of these substances should have the same shape For e.g. BaSO4, KMnO4.
Both SO42– and MnO42– ions show tetrahedral geometry but NaClO3 and NaNO3 do not show
isomorphism because of sp2 hybridization in NaNO3 and sp3 hybridization in ClO3– former is
trigonal planar while later is pyramidal in shape.
Ø In both the compounds polarizing properties of both cation and anion should be same.
(3) When a solution of two isomorphous substance is concentrated to the point of crystallization we
get crystals which are homogeneous and contain both the isomorphous substance in the same
ratio in which they were present in the solution.
Chapter 4 : Hybridization (VSEPR, Bent’s & Drago’s Rule) 57

EXERCISE 4.1
Q.1 Which one of the following has larger bond angle than other in each pair?
(i) NH3 & BF3 (ii) C2H4 & C2H6
(iii) CO2 & NH3 (iv) SF6 & PCl5
Q.2 Explain the hybridization in:-
(a) XeOF2 (b) IF5
(c) ICl2+ (d) ICl2(–)
(e) SiCl4 (f) PCl5
(g) PCl5 ( in solid state) (h) PBr5 (in solid state)
(i) XeF4 (j) XeF6
(k) (CH3)3N (l) I3 (–)
(m) XeF5 (–) (n) CO32(–)
(o) SO42(–) (p) ClO4(–)
(q) PO43(–)
Q.3 PCl5 is possible but PH5 is not. Explain.
Q.4 PCl5 is possible but NCl5 is not. Explain.
Q.5 CCl4 does not undergo hydrolysis but SiCl4 undergoes hydrolysis easily. Explain.

EXERCISE 4.2
Q.1 Arrange the following in order of bond angle.
(i) H2O , H2Se, H2Te (ii) NH3, NF3 , NCl3
(iii) CH4 , PH3 , AsH3 (iv) BF3 , NH3
(v) (CH3)3N , (SiH3)3N
Q.2 CF3(–) is more basic than CCl3 (–) explain
Q.3 Discuss shapes of the following
(a) XeF4 (b) XeOF2
(c) ICl2(+) (d) ICl2(–)
(e) XeF2 (f) XeF5(–)
(g) BrF3
 58 Chemical Bonding

Q.1 H H H
l1 l2 l3
C C C
F Cl Br
F F Cl Cl Br Br

l1, l2 and l3 are the bond lengths of C – H bonds in the given molecules. Correct order of these bond
lengths will be:-
(a) l1 > l2 > l3 (b) l3 > l2 > l1
(c) l1 > l3 > l2 (d) l1 = l2 = l3

H
a
C
Q.2
b H
F g
F

a, b and g are bond angles then

(a) a > b > g (b) b > g >a
(c) a > g > b (d) g > b > a
Q.3 Which among the following will not produce Cl2 on heating?
(a) PCl5 (b) PBr2Cl3
(c) PF3Cl2 (d) All of these will produce Cl2 on heating
Q.4 In which case presence of lone pair of electrons on central atom does not influence the geometry.
(a) XeF2 (b) BrF3
(c) NH3 (d) XeF6
Q.5 Which among the following is not linear?
(a) XeOF2 (b) ICl2+
(c) BrF3 (d) All are non linear

O O
c a f d
Q.6 C C
(–)
HO OH O (–)
b O e

For the following two species following statements are proposed

1. a>b> c 2. a=b= c
3. f= d= e 4. a=c>b
5. f= d> e
Chapter 4 : Hybridization (VSEPR, Bent’s & Drago’s Rule) 59
Out of these statements, correct statements are:-
(a) 1 & 3 (b) 2&4
(c) 3 & 4 (d) 4&5
Q.7 Boron forms trivalent halides of the type BX3. Pick out the wrong statement regarding these halides.
(a) BF3 is more acidic than BCl3
(b) Both BF3 and BCl3 are electron deficient compounds
(c) In BI3 boron does not exhibit any hybridization
(d) BCl3 can not undergo dimerisation to produce B2Cl6
Q.8 Which is correctly matched?
Species Shape
(a) BrF5 Trigonal bi pyramidal
(b) ICl4(+) Tetrahedral
(c) ICl4(–) Tetrahedral
(d) BrF3 T - shape
Q.9 Out of SF4, CF4 and XeF4 the molecules with identical shapes are:-
(a) SF4 & XeF4 (b) CF4 and SF4
(c) CF4 and XeF4 (d) all have different geometries
Q.10 In which of the following cases M – F bond has partial double bond character where M is central atom.
(a) OF2 (b) PF3
(c) CCl3F (d) all of these
Q.11 Which among the following is not linear?
(a) N3 (–) (b) ICl2(–)
(c) XeF2 (d) all are linear
Q.12 Correct order of size of hybridized orbitals is:-
(a) sp3 > sp2 > sp (b) sp > sp2 > sp3
(c) sp3 = sp2 = sp (d) sp2 > sp3 = sp
Q.13 Hybridization of carbon in C3O2 is:-
(a) sp (b) sp2
(c) sp 3 (d) both sp and sp2
Q.14 Which kind of hybridization is present on carbon atoms of Mg 2C3
(a) sp3 (b) sp 2
(c) sp (d) both (a) and (c)
Q.15 You have four alkyl halides
CH3 – CF3 CH2F – CH2F CHF2 – CHF2 CF3 – CF3
(1) (2) (3) (4)
Correct order of C – C bond lengths of these halides will be:-
(a) 4 > 3 > 2 > 1 (b) 1>2>3>4
(c) 3 > 4 > 2 > 1 (d) 2>4>3>1
 60 Chemical Bonding
Q.16 Anionic part of solid N2O4 involves --------- hybridization on central atom
(a) sp (b) sp 2
(c) sp 3 (d) sp 3 d
Q.17 Anionic part of solid ICl3 involves -------- hybridization on central atom.
(a) sp 3 (b) sp 3 d
(c) sp 3 d 2 (d) sp 2
Q.18 x, y & z are the % s character C – H bonds of the following molecules.

H H H H H
x y
C C H C z
F
F F F F F

Correct order of % s character is:-

(a) z > y > x (b) x= y= z
(c) x > y > z (d) x = y > z
Q.19 In which of the following cases cationic part does not involve sp3 hybridization
(a) PCl5 (b) PBr5
(c) XeF6 (d) Both (b) & (c)
Q.20 Correct statement about PCl5, IF7 and SF6 is:-
(a) All S – F bond lengths in SF6 are identical.
(b) All I – F bond lengths in IF7 are identical
(c) All P – Cl bond lengths in PCl5 are identical
(d) In SF6 two S – F bonds are shorter than rest four S – F bonds
Q.21 Which will have regular octahedral shape?
(a) XeF6 (b) ICl6(–)
(c) IF6 (–) (d) None of these
Q.22 Iso structural pair is:-
(a) PO43(–) & NO3(–) (b) NO3(–) & ClO3(–)
(c) NH4(+) & XeF4 (d) None of these
Q.23 The shape of gaseous SnCl2 is:-
(a) Tetrahedral (b) Linear
(c) Angular (d) T - shaped
Q.24 Which of the following is planar:-
(a) XeOF4 (b) XeO3F
(c) XeF4 (d) XeO2F2
Q.25 Which of the following are isoelectronic as well as isostructural
NO3(–), CO32(–), ClO3(–), SO3
(a) NO3(–), CO32(–) (b) SO3, NO3(–)
(c) ClO3 (–), CO3 2(–) (d) CO32(–), SO3
Chapter 4 : Hybridization (VSEPR, Bent’s & Drago’s Rule) 61
Q.26 Correct order of strength of covalent bond is:-
(a) sp2 – sp2 > sp3 – sp3 > sp – sp (b) sp – sp > sp2 – sp2 > sp3 – sp3
(c) sp3 – sp3 > sp2 – sp2 > sp – sp (d) sp2 – sp2 > sp2 – sp2 > sp3 – sp3
Q.27 In which of the following cases bond angle is maximum.
(a) (CN)2 (b) BF3
(c) BrF3 (d) NH4 (+)
Q.28 In which of the following case each carbon atom is sp hybridized.
(a) CH2CO (b) C2(CN)4
(c) C3O2 (d) both (b) and (c)
Q.29 C – C bond in CH3 – CF3 undergoes homolytic dissociation the hybridization on two resulting carbon
atoms is / are:-
(a) sp2, sp3 (b) sp3 both
(c) sp2 both (d) sp2, sp2
Q.30 In which of the following pair both the species has trigonal planar geometry.
(a) BF3 & NH3 (b) BF3 & PCl3
(c) BF3 and IF3 (d) None of these
Q.31 The type of orbital not used by chlorine in ClF3.
(a) p x (b) dz2
(c) pz (d) d x2 – y2
Q.32 The type of orbital not used by Xe in XeF6 is
(a) dx2 – y2 (b) dz2
(c) d xy (d) pz
Q.33 The number of lone pairs on Xe in XeF4, XeO3 and XeF2 are respectively.
(a) 2, 1, 3 (b) 3, 1, 2
(c) 2, 2, 1 (d) 2, 1, 2
Q.34 Which among the following contains longest P – Cl bond?
(a) PCl3F2 (b) PF3Cl2
(c) PF4Cl (d) PCl5
Q.35 XeO3 is not isostructural with
(a) NH3 (b) CH3(–)
(c) ClF3 (d) both (c) & (c)
Q.36 The linear structure is not assumed by
(a) SnCl2 (b) NO2(+)
(c) HCN (d) CS2
Q.37 Which of the following species contains two lone pair and two bond pair around central atom?
(a) CO2 (b) H2O
(c) NH3 (d) BF3
 62 Chemical Bonding
Q.38 Planar structure is shown by:-

(a) CO32(–) (b) BCl3

(c) N (SiH3)3 (d) All the above

Q.39 Using VSEPR theory, predict the species having square pyramidal shape:-
(a) XeF4 (b) BrF5
(c) SF4 (d) SO3
Q.40 The central atom assumes sp3 hybridisation:-
(a) S2 O3 (2–) (b) SO3
(c) BF3 (d) NO3(–)
Q.41 The hybridization of Ag in a [Ag(NH3)2](+) is:-
(a) sp (b) sp 2
(c) sp 3 (d) dsp 2
Q.42 Which of the following is planar?
(a) XeO4 (b) XeO3F
(c) XeO2F2 (d) XeF4
Q.43 In which of the following bond angle is maximum?
(a) NH3 (b) NH4 (+)
(c) PCl3 (d) SCl2
Q.44 Among the following, the pair in which the two species are not isostructural, is
(a) SiF4, SF4 (b) IO3(–), XeO3
(c) BH4(–), NH4(+) (d) PF6(–), SF6
Q.45 Bond angle in XeO3 is
(a) 107° (b) 119°
(c) 92° (d) 103°
Q.46 Which one of the following compounds has sp2 hybridization?
(a) CO2 (b) SO2
(c) N2O (d) CO
Q.47 Which of the following are isoelectronic and isostructural NO3(–), CO32–, ClO3(–) & SO3
(a) NO3(–), CO3–2 (b) SO3, NO3(–)
(c) ClO3(–), CO3–2 (d) CO3–2, SO3
Q.48 In which one of the following pairs, molecules/ions have similar shape?
(a) CCl4 and CH3CH2(–) (b) NH3 and BF3
(c) BF3 and CH3(+) (d)CO2 and H2O
Q.49 Which are the species in which sulphur 3
undergoes sp hybridization?
(1) SF4 (2) SCl2
(3) SO4 2– (4) H2S
Chapter 4 : Hybridization (VSEPR, Bent’s & Drago’s Rule) 63
Select the correct answer using the code given below:-
(a) 1 and 2 (b) 2, 3 and 4
(c) 1, 3 and 4 (d) 1, 2 and 3
Q.50 Which of the following species have undistorted octahedral structures?
(1) SF6 (2) PF6 (–)
(3) SiF62– (4) XeF6
(a) 1, 3 and 4 (b) 1, 2 and 3
(c) 1, 2 and 4 (d) 2, 3 and 4
Q.51 Consider the following molecules or ions.
(i) Chloroform (ii) NH4 (+)
(iii) SO42– (iv) ClO4(–) (v) H3O(+)
sp3 hybridization is involved in
(a) (i), (ii), (v) only (b) (i), (ii) only
(c) (i), (ii), (iii), (iv) (d) (i), (ii), (iii), (iv), (v)
Q.52 The number of lone pairs on Xe in XeF2, XeF4 and XeO2F2 respectively are:-
(a) 3, 2, 1 (b) 2, 4, 6
(c) 1, 2, 3 (d) 6, 4, 2
Q.53 The correct order of bond angles (smallest first) in H2S, NH3, BF3 and SiH4 is:-
(a) H2S < SiH4 < NH3 < BF3 (b) NH3 < H2S < SiH4 < BF3
(c) H2S < NH3 < SiH4 < BF3 (d) H2S < NH3 < BF3 < SiH4
Q.54 In which of the following compounds will the bond angle be maximum?
(a) NH3 (b) Al2Cl6
(c) PCl5 (solid) (d) SnCl2
Q.55 Which of the following two are isostructural?
(a) XeF2, IF(–) (b) NH3, BF3
(c) HCO3(–), SO2 (d) PCl5, IF5
Q.56 Which of the following species has a linear shape?
(a) NO2(+) (b) O3
(c) NO2 (–) (d) SO2
Q.57 What is the hybridization state of the central atom in the conjugate base H3O(+) ion?
(a) sp (b) sp 2
(c) sp 3 (d) dsp 2
Q.58 Which one of the following is a planar molecule?
(a) NH3 (b) SF4
(c) Na2CO3 (d) PBr3
Q.59 Which one of the following molecules has the smallest bond angle?
(a) H2O (b) NH3
(c) H2Se (d) H2S
 64 Chemical Bonding
Q.60 Which of the following is a linear molecule?
(a) SO2 (b) XeOF2
(c) ICl2 (–) (d) BeCl2
Q.61 Which of the following statement applies to CIF3?
I. Geometrical arrangement is pyramidal
II. The molecule is almost T shaped
III. F – Cl – F bond angle is exactly 90°
(a) I and II (b) II and III
(c) only I (d) only II
Q.62 Which shape is associated with ClF4 (–) ion?

(a) Tetrahedral (b) Square planar

(c) T-shape (d) Square pyramid
Q.63 Among the following the pair in which two species are not iso structure is:-
(a) Na2S2O3 and Na2SO3 (b) IO3(–) and XeO3
(c) SO42– and NH4(+) (d) I3(–) and ICl2(–)
Q.64 The bond angle around 'S' in H2S molecule is
(a) > H2O (b) < H2O but > H2Se
(c) > NH3 (d) > H2O as well as NH3
Matrix match: -
Q.65 Column - I Column - II
(A) I3 (–) (p) 2 lone pair around central atom
(B) H3O(+) (q) Pyramidal
(C) XeF2 (r) Linear
(D) BrF3 (s) One lone pair
Q.66 Column - I Column - II
(A) XeF6 (p) Regular structure
(B) XeF5 (–) (q) Distorted structure
(C) XeF4 (r) Two lone pair
(D) BrF3 (s) One lone pair
Q.67 Hybridization Orbitals involved
(A) sp 2 (p) py
(B) sp (q) pz
(C) dsp 2 (r) dx2 – y2
(D) sp 3 d (s) dz2
Q.68 Molecule/ ion Hybridization
(A) Cr2O72– (p) sp 3
(B) MnO4 – (q) sp 2
(C) K2SO4 (r) sp
(D) K2SO3 (s) sp 3 d
Chapter 4 : Hybridization (VSEPR, Bent’s & Drago’s Rule) 65

SUBJECTIVE EXERCISE
EXERCISE 4.1
1. (i) BF3 (120°) (ii) C2H6 (120°) (iii) CO2 (180°) (iv) PCl5 (90°,120°)
2. (a) sp 3 d (b) sp 3 d 2 (c) sp 3 (d) sp 3 d
(e) sp 3 (f) sp 3 d (g) sp 3 ,sp 3 d 2 (h) sp 3
(i) sp 3 d 2 (j) sp 3 d 3 (k) sp 3 (l) sp 3 d
(m) sp 3 d 3 (n) sp 2 (o) sp 3 (p) sp 3
(q) sp 3
3. Due to less electronegativity of hydrogen atom, in phosphorous excitation of 3s electron to 3d sub shell
does not occur

ground state
3s 3p 3d
3
sp hybridisation in PH3
excited state

sp3d hybridisation in PCl 5

4. For the formation of NCl5, N should exhibit sp3d hybridization but N can not show sp3d hybridization as
it does not contain d orbital
5. Si possesses empty d orbital in which Si can receive lone pair of electrons donated by H2O molecules
during hydrolysis which is not possible in CCl4 as carbon does not contain empty ‘d’ orbital.

Cl Cl (+)
.. OH2
Si + H2O
.. Si HCl + SiCl 3OH
Cl Cl
Cl Cl Cl
Cl

EXERCISE 4.2
1. (i) H2O > H2Se > H2Te (ii) NCl3 > NH3 > NF3 (iii) CH4 > PH3 > AsH3
(iv) BF3 > NH3 (v) (CH3)3N < (SiH3)3N
2. Due to back bonding negative charge is delocalized in CCl3(–) & hence, electrons of negative charge are
less available for protonation (reaction with H+ or acid)
 66 Chemical Bonding
3. (a) square planar (b) T-shaped (c) Bent (d) Linear
(e) Linear (f) Pentagonal planar (g) T-shaped

OBJECTIVE EXERCISE
1. (b) 2. (a) 3. (c) It has two axial P–F bonds 4. (a) 5. (d) 6. (c)
7. (a) In BF3 back donation takes place which reduces electron deficiency of boron
8. (d) 9. (d) 10. (b) 11. (d) 12. (b) 13. (a) O = C = C = C = O
+2 1– 3–
14. (d) Mg2 [C C C] 15. (b) 16. (b) 17. (c) 18. (c)

19. (c) 20. (a) 21. (d) 22. (d)

....
Sn
23. (c) 24. (c) 25. (a) 26. (b)
Cl Cl
27. (a) N C C N bond angle 180°
28. (d) N C C C C N O=C=C=C=O

29. (a)
. .
CH3 CF3 CH3 (sp 2 ) + CF3 (sp3)

30. (d) 31. (d) 32. (c) 33. (a) 34. (d) as it contains two axial P–Cl bonds
35. (c) Except ClF3 rest all are pyramidal where as ClF3 has T-shape 36. (a) 37. (b)
38. (d) 39. (b) 40. (a) 41. (a) 42. (d) 43. (b) 44. (a) 45. (d)
46. (b) 47. (a) 48. (c) 49. (b) 50. (b) 51. (d) 52. (a) 53. (c)
54. (b) In Al2Cl6 aluminium is sp2 hybridized & it occurs as:-

Cl Cl Cl
Al Al
Cl Cl Cl

55. (a) 56. (a) 57. (c) 58. (c) The 'C' of sodium carbonate is sp2 hybridized
59. (c) 60. (d) 61. (d) 62. (b) 63. (a) 64. (b)
65. A–p,r B–q,s C–r D– p 66. A–q,s B–r,p C–p,r D–q,r
67. A–p,q B–p,q C–p,q,r D– p,q,s 68. A – p B–p C–p D–q
Chapter 5 : Polarization, Dipole Moment & Hydration Energy 67

5
Polarization, Dipole Moment
& Hydration Energy
We have studied ionic and covalent bonds in chapter - 02. Experiments revealed that no bond is 100% ionic or
covalent. Covalent compounds have some ionic character and vice - versa.
In any ionic compound covalent character can be observed by the help of polarization. On the other hand ionic
nature in covalent compounds can be observed by either of the two ways.
• Henry - Smith method • Dipole moment

Ø5.1 Henry - Smith method

% ionic character = 16D + 3.5 D2…………………………(1)
Where D = Electronegativity difference of the covalently bonded atoms
For example in HF % ionic character is found to be 43 %
XF = 4 XH = 2.1
% ionic character = 16(4 – 2.1) + 3.5(4 – 2.1)2
= 30.40 + 12.63 = 43.03
In equation (1) Pauling electro negativity (X) is used
Note : % ionic character of homonuclear diatomic molecules like O2, N2 and H2 can not be explained
using Henry - Smith method because in these cases electro negativity difference is zero. Their % ionic
character can be observed experimentally. For e.g. in H2 % ionic character is 2% which is developed due
to instantaneous induced dipole moment.
Ø5.2 Dipole moment
When electro negativity difference between covalently bonded atoms is large shared electron pair is
shifted towards more electronegative element and thus, dipole is generated
s s–
A+ .. B XB > XA
Such molecules are called polar molecules.

s+ .. s– ..
H F F F
polar molecule non polar molecule
Strength of dipole can be measured in terms of dipole moment (µ) which is defined as:-
 68 Chemical Bonding
(1) "It is equal to the product of the electronic charge and distance'd' between negative and positive
electric centers in the dipole"

r +q –q
µ = q × d
d
or
r
µ = q × bond length.
(2) Dipole moment is a vector quantity it has direction from +ve to –ve

m1

mRes
= µ12 + µ22 + 2µ1µ2 cos q
q
m2

r 1
µRes µ cos q µ
q

(3) Units of dipole moment

M.K.S = Coulomb meter
C.G.S = e.s.u. cm
Another unit of dipole moment is Debye (D)
1 Debye (D) = 0.33 × 10–29 C × m
1D = 10–18 e.s.u × cm
1 unit charge = 1.6 × 10–19 c or 4.8 × 10–10 e.s.u
(4) Application of dipole moment
(a) With its help we can find out % ionic character in a covalent compound.
% ionic character = (observed µ × 100) / Calculated µ
For example :- Dipole moment of HCl is found to be 1.03 D Bond length of H — Cl bond is 1.27 Å
Hence, by the help of these values we can calculate % ionic character in HCl molecule as follows:-
S+ S–
H Cl
q = 1 unit = 4.8 × 10–10 e.s.u.
µ (Calculated) = 4.8 × 10–10 × 1.27 × 10–8 = 6.10 × 10–18 e.s.u. cm
= 6.10 × 10–18 / 10–18 = 6.10 D
% ionic character = (1.03 × 100) / 6.10 = 16.89 %
(b) If the dipole moment of a species is known then its structure can be predicted easily
For eq. Experimental µ of CO2 is zero, for this reason its shape is linear & not bent
Chapter 5 : Polarization, Dipole Moment & Hydration Energy 69

s– O
mRes = 0
s– s+ s–
O C O
m2
m1 m2
s +C m O s–
mRes = 0 1

Linear (CORRECT) Bent (WRONG)

Similarly µexp of BF3 is zero, thus it acquires triangular planar shape

s–
F
m2

µRes = 0
BS+
m3
F
m1 s–
F
s–
(c) By the help of µ geometrical isomers can be distinguished. In general µ of cis form is found to be
greater than that of trans form.

Cl mRes Cl
H m1 Cl m1
m2
C C C C
m2 H H
Cl H
(Trans) (cis)

µ(cis) > µ (trans)

Let us see some miscellaneous examples

.. ..
mb mb

N N
m1 m1
(1) ma m3 m3 ma
H H F F
m2 H m2 F

µ Res = µ a + µ b µ Res = µa ~ µb
Here µ a = Resultant of µ1, µ2 and µ3. From above diagrams it is clear that
µ of NH3 > µ of NF3
 70 Chemical Bonding

m1 NO2 m1 NO2 m1 NO2

NO2

(2) m2
NO2
m2
m2 NO
2

q = 60° q = 120° q = 180°

(A) (B) (C)

As we know that resultant dipole moment is reciprocal to 'q' therefore, µ A > µ B > µ C

(3) Since CH3 is an electron repelling group therefore, µ C > µ B > µ A

CH3 m2 CH3 CH3

NO2
m2
NO2
m1 NO2 m2
m1 m1
q = 120° q = 60° q = 0°
(A) (B) (C)

Ø5.3 Polarization (Covalent character in ionic compound)

(1) In an ionic compound, covalent character can be observed with the help of polarization. When
cation and anion come close to each other, they form ionic bonds. In isolated conditions both
cation and anion are spherical and symmetrical in shape but as they come closer to each other, the
electron cloud of anion is attracted by the charge of cation, whereas, electron cloud of cation is
attracted by the nucleus of anion. This attraction develops distortion in electron cloud. This
distortion is negligible in cation owing to its small size and electron cloud of cation is strongly
bonded to its nucleus but electron cloud of anion is loosely bonded to its nucleus owing to its large
size which results in to distortion in the size of anion by cation. Thus polarization of anion is
defined as
"The distortion in electron cloud of anion by cation and the tendency of cation to distort anion is
called polarizing power of cation or ionic potential (f) or degree of covalency or charge density."

(2) It must be noted that polarization is favourable if both anion and cation are of incomparable size so
that cation can easily polarize anion.
Chapter 5 : Polarization, Dipole Moment & Hydration Energy 71

+ – (Ionic)

+ –
Polarisation

+ –

+ – (Covalent)

Polarization µ Covalent character

Polarization µ 1 / Ionic character
Polarization µ 1 / Thermal stability
Polarization µ 1 / Solubility in polar solvents like water
(3) Fajan rule - Fajan suggested some rules for effective polarization.
Ø Cation should be small and anion should be large in size
Ø Both cation and anion should have high charge
Ø Cations having pseudo inert configurations have more polarizing power than the cations
having inert and non inert configurations.
Order of Polarizing power of cations is:-
Pseudo configuration > non - inert configuration > inert configuration
On the basis of polarizing power cations can be categorized in three ways.
(a) Cation with inert gas configuration - These cations have 8 electrons in their valence
shell (ns2 np6)
For e.g. Na+, Mg+2 , Al+3, Ca+2 etc
(b) Cations with pseudo inert configuration - The valence shell of these cations have 18
electrons. Their d sub shell is completely filled (ns2 np6 nd10)
For e.g. Zn+2 (3d10), Cu+ (3d10), Ag+, Cd+2, Hg+2 ………..etc
(c) Cations with non inert configuration - These cations hold 20e– in their valence shell.
Their general electronic configuration is ns2 np6 nd10 (n + 1)s2 or (n–1)s2 (n–1)p6
(n–1)d10 ns2
For e.g. Tl+, Pb+2, Bi+3
For more details see inert pair effect

Ø5.4 Application of polarization (Fajan rule) & lattice energy

(A) Covalent Character - If polarization increases, covalent character also increases and ionic character
decreases
72 Chemical Bonding

CuCl > NaCl

Pseudo inert gas AgCl > KCl Inert gas
configuration configuration
CdCl2 > CaCl2

(More Covalent) (Less Covalent)

PdCl2 > CaCl2

(Non inert configuration) (Inert configuration)
(B) Nature of Oxides
MO (Base) + H(+) (acid) MOH
f µ 1 / Basic character µ acidic character
On moving from top to bottom in any group the size of cation increases, thus, ‘f’ decreases and the
basic character increases.
Li2O < Na2O < K2O < Rb2O < Cs2O
(Less basic) (More basic)
MgO < CaO < SrO < BaO
Similarly ZnO (Pseudo inert configuration) is less basic than MgO (Inert gas configuration)
ZnO < PbO < MgO
(Pseudo) (Non inert) (Inert)
Ø All oxides of 's' block elements are basic in nature except BeO which shows amphoteric nature
Ø Oxides of non metal are acidic in nature except N2O, NO and CO which are neutral.
Ø On moving from left to right along a period, acidic character of non metal oxides increases.
MgO < P2O5 < SO3
(Less acidic) (More acidic)
+2 +4 +7
MnO MnO2 Mn2O7
(Basic) (amphoteric) (acidic)
f increases

Ø f = 2.2 to 3.2 amphoteric oxide

f < 2.2 Basic oxide

f > 3.2 acidic oxide

Amphoteric oxides - As2O3, Sb2O3, Bi2O3, GeO, ZnO, Al2O3, BeO, Cr2O3, Ga2O3, PbO, SnO
(C) Colour or intensity of Colour in Compounds -
Polarization µ Intensity of Colour..
More polarization increases distortion in electron cloud, which makes electronic transition easy
and compound seemed to be coloured.
Chapter 5 : Polarization, Dipole Moment & Hydration Energy 73
AgCl AgBr AgI Ag2S
(White) (Light yellow) (Dark yellow) (Black)
(D) Thermal stability - Here we are discussing thermal stabilities of metal carbonates, sulphates,
nitrate, bicarbonates and halides
(1) Metal Carbonates -

MCO3 MO + CO2

1
f µ Polarisation power µ
Thermal Stability

On moving from top to bottom in any group, the size of cation increases and thermal stability
increases
BeCO3 < MgCO3 < CaCO3 < SrCO3 < BaCO3
(More thermally stable)
Thus, to dissociate BaCO3 high temperature is needed, on the other hand BeCO 3 needs low
temperature for dissociation.
Among alkali metals Li has smallest size hence maximum polarization takes place in Li 2CO3
due to incomparable sizes of Li+ (Very small size) and CO32– (large size)

Li2CO3 Na2CO3 K2CO3 Rb2CO3 Cs2CO3

More polarisation less chance of plarisation because of

More covalent comparable sizes of M+ and CO 32–
Thermally unstable

Li2CO3 < Na 2CO3 < K 2CO3 < Rb 2CO3 < Cs 2CO3

Increasing thermal stability

Li2 CO3 Li2 O + CO 2

Na2CO3, K2CO3, Rb2CO3 and Cs2CO3 are ionic in nature due to poor polarization hence
these carbonates are thermally stable and do not easily decompose on heating
(2) Metal sulphate -
T < 1073 K
MSO4 MO + SO 3

T > 1073 K
MSO4 MO + SO 2 + 1/2 O 2

f µ Polarizing power µ covalent character

1
µ Thermal stability
74 Chemical Bonding
On moving from top to bottom in any group, the size of cation increases and thermal stability
increases
BeSO4 < MgSO4 < CaSO4 < SrSO4 < BaSO4
(Less thermally stable) (More thermally stable)
Among alkali metal sulphates only Li2SO4 is thermally unstable

Li2SO4 Na2SO4 K2SO4 Rb2SO4 Cs2SO4

More polarisation less chance of polarisation because

More covalent of comparable sizes of M+ and SO 42–
Thermally unstable

Li2SO4 < Na 2SO4 < K 2SO4 < Rb 2SO4 < Cs 2SO4

Increasing thermal stability

Li2SO4 Li2O + SO3

Na2SO4, K2SO4, Rb2SO4, Cs2SO4, are ionic in nature due to poor polarization hence, these
sulphates are thermally stable and do not easily decompose on heating.

Green vitriol is an exceptional case

FeSO4. 7H2O FeSO4 + 7H2O

2FeSO4 Fe2O3 + SO2 + SO3

(3) Metal nitrate - Metal nitrate produce metal oxide and NO2 on heating

D
Metal nitrate ¾¾ NO2 + Metal oxide
®

Mg(NO3)2 D MgO + 2NO2 + 1/2O2

¾¾®

2LiNO3 D Li2O + 2NO2 + 1/2O2

¾¾®

But nitrates of Na+, K+, Rb+, Rb+ and Cs+ give following reactions-

2MNO3 D 2MNO2 + O2
¾¾®

At high temperature MNO2 further undergoes dissociation as -

2MNO2 D M2O + N2 + 3/2O2

¾¾®
Chapter 5 : Polarization, Dipole Moment & Hydration Energy 75
For e.g.
D D
2NaNO3 ¾¾¾ ® 2NaNO ®
¾¾¾¾ Na2O + N2 + 3/2O2
–O 2 2 High T

Polarization µ Covalent character

1
µ Thermal stability
LiNO3 < NaNO3 < KNO3 < RbNO3 < CsNO3
Be(NO3)2 < Mg(NO3)2 < Ca(NO3)2 < Sr(NO3)2 < Ba(NO3)2

Increasing thermal stability

Oxides of native metals (Ag, Hg, Pt & Au) are thermally unstable & give O2 al ong with metal on

heating. Ag2 O 2Ag + 1/2O2

(4) Metal bicarbonates - Metal bicarbonate dissociates on heating and get converted in to
carbonates
MHCO3 Metal Carbonate + H2O + CO2
For e.g.

2LiHCO3 Li2CO3 + H 2O + CO 2

Li2O + CO 2

But NaHCO3, KHCO3, RbHCO3 and CsHCO3 dissociate as -

2NaHCO3 Na2CO3 + H2O + CO2

no reaction

In LiHCO3 polarization occurs effectively due to uncomparable sizes of Li+ (small) & HCO3–
(big). Thus, due to better polarization LiHCO3 is more covalent in comparison to rest
bicarbonates of alkali metals. Due to more polarization LiHCO3 exists in liquid state

LiHCO3 NaHCO3 KHCO3 RbHCO3 CsHCO3

More polarisation less chance of polarisation due to

More covalent comparable sizes of M+ and HCO3–
(liquid)
(Ionic solids)
76 Chemical Bonding
All bicarbonates of alkaline earth metals exist in liquid form due to effective polarization. These
metal cations are smaller than the cations of alkali metals and they have +2 charge. This is
responsible for effective polarization in bi carbonates of alkali earth metals

Be(HCO3)2 Mg(HCO3)2 Ca(HCO3)2 Sr(HCO3)2 Ba(HCO3)2

(Exist in liquid state)

1
f µ Polarizing power µ Thermal stability

LiHCO3 < NaHCO3 < KHCO3 < RbHCO3 < CsHCO3

Be(HCO3)2 < Mg(HCO3)2 < Ca(HCO3)2 < Sr(HCO3)2 < Ba(HCO3)2

Increasing thermal Stability

(5) Metal halide - Thermal stability of metal halides is checked by lattice energy and not by
polarization
Lattice energy µ Thermal stability of metal halide
Lattice energy µ charge on cation and anion

1
µ
(r + ) + (r – )

KF > KCl > KBr > KI

LiF > NaF > KF > RbF > CsF

Decreasing order of Thermal stability

In the same way metal nitrides and metal oxides can be arranged in order of thermal stability.
Li3N > Na3N > K3N
Li2O > Na2O > K2O > Rb2O

Decreasing lattice energy

Decreasing Thermal stability

As we know, lattice energy is proportional to the product of ionic charges therefore, thermal
stability increases with increase in ionic charges
L.E. = K q1 q2 / r2

+2 –1 +2 – 2 +2 –3
MgF2 < MgO < Mg3N2
q1q2 = 2 q1q2 = 4 q1q2 = 6
Increasing lattice energy & Thermal stability
Chapter 5 : Polarization, Dipole Moment & Hydration Energy 77
Ø5.5 Hydration energy - (Solvation energy)
When a cation or an anion in the gaseous state reacts with a solvent in the liquid state, energy is
liberated. This liberated energy is termed as solvation energy. When the solvent is water the liberated
energy is called hydration energy.
Li + + H2O Li+ + 124.4 Kcal / mol.
(g) (l) (aq)
d– d+
Water is a polar solvent (HO H) . A gaseous cation is attracted by the negative oxygen ends of the
water molecules while the anion is attracted by the hydrogen ends. The greater the charge density
(charge / surface area) of the ion the greater will be the interaction i.e. the greater will be the hydration
energy.
Hydration µ Hydration energy µ 1 / size of ion
µ Charge on ion µ size of hydrated ion
More is the hydration more will be the size of hydrated ion.

H OH
+

+
+
+

–
+

–
+

+– Li+ – + Large size Cs+

+

–
+

+
+
+
+

Small size

Since Li+(aq) is bigger in size in comparison to that of Cs+(aq) hence Li+(aq) will have less ionic mobility
in comparison to Cs+(aq)
Hydration µ 1 / ionic mobility
Interestingly there is a considerable difference in the hydration energy of F(–) and K(+) ions although
they have the same ionic radius (1.36Å). This is due to the fact that F(–) interacts with small H atoms
while K+ interacts with much larger oxygen atom of water. More hydrogen atom can get around a F(–) ion
compared to oxygen atoms around the K(+) ions
Ion Hydration energy Ion Hydration energy
Li+ – 124.4 Kcal / mol F(–) – 121 Kcal / mol
Na+ – 97 Cl(–) – 87
K+ – 77 Br(–) –80
 78 Chemical Bonding
Ø5.6 Solubility of ionic compounds
It is very popular proverb that 'like dissolves like'. Means polar compounds dissolve in polar medium
and non polar compound dissolve in non polar medium. For eq. NaCl is an ionic compound, it dissolves
easily in polar medium like water but NaCl does not dissolve in benzene because benzene is a non polar
solvent. Similarly, naphthalene (C10H8) is a non polar compound can easily dissolve in benzene but it is
insoluble in water. Generally, we check solubility of compounds in water (an universal solvent)
There are three factors for dissolution of a compound in water.
Ø Compound is ionic and undergoes dissociation when dissolved in water to form aqueous ions
AB + H2O A(+) + B(–)
(s) (aq) (aq)
Ø Compound forms hydrogen bond with water (Disused later in chapter - 07)
Ø The molecules of compound easily accommodate in free space present in water molecules
Here we shall discuss the solubility of ionic compound in water.
Key Point - Those students who have not studied thermodynamics are advised to study the
portion written after solubility temperature curve.
When a solute dissolves in a solvent then the value of DG in the whole process is always negative
(DG = – ve) and the value of DS remains positive (DS = +ve)
Solute + Solvent Solution or dissolution of solute
When solute is added in a solvent, the heat of dissolution (DH) will be +ve or –ve from Gibb's
Helmholtz equation.
DG = DH – TDS
If the value of DH is negative, then DG is –ve and compound can easily dissolve in solvent but if
the value of DH is +ve, then to make DG negative TDS should have more value. For this we increase
temperature in order to increase the value of TDS and DG would become –ve.

Hsolution
RT
S = Ae
Solubility

Temperature

Therefore, on increasing temperature, solubility of a compound increases. Normally, the solubility

of ionic compound in water depends on two factors.
Ø Polarization
Ø Lattice energy & hydration energy
Chapter 5 : Polarization, Dipole Moment & Hydration Energy 79
As polarization increase, covalent character increases and ionic character decreases. Thus, ionic
compounds show less solubility in water on increasing polarization.
Polarization µ Covalent character µ 1 / Ionic character
µ 1 / solubility in water
Lattice energy µ 1 / size of ions µ charge on ions
Hydration energy µ 1 / size of ions µ charge on ions
The factors affecting hydration energy & lattice energy are same. Thus, it is difficult to predict the
exact solubility of ionic compound in water because-
Hydration energy (H.E) µ Solubility in water
Lattice energy (H.E) µ 1 / solubility in water

An ionic compound dissolves in water only when H.E > L.E

Here we are showing two cases to explain the solubility of the salts of alkali and alkaline earth
metals in water
Case - I : When the size of anion is small or we can say if the sizes of both anion and cation are
comparable (Like O–2, S–2, OH(–), F(–) & Cl(–)etc), then on moving from top to bottom in a group, there
is apparent decrease of H.E and L.E but the decrease in L.E is found to be more than that of H.E and
hence solubility of salts increase on moving down the group.

Group Size of Cation L.E. H.E. Solubility

Top

bottom (increases) (More decrease) Decrease increases

(Less soluble) LiCl < NaCl < KCl < RbCl < CsCl (More soluble)
(Less soluble) MgO < CaO < SrO < BaO (More soluble)
Br(–) & I(–) ions are not an example of this class because these ions have large sizes.
Case - II : When the size of anion is large, its hydration does not occur properly, thus, on moving down
the group L.E. & H.E. both show decrease but decrease in H.E. is found to be greater than L.E. Hence
solubility decreases.
For eg. SO4–2, CO32–, NO3(–), Br(–), I(–), PO43–

Group Size of Cation L.E. H.E. Solubility

Top

(bottom) (increases) (Decreases) (More decrease) (Decreases)

(More soluble)MgSO4 > CaSO4 > SrSO4 > BaSO4(Least soluble)

(More soluble)NaNO3 > KNO3 > RbNO3 > CsNO3(Least soluble)
 80 Chemical Bonding
(–)
Note: - Although the size of HCO3 is large yet it is an example of Case - I. i.e. solubility of metal
bicarbonates increases on moving down the group (we will discuss it in next chapter).
Let us clear these cases by taking some more examples (descending order of solubility)

MgSO3 > CaSO3 > SrSO3 > BaSO3 (Case - II)

NaCl > NaBr > NaI (Polarization)

NaBr > KBr > RbBr > CsBr (Case - II)

AgF > AgCl > AgBr > AgI (Polarization)

NaNO3 > KNO3 > RbNO3 > CsNO3 (Case - II)

Na2O < K2O < Rb2O < Cs2O (Case - I)

Ø5.7 Some exceptional solubility order

MgF2 < CaF2 < SrF2 < BaF2 < BeF2

Li2CO3 < Na2CO3 < K2CO3 < Rb2CO3 < Cs2CO3

NaI > LiI > KI > RbI > CsI

LiCl > CsCl > RbCl > NaCl > KCl

BeX2 > MgX2 > CaX2 > SrX2 > BaX2 (X = Cl, Br, I)

MgC2O4 < CaC2O4 < SrC2O4 < BaC2O4 < BeC2O4

Chapter 5 : Polarization, Dipole Moment & Hydration Energy 81

Q.1 SnCl2 is white but SnI2 is red explain.

Q.2 CH3Cl has more dipole moment than CH3F explain.

Q.3 Explain why Li shows diagonal relationship in properties with Mg.

Q.4 Out of Li2CO3, Na2CO3, K2CO3, RbCO3 & CsCO3 only Li2CO3 undergoes dissociation to produce CO2.
Explain.

Q.5 AgCl is white AgI is yellow & Ag2S is black explain.

Q.6 SnCl2 melts at 535°C white, SnCl4 melts at - 15°C explain.

Q.7 Arrange the following in descending order of :-

(a) Intensity of colour AgCl, AgBr, AgI

(b) Solubility in water MgSO4, CaSO4, SrSO4 BaSO4

(c) Solubility in water MgF2, CaF2, SrF2 & BaF2

(d) Melting point NaCl KCl RbCl CsCl

(e) Thermal stability NaCl KCl RbCl CsCl

(f) Thermal stability NaNO3 KNO3 RbNO3 CsNO3

(g) Lattice energy MgCl2 MgO Mg3 N2

(h) Solubility in water AgCl AgBr AgI

Q.8 For a diatomic molecule dipole moment is 1.2 D and interatomic spacing is 1 A°. What fraction of charge
is present on each atom? (Ans = 25 %)

Q.9 Dipole moment in water is 1.85 Debye. If bond length of O – H bond is 0.94 Å and bond angle is 105°.
Calculate fraction of charge present on each atom. Given that Cos 52.5° = 0.609 (Ans 67.29%)

Q.10 Dipole moment of HBr is 2.6 × 10–30 coulomb meter. Calculate % ionic character if inter atomic spacing
is 1.41 Å. (Ans = 11.5%)
 82 Chemical Bonding

Q.1 Dipole moment of NH3 is greater than

(a) PCl5 (b) CO2
(c) NF3 (d) all of these
Q.2 The correct order of dipole moment is:-
(a) CF4 > NF3 > NH3 > H2O (b) H2O > NH3 > NF3 > CF4
(c) H2O > NH3 > CF4 > NF3 (d) CF4 > NH3 > NF3 > H2O
Q.3 The % ionic character in LiF if internuclear spacing is 0.156 pm and experimental dipole moment of LiF is
6.32 D, will be:-
(a) 84.5 % (b) 50 %
(c) 58.7 % (d) 17%
Q.4 Which statement is incorrect regarding AgCl and NaCl
(a) Both are colorless (b) AgCl is more covalent than NaCl
(c) Both exhibit isomorphism
(d) NaCl is more soluble in acetone in comparison to AgCl
Q.5 In which case Ist molecule is more thermally stable than 2nd.
(a) MgCO3, Na2CO3 (b) K3N, Na3N
(c) LiF, NaF (d) MgSO4, CaSO4
Q.6 Which among the following will not exist in liquid form?
(a) Mg(HCO3)2 (b) Ca(HCO3)2
(c) LiHCO3 (d) NaHCO3
Q.7 Correct order of solubility in water is:-
(a) NaHCO3 > KHCO3 > RbHCO3 (b) RbHCO3 > KHCO3 > NaHCO3
(c) NaHCO3 = KHCO3 > RbHCO3 (d) RbHCO3 = KHCO3 > NaHCO3
Q.8 Correct order of solubility in water
(a) Na2SO4 > K2SO4 > Rb2SO4 > Cs2SO4 (b) Cs2SO4 > Rb2SO4 > K2SO4 > Na2SO4
(c) Cs2SO4 > Rb2SO4 > Na2SO4 > K2SO4 (d) All have same solubility in water
Q.9 Which will produce SO3 on heating?
(a) FeSO4 (b) MgSO4
(c) BeSO4 (d) CuSO4
Q.10 Which among the following will produce O2 on heating?
(a) AgNO3 (b) NaNO3
(c) HgO (d) All of these
Chapter 5 : Polarization, Dipole Moment & Hydration Energy 83
Q.11 Correct order of covalent character is:-
(a) NaF > KF > LiF > RbF > CsF (b) LiF > NaF > KF > RbF > CsF
(c) CsF > RbF > KF > NaF > LiF (d) CsF > RbF > KF > LiF > NaF
Q.12 Correct order of acidity is :-
(a) PbO > MgO > ZnO (b) MgO > PbO > ZnO
(c) ZnO > MgO > PbO (d) ZnO > PbO > MgO
Q.13 Which among the following is colourless?
(a) AgCl, AgBr (b) ZnS, PbF2
(c) PbI2, Ag2S (d) MgS, CdS
Q.14 Which has maximum dipole moment?

F F

(a) F (b)
F F F

F F
F
(c) (d)

F F

Q.15 In which solvent AgI has maximum solubility

(a) Diethyl ether (b) Water
(c) Acetone (d) C2H5OH
Q.16 Which of the following molecule do not have zero dipole moment?

Cl H Cl H
(a) C C (b) C
H Cl H Cl

(c) CH3C CCH 3 (d) PCl5

Q.17 Standard heat of formation of an ionic compound 'AB' is –67 Kcal/mol, electron affinity of 'B' is
83 Kcal/mol, dissociation energy for B2 is 34 Kcal/mol, Ist I.E. for A is 141 Kcal/mol & heat of sublimation
for A is 48 Kcal / mol. Calculate lattice energy of AB.
(a) –190 Kcal / mol (b) –207 Kcal / mol
(c) –627 Kcal / mol (d) –162 Kcal / mol
 84 Chemical Bonding
Q.18 Which statement is not correct regarding the dipole moments of the following molecules?

Cl H Cl H
C = C = C & C = C = C = C
H Cl H Cl
(1) (2)

(a) µ1 = µ2 = 0 (b) µ1 ¹ µ2 ¹ 0
(c) µ1 > µ2 (d) µ2 > µ1
Q.19 NCl3 NCl2 + Cl DH = +x KJ / mol
NOCl NO + Cl DH = +y KJ / mol
If x & y are the dissociation energies of N – Cl bond in NCl 3 & NOCl respectively then:-
(a) x > y (b) x<y
(c) x = y (d) cannot predict
Q.20 The compound with highest melting point is:-
(a) MgO (b) NaCl
(c) KBr (d) BaO
Q.21 Compound with least boiling point is:-
(a) CH3CH2F (b) CH3CHF2
(c) CF3CF3 (d) CH3CF3
Q.22 Correct order of dipole moment is:-
(a) CH3F > CH3Cl > CH3Br > CH3I (b) CH3I > CH3Br > CH3Cs > CH3F
(c) CH3Cl > CH3F > CH3Br > CH3I (d) CH3F = CH3Cl > CH3Br > CH3I
Q.23 Molecule Dipole moment
(A) CH3F (P) 1.82 D
(B) CH2F2 (Q) 1.97 D
(C) CHF3 (R) 1.65 D
(D) CF4 (S) 0D
Correct matching is:-
(a) A Q, B R, C P,, D S
(b) A P, B Q, C R, D S
(c) A Q, B P, C R, D S
(d) A R, B P, C Q, D S
Chapter 5 : Polarization, Dipole Moment & Hydration Energy 85
Q.24 Molecule Dipole moment
(A) CH3Cl (P) 1.94 D
(B) CH2Cl2 (Q) 1.03 D
(C) CHCl3 (R) 1.60 D
(D) CCl4 (S) 0D
Correct matching is:-
(a) A P, B Q, C R, D S
(b) A R, B Q, C P,, D S
(c) A S, B R, C P,, D Q
(d) A P, B R, C Q, D S
Q.25 In which of the following molecule, the oxygen atom constitutes the positive end of electric dipole?
(a) XeO3 (b) NOCl
(c) F2O (d) XeOF2
Q.26 Which of the bond is most polar?
(a) C — O (b) O— F
(c) C — F (d) N— F
Q.27 Which is not polar molecule?
(a) C2F2 (b) CHCl3
(c) F2O (d) CH2Cl2
Q.28 AB3 has non zero dipole moment. A can exhibit ------- hybridization.
(a) sp 3 (b) sp 3 d
(c) Both (d) none
Q.29 Among the following compounds, the one that is polar and has the central atom with sp2 hybridization
is:-
(a) SiF4 (b) BF3
(c) HClO2 (d) H2CO3
Q.30 Among the following compounds the one that is polar and has the central atom with sp2 hybridization
is:-
(a) HNO3 (b) SiF4
(c) B2H6 (d) HClO4
Q.31 Which one of the following pairs of molecules will have permanent dipole moments for both members?
(a) SiF4 and NO2 (b) NO2 and CO2
(c) NO2 and O3 (d) SiF4 and CO2
 86 Chemical Bonding
Q.32 Select correct statement:-
(a) When a covalent bond is formed, transfer of electrons takes place
(b) Pure H2O does not contain any ion
(c) A bond is formed when attractive forces over-come repulsive forces
(d) HF is less polar than HBr
Q.33 Which of the following are non-polar?
(1) SiF4 (2) XeF4
(3) SF4 (4) BeCl3
(5) NCl3
Select the correct answer using the code given below:-
(a) 1, 2 and 4 (b) 3, 4 and 5
(c) 2, 3 and 4 (d) 1, 3 and 4
Q.34 Which of following has zero dipole moment?
(a) ClF (b) PCl3
(c) SiF4 (d) CFCl3
Q.35 The electronegativities of F, Cl, Br, I are 4.0, 3.0, 2.8, 2.5 respectively. The hydrogen halide with a highest
percentage of ionic character is :-
(a) HF (b) HCl
(c) HBr (d) HI
Q.36 Which of the following statements is true?
(a) HF is a good acid than HI
(b) CH4 contains polar bonds but its resultant dipole moment is zero
(c) CO2 contains polar bonds but its resultant dipole moment is zero
(d) Dipole moment of CO bond in 'CO' is greater than that of CO bond present in CH3COCH3
Q.37 Dipole moment is shown by
(a) 1, 4-dichlorobenzene (b) 1, 2-dichlorobenzene
(c) Trans -1, 2-dichloroethene (d) Trans -2, 3-dichloro-2-butene
Q.38 Which of the following represents a non-polar molecule with polar bonds?
(a) NCl3 (b) NF3
(c) N2 (d) CCl4
Q.39 Out of the four planar molecules given below which one has µ (dipole moment)= 0
(a) cis-ClCH = CHCl (b) trans-ClCH = CHCl
(c) CH2 = CDCl (d) CD2 = CBr2
Chapter 5 : Polarization, Dipole Moment & Hydration Energy 87
Q.40 Which of the following would have a permanent dipole moment?
(a) SiF4 (b) SF4
(c) PCl5 (d) BCl3
Q.41 The halide having the highest melting point is:-
(a) NaF (b) NaCl
(c) KBr (d) LiF
Q.42 The highest dipole moment is of
(a) CCl4 (b) CH3OH
(c) CS2 (d) CH3F
Q.43 The most polar bond is:-
(a) C – F (b) F–O
(c) C – Br (d) C–N
Q.44 The molecule having largest dipole moment among the following is:-
(a) CHI3 (b) CH4
(c) CHCl2 (d) CCl4
Q.45 Which of the following is least soluble in water?
(a) BaF2 (b) SiF4
(c) CaF2 (d) MgF2
Q.46 Ionic reactions take place mainly in:-
(a) Liquid state (b) Solid state
(c) aq. solution (d) Gaseous state
Q.47 Among the following iso structural compounds, identify the compound which has the highest lattice
energy:-
(a) LiF (b) LiI
(c) NaBr (d) MgO
Q.48 Which of the following ions has the highest polarizing power:-
(a) K(+) (b) Ca +2
(c) Al +3 (d) Si +4
Q.49 Low solublility of BaSO4 in water is due to:-
(a) Low dissociation energy (b) Ionic bond
(c) High value of lattice energy (d) None of the above
Q.50 The order of decreasing polarity in compounds:-
CaO, CsF, KCl, MgO is
(a) CaO, CsF, KCl, MgO (b) MgO, KCl, CaO, CsF
(c) KCl, CaO, CsF, MgO (d) CsF, KCl, CaO, MgO
 88 Chemical Bonding
Q.51 Which of the following is least ionic?
(a) KCl (b) AgCl
(c) MgCl2 (d) FeCl2
Q.52 Among LiCl, BCl3, BeCl2, CCl4, the covalent characteristics follow the decreasing order:-
(a) LiCl > BCl3 > BeCl2 > CCl4 (b) CCl4 > BCl3 > BeCl2 > LiCl
(c) LiCl > BeCl2 > CCl4 > BCl3 (d) BeCl2 > LiCl > BCl3 > CCl4
Q.53 The strongest hydrogen bonding is present:-
(a) NH3 & CH3NH2 (b) H2O + NH3
(c) CH3NH2 + C2H5OH (d) HF + H2O
Matrix Match
Q.54 Column - I Column - II
(A) AB2 (µ = 0) (p) Linear geometry
(B) AB3 (µ = 0) (q) Planar geometry
(C) AB2 (µ ¹ 0) (r) One lone pair on central atom
(D) AB3 (µ ¹ 0) (s) Two lone pair on central atom
Q.55 Column - I Column - II
(A) BrF3 (p) µ= 0
(B) PCl5 (q) µ¹ 0
(C) IF7 (r) Two axial bonds
(D) NH3 (s) One equatorial bond
Q.56 Column - I Column - II
(A) SF4 (p) Polar
(B) B3N3H6 (q) Non polar
(C) C6H6 (r) Planar
(D) XeF4 (s) Non planar
Chapter 5 : Polarization, Dipole Moment & Hydration Energy 89

SUBJECTIVE EXERCISE

7. (a) AgI > AgBr > AgCl (b) MgSO4 > CaSO4 > SrSO4 > BaSO4
(c) MgF2 < CaF2 < SrF2 < BaF2 (d) NaCl > KCl > RbCl > CsCl
(e) NaCl > KCl > RbCl > CsCl (f) CsNO3 > RbNO3 > KNO3 > NaNO3
(g) Mg3N2 > MgO > MgCl2 (h) AgCl > AgBr > AgI
8. µ = q × d, 1.2 × 10–18 = q × 10–8, q = 1.2 × 10–10
Thus, fraction of charge present on each atom = (1.2 × 10–10) × 100 / (4.8 × 10–10) = 25 %

H
0.94Å
OB = 0.94Cos 52.5 = 0.572Å
O 52.5° Dipole moment = q × d, q = 1.85 × 10–18
9. B
0.572 × 10–8
H q = 3.23 ×10–10

Fraction of charge = (3.23 × 10–10) × 100 / 4.8 × 10–10 = 67.29

OBJECTIVE EXERCISE

1. (d) 2. (b) 3. (a)

4. (d) NaCl is more ionic than AgCl & it is more soluble in water in comparison to acetone.
5. (c) 6. (d) 7. (b) 8. (a) 9. (a) 10. (d)
11. (a) 12. (d) Extent to polarization µ acidic character 13. (b) 14. (a)
15. (a) Due to polarization AgI has covalent character so it will have highest solubility in non polar medium
(diethyl ether).
16. (b) CH2Cl2 has tetrahedral shape. 17. (a) Use born Haber cycle.

m2 m1
Cl Cl
H H
C = C = C C = C= C = C
18. (c) H Cl H Cl
m1 m2

mRes ¹ 0 mRes = 0
 90 Chemical Bonding
19. (a) 20. (a) MgO has highest lattice energy 21. (c) 22. (c)
23. (c) 24. (d) 25. (c) Because fluorine is more electronegative than oxygen
26. (c) 27. (a) 28. (c) 29. (d) 30. (a) 31. (c)
32. (c) 33. (a) 34. (c) 35. (a) 36. (c) 37. (b)
38. (d) 39. (b) 40. (b) 41. (d) as it has highest lattice energy
42. (d) 43. (a) 44. (c) 45. (b)
46. (c) in ionic compound ions are bonded by strong electrostatic forces of attractions, thus, to break
these forces a polar medium is required thus ions react with one another in polar medium like water.
47. (d) 48. (d) 49. (c) 50. (d) 51. (b) 52. (b)
53. (d)
54. A - p ; B - q ; C - r, s ; D - r, s
55. A - q, r, s ; B - p, r ; C - p, r ; D - q
56. A - p, s ; B - p, r; C - r, q ; D - p, r
Chapter 6 : Molecular Orbital Theory & Metallic Bonding 91

6
Molecular Orbital Theory
& Metallic Bonding
Before we discuss molecular orbital theory it is necessary to understand the term paramagnetism and
diamagnetism.
Paramagnetic substances are those substances which attract towards magnetic field if they are placed in a
magnetic field whereas diamagnetic substances are repelled by magnetic field.

N S N S

(Paramagnetic substance) (Diamagnetic substance)

The magnetic behavior of a substance is measured by the term magnetic moment (µ)

(µ) = n(n + 2) B.M

Where n = number of unpaired electrons present in the substance

B.M. = Bohr magneton (unit of magnetic moment)
It means that if unpaired electrons are present in a substance its magnetic moment (m) will be non zero and it well
be a paramagnetic substance.
Similarly it substance does not contain unpaired electrons its magnetic moment will be zero and substance will
be diamagnetic. For e.g. Fe+2 (3d6) and Zn+2(3d10), former is paramagnetic and later is diamagnetic.

Fe+2 (3d6)

n = unpaired electrons = 4

µ = n (n + 2) = 2(2 + 4) = 2 6 B.M. (Paramagnetic)

Zn+2(3d10 )

n = 0, µ = 0 (Diamagnetic)
 92 Chemical Bonding

Ø6.1 Molecular orbital theory (M.O.T.)

This theory was proposed by Robert Mulliken and he explained the paramagnetic behavior of O2 with the help
of this theory which is diamagnetic according to valence bond theory.
Several important features of M.O.T. are given below.
(1.) Atomic orbitals (A.O.) of the individual atoms can be combined to give rise to molecular orbitals
(M.O.). The number of molecular orbitals formed is equal to the number of atomic orbitals involved
in combination. It should be noted that the energies of the atomic orbitals of the combining atoms
must be close to each other.
(2.) Two atomic orbitals produce two molecular orbitals, one of which has energy lower than the energy
of combining atomic orbital and the other has energy higher than the energy of combining atomic
orbitals. The lower energy molecular orbital is called bonding molecular orbital (B.M.O.) and the
higher energy orbital is called anti bonding molecular orbital (ABMO).

ABMO

*
E s 1s
N
E
R
G 1s 1s
Y BMO

s 1s
A.O. A.O.
M.O.
(Linear combination of atomic orbitals)

(3) B.M.O. is formed by addition of wave function whereas ABMO is formed by subtraction of wave
function.

A + B AB
Wave functions yA yB

(Atom) (Atom) (Molecule)

B.M.O. are formed by constructive interference of wave functions (in phase)

Chapter 6 : Molecular Orbital Theory & Metallic Bonding 93
y y
A + B

yA
a a+b

b
More amplitude and less
energy (BMO)

ABMO are formed by destructive interference (out of phase)

y y
A B

a a+b

b less amplitude and more

energy (BMO)

(4.) In B.M.O. electron density increases in the internuclear region whereas in ABMO electron density
decreases in inter nuclear region.

node

+ + + +
A B A B
B.M.O (A.B.M.O)

(5.) In ABMO there is one nodal plane bisecting perpendicularly the internuclear axis.
(6.) BMO stabilizes the molecule whereas ABMO destabilizes the molecule.
(7.) Head on overlap or mixing of atomic orbital generates s molecular orbital whereas side wise or
lateral overlap of atomic orbital generates p molecules orbital.
s ABMO s* s BMO s
p ABMO p* p BMO p
(8) Shapes of molecular orbitals -

In phase
Ø + + + constructive
+ +
interference
1s or 1s or s 1s or s 2s
2s 2s
94 Chemical Bonding

out of phase –
Ø + – + destructive
+
interference
or nodal plane
s 1s* or s 2s*
+ + –

In phase – + –
Ø – + + + –

2pz 2pz s 2pz

– + – + – out of phase – + – +
Ø
or
s * 2pz
– + – – +

+ +
+
+ In phase . .
Ø –
– –
2px or 2py 2px or 2py p 2px or p 2py

+ +
out of phase + –
Ø –
– +
– –
or
+ – p * 2px or p * 2py
+
– +
2px or 2py 2px or 2py
Chapter 6 : Molecular Orbital Theory & Metallic Bonding 95
(9.) Filling of molecular orbitals
Sequence (A) When total electrons are more than 14
s1s, s*1s, s2s, s*2s, s2pz, p2px = p2py, p*2px = p*2py, s*2pz
Sequence (B) When total electrons are less than equal to 14
s1s, s*1s, s2s, s*2s, p2px = p2py, s2pz, p*2px = p*2py, s*2pz
These molecular orbitals can be represented by the following molecular orbital diagram.
s* 2pz

E p* 2px p* 2py
N
E
R 2p 2p
G p2px p2py
Y

s 2pz

s*2s

2s 2s

s2s

s*1s

1s 1s

s1s

A.O. M.O A.O.

Electrons are distributed among the molecular orbitals according to Aufbau's, Hund's and Pauli's
Principle i.e.

Ø Each molecular orbital can accommodate a maximum of two electrons of opposite spins

Ø Electrons occupy lowest energy molecular orbital. Higher energy orbitals will not be filled as
long as low energy orbitals are available.
96 Chemical Bonding
(10) Bond order = 1/2 (n b – na)
Where nb = electrons in BMO and
na = electrons in ABMO
Bond order µ Bond dissociation energy
µ Stability µ 1 / Bond length
If two species have same bond order then that species will be more stable in which more number
of electrons are present in BMO
Bond order (B.O.) = 1 (single bond)
B.O. = 2 (double bond)
B.O. = 3 (Triple bond)
B.O. = 0 (Molecule does not exist)
(11) Any species is found to be coloured if it possesses unpaired electrons.
Let us take some examples to clear above points
(a) H2 Total electrons = 2
s1s2 s*1s0
Bond order = 1/2 (2 – 0) = 1
i.e. two H atoms are joined together by single bond

s*1s
E
N
E
R 1s 1s
G
Y
s1s

Since unpaired electron is absent in H2 thus it is colorless and diamagnetic

n = 0 è µ = n(n + 2) = 0 B.M.

(b) Be2 Total electrons = 8 thus, sequence B will be used

s1s , s*1s2, s2s2, s*2s2
2 or KK s2s2, s*2s2,
B.O. = 1/2 (4 – 4) = 0 It indicates that Be2 does not exist in nature
(c) O2 Total electrons = 16 thus, sequence A will be used
s1s , s*1s , s2s , s*2s , s2pz , p2px2
2 2 2 2 2 = p2py2, p*2px1 = p*2py1
or KK s2s2, s*2s2, s2pz2, p2px2 = p2py2, p*2px1, = p*2py1
B.O. = 1/2 (10 – 6) = 4 / 2 = 2, i.e. double bond
Chapter 6 : Molecular Orbital Theory & Metallic Bonding 97
Since unpaired electrons are present in p*2px and p*2py molecular orbitals thus, O2 is
paramagnetic in nature.

µ = n(n + 2) = 2(2 + 2) = 2.828 B.M

Presence of unpaired electron makes O2 coloured. In liquid state O2 has blue colour.

E p*2px p*2py
N
E
R 2p
G p2px p2py
Y

s 2pz

*
s 2s

2s

s2s

*
s 1s

1s

s1s

O O2 O

(d) CO Total electrons = 6 + 8 = 14

Thus, sequence 'B' will be used.
s 1s2, s*1s2, s2s2 s*2s2, p2px2 = p2px2, s2pz2
98 Chemical Bonding
KK s2s2 p*2s2 p2px2 = p2py2, s2pz2
B.O. = 1 / 2 (10 – 4) = 6 / 2 = 3, i.e. CºO
Since unpaired electrons are absent hence, it is diamagnetic and colourless.

E p*2px p*2py
N
E
R 2p
G s2pz
Y

p 2px p 2py

*
s 2s

2s

s2s

*
s 1s

1s

s1s

C CO O
(e) O2, O2+, O2(–)
O2 (16e(–)) s1s2 s*1s2 s2s2 s*2s2 s2pz2 , p2px2 = p 2py2 ,p*2px1 = p*2py1
B.O. = 1 / 2 (10 – 6) = 2
O2+ (15e(–)) s1s2 s*1s2 s2s2 s*2s2 s2pz2 p2px2 = p2py2, p*2px1 = p*2py 0
B.O. = 1 / 2 (10 – 5) = 2.5
O2(–) (17e(–)) s1s2 s*1s2 s2s2 s*2s2 s2pz2 p2px2 = p2py2 , p*2px2 = p*2py1
Chapter 6 : Molecular Orbital Theory & Metallic Bonding 99
B.O. = 1 / 2 (10 – 7) = 1.5
B.O. O2+ > O2 > O2(–)
Sequence for stability & bond dissociation energy is O2+ > O2 > O2(–)
Sequence for bond length is O2 < O2 < O2(–)
(f) N2, N2+, N2(–)
N2(14e–) s1s2 s*1s2 s2s2 s*2s2 p2px2 = p2py2 ,p2pz2
B.O. = 1 / 2 (10 – 4) = 3
N2+(13e(–)) s1s2 s*1s2 s2s2 s*2s2 p2px2 = p2py2 , p2pz1
B.O. = 1 / 2 (9 – 4) = 2.5
N2(–) has 15 electrons but we do not use sequence A because the selection of sequence (A or B) is
based on the number of electrons which are present in the molecular state of species. Since N2
contains 14e– thus sequence B will be used for N2+ and N2(–)
N2(–) (15e–) s1s2 s*1s2 s2s2 s*2s2 p2px2 = p2py2 p2pz2 p*2px1 = p*2py
B.O. = 1 / 2 (10 – 5) = 2.5
B.O. = N2 > N2(+) = N2(–)
Since N2(–) has more electrons in its BMO in comparison to that of N2+ thus, N2(–)will be more
stable than N2+
Stability N2 > N2(–) > N2(+)
Bond length N2(+) > N2(–) > N2
Similarly we can arrange C2, C2+ and C2(–), H2, H2+ and H2(–) in order of their increasing stabilities.

Ø6.2 Application of M.O.T. for hetero nuclear diatomic systems

In section 6.1 we have applied M.O.T on CO molecule but M.O.T does not seems to be as exact on hetero
nuclear system (like NO, CO…… etc) as it is on homo nuclear system (like H2, O2, N2…..) After applying
M.O.T. on hetero nuclear molecule, the bond order, bond length and magnetic behavior which we get,
shows different values other than experimental values. For e.g. on applying M.O.T on CO and CO+, their
bond orders come out to be 3 & 2.5 respectively.
CO (14e–) s1s2 s*1s2, s2s2 s*2s2, p2px2 = p2py2, s2pz2
B.O. = 1 / 2 (10 – 4) = 6 / 2 = 3
If one electron is removed from BMO CO+ is formed.
CO+ (13e–) s1s2 s*1s2 s2s2 s*2s2 p2px2 = p2py2, s2pz1
B.O. = 1 / 2 (9 – 4) = 5 / 2 = 2.5
Because bond order of CO is more than CO+ therefore in CO+ the C– O bond length must be more than
that of CO but we do not find it
Theoretically - Bond length of C – O bond in CO < CO+
Experimentally - Bond length of C – O bond in CO > CO+
 100 Chemical Bonding
Thus, Mulliken thought that when CO+ formed out from CO then electron would emit out from ABMO
rather than BMO. Then only the bond order of CO+ must be more than CO and the experimental value of
CO bond length would match with theoretical value.
He also proposed new M.O. diagram
CO CO+

s*2pz s *2pz

p *2px p *2py p *2px p *2py

E E
s*2s N s*2s
N
E E
R p 2px p 2py R p 2px p 2py
G G
Y s2pz Y s2pz

s2s s2s

s*1s s*1s

s1s s1s
B.O. in CO = 1 / 2 (10 – 4) = 3
B.O. in CO+ = 1 / 2 (10 – 3) = 3.5
But this M.O. diagram failed to describe the crystal field, ligand and coordination properties like synergic
bond of CO.
Ø6.3 M.O. diagram by Coulson
The proposed M.O. diagram by Mulliken was failed to explain ligand properties of CO hence, Coulson
had presented a new M.O. diagram which was based on the principle that s molecular orbital is formed
by the mixing of hybrid orbitals rather than the mixing of pure atomic orbitals
s*sp
sp sp
E
N sp sp
E
C O
R
G (V.B.T. Picture)
Y
ssp
(–) (+)
He assumed CO as: -
C O or C O

6 + 1 = 7e – 8 –1 = 7e–
Chapter 6 : Molecular Orbital Theory & Metallic Bonding 101
We can write electronic configuration of C(–) and O(+) as
(–)
C
1s2 2s2 2p3

sp hybridisation
( More stable p p
x y
than p & p )
x y

(+)
O
1s2 2s2 2p3

sp hybridisation
p p
x y
sp hybridised orbitals

s*sp

p 2px p 2py

p p
x y

sp (C) lone pair p p

x y

sp sp p 2px p 2py

sp (O) lone pair

sp sp

(NBO) ssp (NBO)

2 2
1s 1s
(–) (–)
O O
 102 Chemical Bonding
Ø 6.4 Metallic bonding
There are more than 80 metal elements in the periodic table except mercury
(m.p =–35°C) and gallium (mp = 29.8° C), rest of the metals are solid while these two are liquid.
Metals have some characteristic properties which are shown below.
Ø They are good conductor of heat and electricity.
Ø On heating metal releases e(–) (thermo ionic emission) or when light of proper wavelength is
allowed to fall on it's surface, it releases electron from its surface (Photo electric effect)
Ø They possess a unique lusture as their surface is good reflector of light and appears shining.
Ø They can be beaten in to sheets (malleable) and can be drawn in to wires (ductile)
Ø When reacting with non metals, they form cation.
+2 –2
Mg + 1 / 2 O2 MgO
(Metal) (non metal)

An element is said to be metal if it looses its outer most electrons easily to form cation
These specific properties of metals can not be explained by covalent and ionic mode of linkage as, ionic
bond does not form between similar elements and for the formation of covalent bond, it is necessary to
have more electrons in valence shell of element so that it completes its octet. The possible of the
formation of ionic and covalent bond is again ruled out in a metal because metals are good conductors
of electricity where as ionic and covalent compounds are bad conductor of electricity in their solid state.
Several theories are put forward to explain metallic bonding and unique properties of metals. Amongst
several theories, two theories are commonly discussed.
(1) Electron sea model
(2) Band theory
1- FREE ELECTRON THEORY OR ELECTRON SEA MODEL:-
Classical electron sea theory was proposed by Drude and late it was developed by Lorentz. Some
important features of this theory are as follows.
Ø Atoms present in metal hold many vacant orbital in their valence shell for e.g. Li (1s2, 2s1 2p°) has
vacant 2p sub shell and Mg(1s2 2s2 2p6 3p° 3d°) has vacant 3p & 3d sub shells.
The ionization energy of these atoms is low so that some of these atoms easily drop electrons from
their outermost shell and form cation. These cations are called kernels. For e.g. Li forms Li+ (Kernel)
and Mg forms Mg+2 (Kernel)
Ø Because nucleus is present in these Kernels, therefore they are heavy and hence, occupy fixed
position in metal. The electrons which are lost by atoms do not attach with kernel but they are free
to move in the space present between Kernels just like the molecules of gas. Presence of large
number of vacant orbital helps these electrons to move freely. Thus, this model is called electron
sea model or electron gas model.
Chapter 6 : Molecular Orbital Theory & Metallic Bonding 103
"The simultaneous force of attraction between kernels and mobile electrons is known as metallic
bond".
Ø Metallic bond is non-directional and weaker than covalent bond.

. . .. . . . . .. . .
+ + + +
. . . . . . . .. .
. + .+
. + +
. . .. . . . . . . . . .
. . .
.. + . +. . + +
. . . . . .
By the help of this model we can explain some physical properties of metals.

Ø If the number of mobile electron increases the strength of metallic bond also increases. This is why
alkali metals are softer than alkaline earth metals because in alkali metals atom can loose only one
electron form their outer most shell whereas alkaline earth metals can loose two electrons from their
outermost shell. Therefore, in alkaline earth metal mobile electrons are more as comparative to alkali
metals and the result is that, in alkaline earth metals the strength of metallic bond is more than alkali
metals.
Ø Because of the presence of mobile electrons these electrons carry electric current from one place to
another in a metal. Thus, metal is a good conductor of electricity.

Ø When a part of metal is subjected to heat, the kinetic energy of mobile electrons in that part
increases. These electrons transfer their kinetic energy to the electrons of cooler part of metal by
means of collision which in turn get energetic and move farther. Thus heat gets conducted from one
part of metal to the other.

Ø Since mobile electrons are not bound by the help of particular bond so they can absorb and reemit
light of all wavelengths a metal thus becomes a good reflector (Metallic luster).

Ø Metals exhibit properties like malleability and ductility due to non directional nature of metallic
bond. The position of kerenels altered when stress is applied on metal but there is no distortion of
crystals. The adjacent layers of kerenels slip one over another but the electronic environment
remains the same. Thus, crystal lattice gets deformed because kerenels move from one site to other.
This is the way a metal can be beaten in to thin sheets and can be drawn in to thin wires.
Limitations of free electron theory:-
(a) It can not explain that why the molar heat capacity of metals is not considerably higher than that of
non metals. The mobile electrons are expected to make a significant contribution to the heat capacity.
(b) This theory can not explain why certain metals behave as semi conductor in solid state.
104 Chemical Bonding
2- BAND THEORY: - This theory is an extension of the molecular orbital theory to metallic structure.
We know from M.O.T that when two atomic orbitals (A.O) combine, we get two molecular orbitals
(M.O), out of it one is B.M.O and other is A.B.M.O. Similarly if 'n' atomic orbitals combine with each
other, they produce 'n' M.O's, out of it half are bonding type and the remaining anti bonding type.
In metallic crystals 'n' may be equal to 6 × 1023 (Avogadro number). Therefore, 3 × 1023 bonding and
3 × 1023 anti bonding molecular orbitals come out of it. These molecular orbitals are closely spaced
and involves in the formation of bond.

2s1 ABMO
2s1
Li2
BMO

ABMO
2s1 2s1 2s1
Li3 non bonding M.O

BMO

ABMO
2s1 2s1 2s1 2s1
Li4

BMO

2s1 2s1 2s1 empty

Lin

filled with electrons

We remember that each M.O can accommodate only two electrons. The lower half of the levels that is
B.M.O. is occupied by electrons, whereas the upper half i.e. A.B.M.O remain unfilled. For example when
lithium crystal is placed in an electric field, a few electrons acquire enough energy to move in to higher
unoccupied anti bonding orbitals. These high energy electrons carry the current.
In alkaline earth metal like Mg ‘s’ sub shell is fulfilled, therefore, the band form with the 3s orbitals of Mg
atoms are fulfilled & Mg does not conduct electricity at room temperature. But in Mg, 3s band overlaps
with 3p band as shown is figure.
Chapter 6 : Molecular Orbital Theory & Metallic Bonding 105

3p (3p band)
E
N
E
R over lapping of bands
G
Y
3s1
(3s band)

Therefore, it is easy for highest energy electron to jump in empty band and thus, Mg conducts electricity.
The lower energy bands where electrons are present are called valence band (V.B) & the bands in which
electrons jump are called conduction band. (C.B). It is seen that, lower is energy difference between V.B
and C.B more is the electrical conductance. On the basis of energy difference between V.B and C.B
substance can be classified as:-

Conductor Semiconductor Insulator

C.B
E
N
E
R C.B
Very large
G energy gap
Y C.B Small energy gap or forbidden
Fine line gap or or narrow gap gap.
V.B overlapping V.B V.B
 106 Chemical Bonding

Q.1 Suggest the type of molecular orbital formed in the following combinations assuming 'y' is bonding axis

(a) 2p x + 2p x (b) 2p y – 2p y

(c) 2pz – 2p z (d) 2p y + 2p y

Q.2 Explain why Be2 does not exist.
Q.3 Explain why O2 in found in the lower layer of atmosphere & O3 is found in the upper layer of atmosphere
however O3 is heavier than O2.
Q.4 O2 appears coloured in liquid state explain.
Q.5 What happens with respect to N – O bond length when NO is ionized to NO +.
Q.6 Out of N2+ & N2– which will require more bond dissociation energy & why?

Q.1 Which among the following has node?

(a) s2s (b) 2s
(c) s*2s (d) both (b) & (c)
Q.2 Which of the following has fractional bond order?
(a) O2 2– (b) O22+
(c) H2 – (d) CO
Q.3 Which is not true about the following four species?
CN–, CO, NO+, N2
(a) all are linear (b) all are iso electronic
(c) all are paramagnetic (d) Except N2 rest all have non zero m
Q.4 Correct order of energy is:-
(a) BMO > non bonding orbital > ABMO
(b) non bonding orbital > BMO > ABMO
(c) BMO > ABMO > non bonding orbital
(d) BMO = non bonding orbital > ABMO
Q.5 Which of the following pairs have identical values of bond order?
(a) H2 & He2 (b) H2(+) & H2(–)
(c) CN(–) & O2 (d) O22(+) & H2(+)
Chapter 6 : Molecular Orbital Theory & Metallic Bonding 107
Q.6 Which of the following is correct about CO?
(a) Energy of BMO is close to the atomic orbital of oxygen.
(b) Energy of ABMO is close to the A.O of oxygen
(c) Energy of BMO is close to the A.O of carbon
(d) During CO+ formation, one electron is removed from p2px
Q.7 Fe is harder than Na because
(a) Size of Na atoms is smaller than Fe atoms
(b) Na can loose only one e– & hence in Na metallic bonds are weaker than Fe.
(c) Size of Fe atoms is smaller than Na & hence atoms of Fe are more closely packed
(d) E.A. of Na is smaller than Fe
Q.8 Which is an example of p - type semi conductor?
(a) Silicon is doped with P (b) Al is doped with silicon
(c) Ge is doped with Ga (d) Tl is doped with Pb
Q.9 Diamagnetic species is:-
(a) O2 2– (b) C2
(c) F2 (d) all of these
Q.10 Increasing order of 'C– O' bond length in CO, CO2 and CO32– is
(a) CO > CO2 > CO32– (b) CO2 > CO > CO32–
(c) CO32– > CO2 > CO (d) CO32– = CO2 > CO
Q.11 Which among the following can not be treated by MOT for bond order determination?
(a) HF (b) NO
(c) LiF (d) both (a) & (c)
Q.12 Among the oxides of nitrogen N2O, NO and NO2, the molecules having unpaired electrons are
(a) N2O, NO (b) NO, NO2
(c) N2O, NO2 (d) N2O, NO, NO2
Q.13 – + + (–)
Out of CN , NO , CN & O2 the species having same bond orders are
(a) CN(–) & O2(–) (b) CN(+) & O2(–)
(c) NO(+) & CN(–) (d) NO(+) & O2(–)
Q.14 If 'y' is bonding axis then shape of the orbital formed by 2p x + 2px will be?

+ – +
(a) + (b)
– –

(c) + + (d) – + –
 108 Chemical Bonding
Q.15 If 'x' in bonding axis then the shape of the orbital formed by 2p x + 2px will be?

+ – +
(a) + (b)
– –

(c) + + (d) – + –

Q.16 If 'z 'is bonding axis then the shape of the orbital formed by 2p x + 2py will be?

+ – +
(a) + (b)
– –

(c) + + (d) no bond formation takes place.

Q.17 Correct order of bond dissociation energy is:-

(a) N2 > N2+ = N2– (b) N2+ = N2– > N2
(c) N2 > N2+ > N2– (d) N2 > N2– > N2+
Q.18 Correct order of bond dissociation energy is:-
(a) O2 > N2 > CO (b) O2 > CO > N2
(c) CO > N2 > O2 (d) N2 > CO > O2
Q.19 The molecular orbital shown in the diagram is

– + – +
.

(a) p2py (b) p*2px

(c) p2pz (d) p*2pz
Q.20 In a homonuclear diatomic molecule, higher the bond order, larger will be
(a) Bond length (b) Bond strength
(c) Paramagnetic nature (d) Ionic character
Chapter 6 : Molecular Orbital Theory & Metallic Bonding 109
Q.21 In which set of molecules all the species are paramagnetic?
(a) C22+, O2, N2 (b) C22+, O2, NO
(c) C22+, F2, O2 (d) C22+, O2, Li2
Q.22 In the formation of NO(+) from NO, the electron is removed from
(a) a s orbital (b) a p orbital
(c) a s* orbital (d) a p* orbital
Q.23 Which one of the following does not exhibit paramagnetism?
(a) NO (b) NO2
(c) ClO2 (d) ClO2(–)
Q.24 Which of the following is non-existent according to molecular orbital theory?
(a) H2 (–) (b) O2 (–)
(c) He2 (d) O2 (+)
Q.25 The species having highest bond order is
(a) O2 (b) O2 (–)
(c) O2 (+) (d) O2 2(–)
Q.26 Which of the following theory provides explanation about paramagnetic nature of oxygen?
(a) Electronic theory of valency (b) Valency bond theory
(c) Molecular orbital theory (d) All of the above
Q.27 Which of the following species is paramagnetic?
(a) CO2 (b) NO
(c) O22(–) (d) CN(–)
Q.28 Paramagnetism is exhibited by molecules which
(a) are not attracted by magnetic field (b) contain only paired electrons
(c) contain unpaired electrons (d) carry positive charge
Q.29 Which of the following M.O. has two nodal planes per-pendicular to each other?
(a) s2s (b) p2px
(c) p*2py (d) s*2pz
Q.30 Which of the following is not paramagnetic ?
(a) NO (b) S2(–)
(c) O2 (–) (d) N2
Q.31 The number of electrons that are paired in oxygen molecule is:
(a) 16 (b) 12
(c) 7 (d) 14
 110 Chemical Bonding

Q.32 Which of the following species should be most stable?

(a) H2 (+) (b) H(+)
(c) H (d) H(–)
Q.33 The bond order in NO is 2.5 while that in NO(+) is 3. Which statement is true for these two species
(a) Bond length is unpredictable
(b) Bond length in NO is greater than that in NO(+)
(c) Bon length is NO(+) is equal to that in NO
(d) Bond length in NO(+) is greater than that in NO.
Q.34 The bond order in O2(+) is the same as in:-
(a) N2 (+) (b) CN(–)
(c) CO (d) NO(+)
Q.35 The bond strength increases:-
(a) With increasing bond order
(b) With increasing extent of overlapping of orbitals
(c) With decreasing difference between energies of overlapping orbitals
(d) All of the above
Q.36 Among KO2, AlO2(–), BaO2 and NO2(+), unpaired electron is present in:-
(a) NO2(+) and BaO2 (b) KO2 and AlO2(–)
(c) KO2 only (d) BaO2 only
Q.37 Among the following, the paramagnetic compounds is:-
(a) Na2O2 (b) O3
(c) N2O (d) RbO2
Q.38 The species having bond order different from that in CO is:-
(a) NO(–) (b) NO(+)
(c) CN(–) (d) N2
Q.39 The theory related to metallic bond is
(a) Band theory (b) Lorentz's electron gas model
(c) Ruchell model (d) Both (a) and (b)
Q.40 Which one of the following is paramagnetic?
(a) O2 (–) (b) CN(–)
(c) C O (d) NO(+)
Chapter 6 : Molecular Orbital Theory & Metallic Bonding 111
Q.41 The correct order in which the O – O bond length increases in the following is:-
(a) H2O2 < O2 < O3 (b) O3 < H2O2 < O2
(c) O2 < H2O2 < O3 (d) O2 < O3 < H2O2
Q.42 Matrix Match
Column - I Column - II
(A) O2+ (p) Colourless
(B) NO+ (q) Coloured
(C) NO– (r) Diamagnetic
(D) F2 (s) Paramagnetic
Q.43 Column - I Column - II
(A) B2 (p) Paramagnetic
(B) N2 (q) Undergoes oxidation
(C) O2 – (r) Undergoes reduction
(D) O2 (s) Bond order > 2
Q.44 Molecule / Species Bond order
(A) H2 2– (p) 0
(B) Ne2 (q) 1
(C) N2 (r) 2
(D) O2 – (s) 3
(t) 1.5
Q.45 Column - I Column - II
(A) H2 + (p) Diamagnetic
(B) CO (q) Paramagnetic
(C) N2 (r) B.O. = 2
(D) O2 2– (s) B.O. = 3
 112 Chemical Bonding

SUBJECTIVE EXERCISE

1. (a) p2p x (b) s*2py (c) p*2pz (d) s2py

3. O2 is paramagnetic & thus, attracted by earth's magnetic field
5. Decreases

OBJECTIVE EXERCISE

1. (d) 2. (c) 3. (c) 4. (a) 5. (b)

6. (a) 7. (b)
8. (c) When Ge is doped with Ga then Ga forms 3 covalent bonds with three Ge but it is unable to form 4th
covalent bond & a hole is generated which makes the solid p- type semiconductor (See figure
given below)

Ge Ge Ge
.. . ..
.. ..
.. ..
.. ..

.. ..

Ge Ga Ge

Ge Ge Ge Hole

9. (d)
10. (c) carbonate ion, carbon dioxide & CO have bond orders 1.33, 2 and 3 respectively.
11. (c) 12. (b) 13. (c) 14. (b) 15. (d)
16. (d) 17. (d) 18. (d) 19. (d) 20. (b)
21. (b) 22. (d) 23.(d) 24. (c) 25. (c)
26. (c) 27. (b) 28. (c) 29. (c) 30. (b)
31. (d) 32. (d) 33. (b) 34. (a) 35. (d)
36. (c) RbO2 , KO2 & CsO2 are superoxides & contains unpaired electrons & thus, these are paramagnetic
37. (d) 38. (a) 39. (d) 40. (a)
41. (d) due to resonance in O3 bond order is 1.5 while in dioxygen & hydrogen peroxide bond orders are 2
& 1 respectively
42. A — q,s B — p,r C — q,s D — p,r
43. A—p,r B—s C— p,q D—p,q
44. A— p B— p C—s D—t
45. A— q B — p,s C — p,s D — p
Chapter 7 : Hydrogen Bond & Inter Molecular Forces of Attractions 113

7
Hydrogen Bond & Inter
Molecular Forces of Attractions
Ø7.1 Hydrogen bond
1. When two dipoles come towards each other then the negative end of one dipole is attracted by the
positive end of the other dipole. This is known as dipole - dipole attraction.
s–
O
s+ s– s+ CH3
C O C
CH3
CH3 CH3
However, hydrogen contains one electron in its 1s orbital but it forms covalent bond with other
elements. If hydrogen forms covalent bonds with any strong electronegative element, such bonds
are strongly dipolar and the dipole - dipole attraction between this dipole is known as hydrogen
bond s+ s– s+ s–
H F H F
2. Hydrogen bonding is mainly shown by N, O and F. Except in some organic compounds Cl does not
show hydrogen bonding because of its large size.
3. The strength of hydrogen bond lies between 8 KJ/mol to 42 KJ/mol.
4. Hydrogen bond can be classified as -
(a) Intermolecular - H - bond
(b) Intramolecular - H - bond
(a) Intermolecular hydrogen bond: - It is formed between two different molecules of the same or
different substances. For e.g.
HF F F F F

H H H H
H 2O H H H
H O H O H O

Alcohol in water H C 2H5 H C 2H5

H O H O H O H O
114 Chemical Bonding
(b) Intramolecular hydrogen bond: - It is formed between the hydrogen atom and F,N. or 'O' atoms
present in the same molecule
H O
C N
O O
O H O H
(Ortho hydroxy benzaldehyde) (Ortho nitro phenol)
or
Salicyldehyde
Intermolecular hydrogen bond results in to association of molecules. Thus molecules come close
to one another & consequently melting point, boiling point, viscosity and surface tension increase.
In intramolecular hydrogen bond in place of association, cyclisation of the molecule takes place,
consequently, the effect of intramolecular hydrogen bond on the physical properties is negligible.
Due to the presence of hydrogen boding in the molecules, they come close to each other and thus
viscosity increase. Presence of hydrogen bonding restricts the conversion of liquid molecules in
vapour state and the vapour pressure decreases and more temperature is required to boil such
liquids, therefore, the boiling point increases. If any compound forms hydrogen bond with the
molecules of H2O then it dissolves in water.
To understand above facts some examples are given below.
1. Glucose, sucrose fructose and ethyl alcohol are soluble in water due to the formation of hydrogen
bond because in these compounds O - H bond is present which forms hydrogen bond with O - H
bond of water.
H C2H5 H C2H5
H O H O H O H O
2. Due to the presence of hydrogen bond in water its molecules are found close to each other. Thus,
it exists in liquid state whereas the big size of sulphur and low electro negativity restricts hydrogen
bonding in H2S. This inability of forming hydrogen bond keeps away all the molecules of H2S
resulting in the gaseous state of H2S. Hence H2O is liquid whereas H2S is gas.
3. Conditions for the formation of hydrogen bond
Ø Hydrogen should be bonded with highly electronegative element such as N.F. and O
Ø The size of electronegative element must be small and it must have lone pair of electrons.

H H
(+) (+) (no. H - bonding as 'N' does not
N N
has lone pair of electrons)
H H H H
H H

H –C = C –H H –C = C –H (no - H - bonding as size of 'C' is large

and it does not contain lone pair of
(50% 's' character highly electrons)
electronegative)

Ø The strength of H - bond lies between 8 kJ/mol to 42 kJ/mol, so these bonds easily break at
high temperature, therefore, temperature should be less
Chapter 7 : Hydrogen Bond & Inter Molecular Forces of Attractions 115

Ø7.2 Influence of hydrogen bonding on physical properties

Hydrogen bonding µ 1 / vapour pressure
µ Boiling point
µ Melting point
µ Solubility µ viscosity
1. One carbon atom does not bear two OH groups and readily looses water

OH
CH3 — CH H2O + CH3CHO
OH
(unstable) (stable)

When two OH groups are present on single carbon then intra molecular hydrogen bonding takes
place as follows

O —H
CH3 — CH q q < 109° 28'
O—H
sp3

Thus, the OH groups come close to each other, this reduces bond angle (q < 109° 28') and develops
strain on sp3 hybridized carbon atom. In order to reduce the strain compound release H2O molecule
and comes in to stable state.
If there is a possibility to form hydrogen bond on the adjacent carbon atom then in those conditions
compound does not release H2O. For e.g. Chloral hydrate CCl3CH(OH)2 is a stable compound and
does not loose water at room temperature.

Cl HO

Cl C C H

Cl HO
2. Solubility of bicarbonates of alkali and alkaline earth metals increase on moving down in a group in
periodic table. To clear this concept one should know about the structure of bicarbonate.
In bicarbonate ion, intramolecular H - bond is present which is shown below.

O
O = C H Intra molecular - H - bond

O(–)
Void

Due to this H – bond, a void develops in bicarbonate ion which is occupied by metal cation. Now
as the size of metal cation increase, the H – bond begins to weaken and hydration of bicarbonate,
becomes easy resulting in increasing solubility
116 Chemical Bonding
O O O
O = C H O = C H O = C H
Li+ Na+ K+

O(–) O(–) O(–)

Strength of hydrogen bond decrease

Chances of hydration increases

Solubility increases.
3. Density of ice is lesser than water
The H2O molecules of water are attached with hydrogen bonding and forms structures like honey
comb. All oxygen forms four bonds, two covalent bonds with hydrogen and two hydrogen bonds
with two H2O molecules. Due to the cage like structure of ice, its volume increases and density
decreases. (d = m/v)

H H

O ICE
H H
H H
O
O
H H

O
O

H
H
O
H
H
On heating ice, some hydrogen bonds break up and H2O molecules go in to cage which decrease
volume and density increases
H H

H H
H H
H2O O WATER
O
H2O

H
Chapter 7 : Hydrogen Bond & Inter Molecular Forces of Attractions 117
The density of water is maximum at 4°C because beyond 4°C more thermal expansion occurs which
increases volume of water and decrease density (d = m/v)
Ice 4 hydrogen bonds (as shown above)
Water 2 hydrogen bonds
H H H
H O H O H O
Water vapours no hydrogen bond
4. Hydrogen bond two also influences the acidic strength. In ortho nitro phenol intra molecular
hydrogen bond is present in between OH and NO2 groups

O
N O NO2
H HO
O
(ortho nitrophenol) (para nitrophenol)

Thus, presence of hydrogen bonding reduces the ability of OH group to release H+ ion and
consequently ortho nitro phenol becomes less acidic than para nitro phenol.
5. Viscosity of ethyl alcohol is less than glycerine because there is only one hydrogen bond between
the two molecules of ethyl alcohol whereas there are three hydrogen bonds between the two
molecules of glycerine, Therefore, the molecules of glycerine are much closer to each other than the
molecules of alcohol. Thus, glycerine is more viscous than ethyl alcohol.
C2H5 C2H5 C2H5
H O H O H O Ethyl alcohol

H
CH2 O HO CH2
H
CH2 O HO CH Glycerine

CH2 O HO CH2
H

(Ethyl alcohol) (Ethylene glycol) (Glycerine)

C2H5OH CH2OH CH2OH
CH2OH CHOH
CH2OH
 118 Chemical Bonding

Number of hydrogen bonds increases

Viscosity increases

Boiling point increases

6. Acid strength of hydrogen halides
HF < HCl < HBr < HI
On moving from HF to HI, the size of halogen increase and bond length of H — X bond increase
Thus, when we move from HF to HI covalent bond becomes longer and weaker and breakes easily,
consequently HI is better acid than HBr which is further more acidic than HCl and HF. Along with
this acid strength is also influenced by hydrogen bonding because the molecules of HF attach with
one another by the help of hydrogen bonding therefore, HF does not release H+ easily even on
breaking of H —F bond. Thus HF is least acidic among all hydrogen halides because in successive
halides hydrogen bonding is absent.
7. Hydrogen bonding also influences dipole moment.
m 1 OH m 1 OH

H F m H SH
2
m2

H H H H
H H
(i) (ii)
In (i) case, OH and F come closer to each other due to intra molecular hydrogen bond which reduces
the angle between µ1 & µ2 (less than 60°) and because
µ Res µ cos q µ 1 / q
Therefore, the dipole moment of (i) is greater than (ii)
8. On adding KF in HF, KHF2 forms but HBr and HI do not form KHBr 2 and KHI2
KF + HF KHF2
KBr + HBr KHBr 2 (not possible)
KI + HI KHI2 (not possible)
Hydrogen boding is responsible for the formation of KHF2
(+) (–)
K [ F–H………
F]
Ø7.3 Intermolecular forces of attractions
Besides the primary forces responsible for the formation of covalent, ionic and coordinate bonds there
are secondary forces that operates between molecules. These forces are present in all states of matter
and are responsible for structural features as well as physical properties of matter. These forces are
called intermolecular forces. These are discovered by the Dutch scientist Van - der - waal therefore, these
intermolecular forces are also called Van - der - waal forces of attractions. These forces of attractions are
very weak. Their strength is less than 8 kJ/mol. These are mainly of three types.
Chapter 7 : Hydrogen Bond & Inter Molecular Forces of Attractions 119
(a) Dipole - dipole attraction (Keesom forces)
(b) Dipole - induce dipole attractions (Debye forces)
(c) Dispersion forces or London forces or instantaneous dipole attraction.
(a) Dipole - dipole attraction - When two dipoles come close to each other then the negative end of one
dipole is attracted by the positive end of the other dipole. This attraction is known as dipole - dipole
attraction.

s–
O
s+ s– s+
CH3
C --------------------- O = C (dipole-dipole attraction in acetone)
CH3 CH3
CH3

Hydrogen bonding is also a type of this class.

Strength of H – bond > Strength of other dipole – dipole attraction.

Due to more electropositive nature and small size of hydrogen the strength of hydrogen bond is
more than other dipole - dipole attraction. Thus, the boiling point of acetone is 56°C where as the
boiling point of CH3OH is 65°C because in acetone CH3OH dipole – dipole attraction and H –
bonding are present respectively.

CH3 CH3 CH3

H O H O H O
(b) Dipole - induce dipole attraction - This type of forces exist when one molecule has permanent
dipole and other molecule or atom has no dipole. Polar molecule distorts the electron density of
non-polar species towards its +ve or –ve end, due to which a dipole is induced on non-polar
molecule.

s+ s–

+ –

(dipole) (induced - dipole)

s+ s– s+ s–
H F H H

(dipole) (induced-dipole)

These forces are responsible for the formation of noble gas hydrates.
(c) Dispersion forces or London forces or instantaneous dipole or induced dipole interactions - Since
permanent dipoles do not exist in homonuclear diatomic molecules H2, N2, O2, Cl2 etc a different
type of attractive force must be postulated to explain the liquid and solid state of such substances.
120 Chemical Bonding
Over a period of time the two bonding electrons in H2 molecules are as close to one nucleus as to
the other. The molecule therefore does not possess any permanent dipole. But any given moment
the electron density may be concentrated at one end of the molecule and fraction of a second later
this may be concentrated at the other end of the molecule. Thus instantaneous dipoles are generated.
These instantaneous dipole induce similar dipoles in neighboring molecules. These instantaneous
dipoles lead to an attractive force between the molecules.

s+ s– s+ s–

H H H H

The strength of such induced dipoles interaction depends on the polarizability of the molecule. The
ease of polarization again depends on the size of the molecule.
Polarizing tendency µ size of molecule
µ number of electrons
µ molecular weight
This in why F2 and Cl2 are gases (less polarization & less magnitude of London forces) and I2 is
solid (more polarization and more magnitude of London forces)

F2 Cl2 Br2 I2

gases liquid solid

Mol. Wt. increases

London force increases

These forces of attractions are responsible for the liquefaction of gases.
Consider some more examples of this class
CH3F < CH3Cl < CH3Br < CH3I
(less b.p) (More b.p)
CH3Cl < CH3Cl2 < CHCl2 < CCl4
(less b.p) (More b.p)
CH3F > CH2F2 > CHF3 > CF4 (Exceptional case)
(less b.p) (More b.p)
In addition to these inter molecular forces, ion dipole and ion - induce dipole attractions are also
observed. But these forces of attractions are not Van - der - waal forces of attractions. Here we are
doing a small discussion on these forces of attractions.
Chapter 7 : Hydrogen Bond & Inter Molecular Forces of Attractions 121
(1) Ion - dipole attraction:-These forces of attractions exist between ion (Cation or anion) and
polar molecule. The cation is attracted by the -ve end of dipole while the anion is attracted by
the positive end of dipole.

+ –
+ – d+ d–
– +
+ – H OH
+ – Na+Cl– + –
+ –
+ – – +

+ –

These forces are responsible for the solvation of ionic compound in polar medium like water.
(2) Ion - induced dipole: - These forces of attractions exist between ion and non polar molecule.
When non polar molecules come closer to the ion, ion distorts the electron density of non
polar molecule and induces dipole moment in it. These forces are responsible for the solubility
of ionic compound in non polar.
Solvents: - For example F(–) and CCl4, NO3(–) and CS2
Descending order of forces of attractions is given below.
ion - ion > ion - dipole > dipole - dipole > ion - induced dipole > dipole - induced dipole
> London forces
 122 Chemical Bonding

Q.1 Which will have highest critical temperature?

(a) HF (b) HCl
(c) H2O (d) NH3
Q.2 Basicity of HF is
(a) 1 (b) 2
(c) 3 (d) Zero
Q.3 Which of the following compounds would have significant intermolecular H - bonding?
H2S, CH3COOH, HCl, CH3CH2F
1 2 3 4
(a) 1, 2, 3, 4 (b) 2, 3, 4
(c) 2, 4 (d) 2
Q.4 Compound with highest dipole moment is:-

F
F

(a) (b)
OH
OH

F Cl
OH OH
(c) (d)

Q.5 The order of strength of H – bond is

(a) NH ….. N > ClH..…Cl > OH…....O > FH ……F
(b) ClH ……Cl > NH .….N > OH.….O > FH ……F
(c) ClH ……Cl < NH ..…N < OH.….O > FH…….F
(d) FH …..…F > OH ……O > NH…..N > ClH ……Cl
Q.6 Which of the following reaction is possible?
(a) KCl + HCl KHCl2
(b) KBr + HBr KHBr2
(c) KF + HF KHF2
(d) KI + HI KHI2
Q.7 Which of the following intermolecular forces of attractions are responsible for the liquefaction of N2?
(a) Dipole - dipole attraction (b) London forces
(c) H - Bonding (d) Dipole - induce dipole attraction
Chapter 7 : Hydrogen Bond & Inter Molecular Forces of Attractions 123
Q.8 Which is not correctly matched?
(a) NO3– & CHCl3 ion - dipole attraction
(b) HF & NH3 dipole - dipole attraction
(c) CF4 & HF dipole - dipole attraction
(d) H2 & HF dipole - induce dipole attraction
Q.9 In which case intra molecular H – Bonding is present
(a) H3BO3 (b) CH3CHOHCHCOCH3
(c) CH3OH (d) CH3COOH
Q.10 Which is unstable at room temperature?

OH OH
(a) CH3CH (b) CH3 – CH – OCH3
CH3

(c) NaHCO3 (d) KHF2

Q.11 Correct order of boiling point is:-
(a) HF > HCl > HBr > HI (b) HI > HBr > HCl > HF
(c) HF > HI > HBr > HCl (d) HI > BHr > HF > HCl
Q.12 Correct order of boiling point is?
(a) BiH3 > SbH3 > NH3 > AsH3 > PH3
(b) NH3 > BiH3 > SbH3 > AsH3 > PH3
(c) NH3 > PH3 > AsH3 > SbH3 > BiH3
(d) BiH3 = NH3 > SbH3 > AsH3 > PH3
Q.13 Cl does not exhibit H – bonding significantly because
(a) Cl is less electronegative (b) Cl is more electronegative
(c) Cl has large size (d) Cl has small size
Q.14 Correct order of vapour pressure is:-
(a) C6H6 > CH3COCH3 > H2O (b) H2O > C6H6 > CH3COCH3
(c) CH3COCH3 > H2O > C6H6 (d) CH3COCH3 > C6H6 > H2O
Q.15 The forces of attraction which are responsible for liquefaction of inert gases are:-
(a) Keesom forces (b) London forces
(c) H - bonding (d) Covalent bond
 124 Chemical Bonding
Q.16 Arrange the following molecules in order of strength of London forces

CH3 CH3
CH3CH2CH2CH2CH3 CH3 – CHCH 2CH3 CH3— C — CH3
CH3

1 2 3
(a) 1 > 2 > 3 (b) 2 > 3 > 1
(c) 3 > 2 > 1 (c) 1 = 2 = 3
Q.17 Which is highly soluble in water?
(a) CH3OH (b) CH3NH2
(c) CH3F (d) CH3OCH3
Q.18 The strongest hydrogen bonding is present:-
(a) NH3 (b) N2O
(c) CH3NH2 (d) HF
Q.19 The pair of compounds which likely to form the strongest hydrogen bond is:-
(a) SiH4 and SiCl4 (b) CH3COOH and CH3COCH3
(c) CH3COOH and HCOOH (d) H2 and H2O
Q.20 Among H2O, H2Se and H2Te, the one with highest boiling point is
(a) H2O because of hydrogen bonding
(b) H2Te because of high molecular mass
(c) H2S because of hydrogen bonding
(d) H2Se because of lower molecular mass
Q.21 In which of the following substances, the intermolecular forces are hydrogen bonds?
(a) Hydrogen chloride (b) Hydrogen sulphide
(c) Dry ice (d) Ice
Q.22 Which of the following is a non-directinal bond?
(a) Dative bond (b) Covalent
(c) Hydrogen bond (d) None of these
Q.23 In which of the following species, the O-atom constitutes the positive end of electrical dipole?
(a) CH3CONH2 (b) C2H5OH
(c) OF2 (d) HO – CH2CH2F
Q.24 CuSO4.5H2O contains which type of bonds?
(a) Covalent only
(b) Covalent and co-ordinate
(c) Covalent, coordinate, ionic and H-bonds
(d) Ionic and covalent only
Q.25 Which one of the following molecules will form a linear polymeric structure due to hydrogen bonding?
(a) Urea (b) H2O
(c) H2O2 (d) HF
Chapter 7 : Hydrogen Bond & Inter Molecular Forces of Attractions 125
Q.26 H2O is dipolar, whereas BeF2 is not. It is because
(a) Both have same structures but electronegativity of 'F' is greater than that of 'O'
(b) H2O involves hydrogen bonding whereas BeF2 is a discrete molecule
(c) H2O is linear and BeF2 is angular
(d) H2O is angular and BeF2 is linear
Q.27 Which type of bond is not present in liq HNO2?
(a) covalent (b) coordinate & H – Bond
(c) H – Bond (d) coordinate
Q.28 Naphthalene is an organic compound containing two fused benzene rings. It is solid, the force of
attraction which is responsible for its physical appearance is:-
(a) van der Waal's forces (b) Electrostatic forces
(c) Hydrogen bonding (d) None of these
Q.29 The higher values of latent heat of water than other liquids have been accounted in terms of:-
(a) High dielectric constant (b) Polarity
(c) H - bonding (d) None of these
Q.30 H - bonding is not present in:-
(a) Glycerine (b) Water
(c) NH4OH (d) Urea
Matrix Match
Q.31 Molecule No. of H - Bonds
(A) H3BO3 (p) 0
(B) H2O (0°C) (q) 1
(C) H2O (100°C) (r) 2
(D) CH3COOH (s) 3
(t) 4
Q.32 Mixture Forces of attraction
(A) CCl4 + HF (p) London force
(B) HF + NO3 (–) (q) Dipole - dipole
(C) CCl4 + CO2 (r) Ion - dipole
(D) CO2 + CHCl3 (s) Ion - induce dipole
(t) Dipole - induce dipole
Q.33 Column - I Column - II
(Decreasing order) (Physical properties)
(A) H2O > H2S > H2Se > H2Te (p) Acid character
(B) NH3 > PH3 > AsH3 > SbH3 (q) Thermal stability
(C) H2O > H2Te > H2Se > H2S (r) Boiling point
(D) HI > HBr > HCl > HF (s) Reducing character
 126 Chemical Bonding

OBJECTIVE EXERCISE
1. (a) critical temperature µ intermolecular forces of attraction
2. (b) 3. (d)
4. (c) due to intermolecular -H-bonding angle between µ1 & µ2 reduces (less than 60°) which increases
dipole moment of molecule

m2
OH
F m1

(+) (–)
5. (d) 6. (c) K [ F–H F] 7. (b)

8. (c) dipole induce dipole attraction 9. (b)

10. (b) due to intramolecular –H–bonding bond angle becomes less than 109° 28' & thus, it releases
CH3OH as follows

OH
CH3 CH CH3OH + CH3CHO
q < 109° 28' OCH3

11. (c) In HF hydrogen bonding takes place while in HI, HBr & HCl Van-der-waal forces of attractions are
present . Since strength of hydrogen bond is more in comparison to Van-der-waal forces hence, HF
has highest boiling point.
12. (a) 13. (c)
14. (a) vapour pressure µ 1 / intermolecular forces of attraction
15. (b) 16. (a) London forces µ surface area 17. (b)
18. (d) 19. (c)
20. (a) in water H-bond is present while in rest hydrides weak van-der-waal forces are present
21. (d) 22. (c) 23. (c) 24. (c)
25. (d) 26. (d) 27. (d) 28. (a)
29. (c) 30. (c)
31. A—s B—t C—p D—r
32. A—s B—r C—p D—t
33. A—q B—q C—r D—r, s
Chapter 8 : Miscellaneous Problems 127

8
Miscellaneous Problems
Q.1 In which C — C bond, the mean percentage 'p' character of sigma bond is 58.5%
(a) sp2 – sp (b) sp3 – sp2
(c) sp3 – sp (d) sp3 – sp3
Q.2 What will be C — C bond length in propane if distance between two terminal 'C' is 2.53 Å and
sin54.75° = 0.82
(a) 1.54 Å (b) 1.265 Å
(c) 3.08 Å (d) 5.06 Å
Q.3 In SO3 two pp - dp bonds are present. The'd' orbitals of sulphur taking part in these p bonds are:-
(a) dz2, dxy (b) dx2y2, dz2
(c) dxy, dyz (d) dxy, dx2 – y2
Q.4 In which of the following these is maximum chances of pp – dp bonding?
(a) BCl3 (b) NBr3
(c) NH2 (–) (d) BF3
Q.5 There are twelve electrons in the valence shell of central atom in a molecule. These electrons are
arranged in such a way that 66.67% of total electron forms bond while remaining electrons is non
bonding electrons. The actual shape of molecule will be:-
(a) Square planar (b) 'T' shape
(c) Linear (d) Octahedral
Q.6 Which contains 33.33% d character.
(a) PF6 (–) (b) AlF6–3
(c) XeF6 (d) both (a) & (b)
Q.7 C2H2 is isostructural with
(a) C3O2 (b) CO2
(c) ICl2(–) (d) all of these
 128 Chemical Bonding
Q.8 Compounds Boiling point
(A) CH3OH (P) 65°C
(B) CH3COOH (Q) 118°C
(C) CH3COCH3 (R) 56°C
Correct matching is:-
(a) A®R, B®P, C®Q (b) A®P, B®Q, C®R
(c) A®R, B®Q, C®P (d) A®Q, B®P, C®R
Q.9 Which will distill at last?
(a) liquid CO2 (b) liquid F2
(c) liquid N2 (d) liquid O2
Q.10 In which case bonds are non directional
(a) NH2 (–) (b) SrCl2
(c) BeCl2 (d) CH3(–)
Q.11 Weakest pi bond will be present in:-
(a) CH3 Si O CH3 (b) POCl3
(c) HO – Cl = O (d) CH3COCH3
Q.12 AB2C2 can exist in two forms

B B

C A C & C A B

B C
(I) (II)

In these forms A exhibits dsp2 hybridization. If A – C distance is 2.32 Å thus C – C distance in I & II
respectively are:-
(a) 3.28 Å, 4.64 Å (b) 5.64 Å, 4.64 Å
(c) 4.64 Å, 3.28 Å (d) 3.28 Å, 5.64 Å
Q.13 Consider the two covalent compounds AB & XY
AB , µ = 8.98 D, bond length = 2.98 Å
XY, µ = 7.45 D, bond length = 2.3 Å
Select the correct statement:-
(a) AB is more ionic than XY
(b) XY is more ionic than AB
(c) Both are equally ionic
(d) AB is more ionic than XY but XY is more soluble in polar solvents in comparison to AB
Chapter 8 : Miscellaneous Problems 129
Q.14 In which case maximum lp - bp repulsions are present

B B
.. B
(a)
.. A (b)
.. A
.. B
B B

..
B
(c) B A (d)
..
NH3
B
B

Q.15 Among NO2, AlO2(–), BaO2 and KO2, unpaired electron is present in:-
(a) KO2 & NO2 (b) AlO2(–), KO2
(c) BaO2, NO2 & KO2 (d) KO2, NO2, AlO2(–)
Q.16 If a molecule MX3 has zero dipole moment, the sigma bonding orbitals used by M (atomic number < 21)
are
(a) Pure p (b) sp hybrid
(c) sp2 hybrid (d) sp3 hybrid
Q.17 The ion which is isoelectronic with CO & has same bond order as well as magnetic behaviours is:-
(a) CN– (b) O2+
(c) O2 – (d) N2+

Q.18 [H] CH CH OH
CH3CHO ¾¾¾ ® 3 2
In the above reduction process the % of s character change in the hybrid orbital of bold carbon atom is:-
(a) 24.99 % (b) 33.33 %
(c) 66.67 % (d) 50 %
Q.19 The luster of metal is due to:-
(a) High polish of metal
(b) Reflection of light due to the presence of free electrons
(c) Absorption of light by Kernels
(d) Chemical inertness of metals
Q.20 Consider the following reaction:-
(+) (–)
X2 + Y2 X2 + Y2
(16e) (14e)

Which of the following statement is wrong:-

(a) In X2(+), X – X bond weakens (b) In Y2(–), Y – Y bond weakens
(c) In X2(+), X – X bond order increases (d) Y2(–), becomes paramagnetic
 130 Chemical Bonding
Q.21 Lowest degree of paramagnetism per mol at 298 K will be shown by
(a) CuSO4, 5H2O (b) FeSO4, 6H2O
(c) NiSO4, 6H2O (d) MnSO4, 6H2O
Q.22 Which statement is true?
(a) Dipole moment is a measure of ionic character in covalent compound and a molecule with polar
bonds will always have some dipole moment
(b) Dipole moment is a vector quantity and a molecule having polar bonds can have zero dipole
moment
(c) A molecule can have a dipole moment even in the absence of polar covalent bonds
(d) AB2 (µ = 0) and AB2 (µ ¹ 0) will have same geometries
Q.23 Least bond angle around central atom will be in:-
(a) SbH3 (b) CO32(–)
(c) H2O (d) I3 (–)
Q.24 Which among the following possess highest covalency:-
(a) CaCl2 (b) ZnCl2
(c) NaCl (d) CsCl
Q.25 In which case metal - metal bond is present:-
(a) Green vitriol (b) Calomel
(c) Chilli salt peter (d) Plaster of pairs
Q.26 The nodal plane in the p bond of ethane is located in:-
(a) The molecular plane
(b) A plane parallel to the molecular plane
(c) A plane perpendicular to the molecular plane which bisects the carbon - carbon sigma bond at 90°
(d) A plane perpendicular to the molecular plane which contains the carbon - carbon bond
Q.27 The shape of the product 'X' will be:-
KI (aq) + I2 'X'
(a) Linear (b) Angular
(c) 'T' (d) Triangular
Q.28 Out of AgI, CdI2, RbCl & Ag2S, the coloured compounds are :-
(a) All of these (b) None of these
(c) AgI & CdI2 (d) AgI, CdI2 & Ag2S
Q.29 Least C – C bond length will be found in:-
(a) CCl3 – CCl3 (b) CCl3 – CH3
(c) CH3 – CH3 (d) CF3 – CF3
Q.30 Which among the following species will favour reduction process:-
N2, O2, O2(+), CO, CN(–)
(a) O2 (+) (b) N2 & O2
(c) CO, CN(–) & O2(+) (d) None of these
Chapter 8 : Miscellaneous Problems 131
Q.31 Hybrid state of nitrogen in (SiH3)3N is:-
(a) sp (b) sp 2
(c) sp 3 (d) May be sp or sp2
Q.32 In which case most stable H – bond will form?

OH O OH O
OH

O
(I) (II) (III)

(a) I (b) II
(c) III (d) II & III
Q.33 In which case bold carbon atom is sp3 hybridised:-
. .
(a) CH3 (b) CF3

(+) .
(c) CH3 (d) CH3CH2

Q.34 Which ion has higher polarizing power:-

(a) Pb+2 (b) Mg+2
(c) Zn+2 (d) Na(+)
Q.35 In which case, two nodal planes are present:-
(a) s2pz (b) p2px
(c) s*2s (d) None of these
Q.36 Highest bond order will be found in:-
(a) ClO4(–) (b) PO43(–)
(c) SO32(–) (d) NO3(–)
Q.37 Which of the following species have non linear geometry:-
(1) SnCl2 (2) ICl2(–)
(3) XeF2 (4) C3O2
Select the correct answer using the codes given below:-
(a) 1 (b) 1 & 2
(c) 2, 3 & 4 (d) 3
Q.38 Which will conduct electricity:-
(a) Na2SO4 in benzene (b) Solid NaCl
(c) RbCl in molten state (d) AgCl in molten state
Q.39 The pair of species / molecules having pyramidal geometry is:-
(a) H3O(+) & NH4(+) (b) ClF3 & NH3
(c) XeO3 & H3 O(+) (d) ClF3 & XeO3
 132 Chemical Bonding
Q.40 A compound is made up of three elements X, Y & Z having oxidation states +4, +5 & –2 respectively.
Possible formula of the compound will be:-
(a) X4(YZ4)4 (b) X2(YZ3)2
(c) X(YZ2)2 (d) X3(YZ2)3
Q.41 Match list I (Molecules) with the list-II (bond angles) and select the correct answer if x > y > z > t
List - I List - II
A NH3 1 x
B CH4 2 y
C H2S 3 z
D H2O 4 t
A B C D
(a) 4 3 1 2
(b) 1 2 4 3
(c) 3 4 1 2
(d) 2 1 4 3
Q.42 A di atomic molecule has a dipole moment of 1.2 D. If its bond distance is 1.0 A° what fraction of an
electronic charge exists on each atom?
(a) 25 % (b) 50 %
(c) 66.67 % (d) 33.33 %
Q.43 Select the correct reaction
(a) BCl3 + 3H2O H3BO3 + 3HCl
(b) NCl3 + 3H2O H3NO3 + 3HCl
(c) BCl3 + 3H2O BH3 + 2HOCl
(d) BCl3 undergoes hydrolysis but NCl3 does not.
Q.44 The correct order of increasing % s character in C– H bond will be:-
(1) CHCl3 (2) CHF3
(3) CHBr3 (4) CH4
(a) 4 > 1 > 2 > 3 (b) 1 > 2 > 3 > 4
(c) 4 > 3 > 2 > 1 (d) 2 > 3 > 1 > 4
Q.45 Carbon and silicon belong to 14th group & both of them oxides of the type MO2 select the correct
statements about CO2 & SiO2.
I. CO2 is linear while SiO2 has 3D network.
II. CO2 is covalent while SiO2 is ionic.
III. In CO2, C forms double bonds with oxygen while in SiO2 silicon forms single bonds with oxygen.
IV. Both CO2 & SiO2 have linear geometry.
V. Si can not form stable p bond with oxygen.
(a) I, II & IV (b) I, II, III & IV
(c) I, III & V (d) I & IV
Chapter 8 : Miscellaneous Problems 133
Q.46 Out of 1, 2, 3 & 4 thermally unstable compounds are:-
(1) PbCl4 (2) SrCO3
(3) BiCl5 (4) PbBr2
(a) 1, 2 & 3 (b) 2 , 3 & 4
(c) Only 2 (d) 1, 3 & 5
Q.47 In BiI3 iodine is present as:-
(a) I(–) (b) I3 (–)
(c) I3 3(–) (d) I2….I(–)
Q.48 Correct order of acidity of oxides will be:-
(a) ZnO > PbO > MgO > CaO > SrO
(b) PbO > ZnO > MgO > CaO > SrO
(c) MgO > CaO > SrO > ZnO > PbO
(d) ZnO > CaO> SrO > PbO > MgO
Q.49 Out of BeO, MnO2 and Cr2O3 amphoteric oxides are:-
(a) BeO only (b) MnO2 only
(c) BeO and MnO2 (d) All of these
Q.50 Correct sequence of ionic mobility in aqueous medium will be:-
(a) Li+ > Na+ > K+ > Rb+ > Cs+ (b) Cs+ > Rb+ > K+ > Na+ > Li+
(c) Li+ Cs+ < Rb+ < K+ < Na+ (d) Li+ > Na+ K+ > Rb+ > Cs+
Q.51 Which will have highest electrical conductance at room temperature?
(a) LiHCO3 (b) NaHCO3
(c) RbHCO3 (d) CsHCO3
Q.52 Which among the following can be crystallized?
(a) MgHCO3 (b) LiHCO3
(c) Ca(HCO3)2 (d) Cs(HCO3)2
Q.53 When CO+ is produced from CO electron is lost from
(a) p2px (b) s2pz
(c) s*2s (d) p*2px
Q.54 Match list - I (species) with the list - II (bond order) and select the correct answer if x > y > z > t
List - I List - II
A N2 1 x
B CO + 2 y
C O2+ 3 z
D H2 + 4 t
A B C D
(a) 1 2 4 3
(b) 2 1 3 4
(c) 1 4 3 2
(d) 2 3 4 1
 134 Chemical Bonding
Q.55 In CO molecule direction of dipole moment will be from
(a) 'C' to 'O' (b) 'O' to 'C'
(c) may be 'C' to 'O' or from 'O' to 'C (d) It is non polar molecule
Q.56 The molecules which do not exist in nature are
SH6 PH5 BrF7 HN3 C3Cl2H2
(1) (2) (3) (4) (5)
(a) 1, 2, 3 & 5 (b) 1, 2 & 5
(c) 1, 2 & 4 (d) 1, 2 & 3
Q.57 The C = C bond dissociation energy of olefins is 146 Kcal / mole whereas C – C bond dissociation energy
of paraffins is 83 Kcal / mol. Pick out the correct statement.
(a) Olefins are more reactive than paraffins
(b) Paraffins are more reactive than olefins
(c) Both are equally reactive
(d) At room temperature oleffins are reactive in comparison to paraffins but above 50° C paraffins are
more reactive than oleffins
Q.58 Which among the following is non polar?
(a) SO3 (b) SO2
(c) CO (d) H2O
Q.59 SO3 on trimerization gives (SO3)3 or S3O9.
The number of S – S bonds in this trimer will be:-
(a) 1 (b) 2
(c) 3 (d) zero
Q.60 The pp - dp bonding is present in
SO3 N2O5 P4O10 XeOF4
(1) (2) (3) (4)
(a) 1 & 4 (b) 1, 2 & 4
(c) 4th only (d) 1, 2, 3 & 4
Q.61 The hybridization of the central atom will change when
(a) NH3 combines with H(+)
(b) AlH3 combines H(–)
(c) NH3 forms NH2(–)
(d) H2O forms H3O(+) on reaction with H(+)
Q.62 Which among the following will have largest size?
(a) Fe+3(aq) (b) Al+3(aq)
(c) Mn+2(aq) (d) K+(aq)
Q.63 Largest bond angle will be found in
(a) NO2(+) (b) NO2(–)
(c) NO3(–) (d) NO2
Q.64 Softness of gypsum is due to
(a) Ionic bonding (b) Covalent boding
(c) Hydrogen bonding (d) London forces
Chapter 8 : Miscellaneous Problems 135
Q.65 The number of p* electrons in O2 2– is

(a) 2 (b) 1
(c) 4 (d) 3
Q.66 Hybridization of N in solid N2O5 is
(a) sp2 & sp2 (b) sp3 & sp2
(c) sp2 & sp3 (d) sp & sp2
Q.67 Which among the following will attach more number of H2O molecules around itself?
(a) Zn+2 (b) Fe+2
(c) Mg+2 (d) Ca+2
Q.68 Maximum number of pp - dp bonds are present in:-
(a) SO3 (b) XeO4
(c) HClO3 (d) XeO2F2
Q.69 Which of the following statement is correct?
(a) When a covalent bond is formed, transfer of electron takes places.
(b) Ordinary water does not contain any ion.
(c) A bond is formed when attractive forces over come repulsive forces.
(d) HF is less polar molecule than HBr
Q.70 The graph between energy and distance between atoms in the formation of molecule can be shown as :

e
n II
e
r
g
y I

Pick out the correct statement about I & II

(a) II represents BMO (b) I represents asymmetric BMO
(c) I represents symmetric BMO (d) I represents ABMO while II represents BMO
Q.71 In solid BeCl2 hybrid state of Be is:-
(a) sp (b) sp 2
(c) sp 3 (d) sp 3 d
Q.72 In which of the following case bond order increases and magnetic moment decreases?
(a) (+) +e (b) –e (+)
CO CO NO NO
–e –e
(c) H2 H2(+) (d) O2 O2(+)
Q.73 The ratio of % of s and % d character in the hybrid orbital of central atom in a molecule is 1 : 1.
The molecule is :-
(a) SF4 (b) XeF4
(c) PCl5 (d) XeF6
 136 Chemical Bonding
ASSERTION & REASON TYPE QUESTIONS

(a) Both Assertion & Reason are correct but Reason is correct explanation of Assertion
(b) Both Assertion & Reason are correct but Reason is not correct explanation of Assertion
(c) Assertion is correct & Reason is incorrect
(d) Assertion is incorrect & Reason is correct

Q.74 Assertion (A) : Coordinate bond is semi ionic in nature

Reason (R) : It is formed by the formation of ionic bond followed by covalent bond
Q.75 Assertion (A) : Bond order of CO is greater than CO+
Reason (R) : In the formation of CO+ from CO electron is lost from s2*s
Q.76 Assertion (A) : Some times ionic solids conduct electricity in little amount at room temperature.
Reason (R) : At room temperature defects are present in the crystal.
Q.77 Assertion (A) : 2NO2 N2O4
Coloured Colourless
Reason (R) : On dimerisation NO2 releases unpaired electrons
Q.78 Assertion (A) : Bond angle in F2O is 110°, while it is 103° in Cl 2O
Reason (R) : In Cl2O back bonding takes place
Q.79 Assertion (A) : Al(OH)3 is amphoteric in nature
Reason (R) : Al – O and O – H bond strengths are almost equal there exist almost equal probability of
their breaking
Q.80 Assertion (A) : PCl5 exists but PH5 does not
Reason (R) : Chlorine is an electronegative element and can transfer electron of ‘P’ from 3s to 3d orbital
Q.81 Assertion (A) : Solubility of sulphates of alkaline earth metals in water decreases on moving down the
group
Reason (R) : Decrease in hydration energy is more prominent than decrease in lattice energy
Q.82 Assertion (A) : In B2H6 all B – H bonds are identical
Reason (R) : It contains two banana bonds
.
Q.83 Assertion (A) : Hybridization of carbon in CH3 is sp2

Reason (R) : The orbital in which unshared electron is present has high energy and does not takes part
in hybridization
Q.84 Assertion (A) : PbCl4 is thermally unstable
Reason (R) : Polarizing power of Pb+2 is greater than Pb+4
Q.85 Assertion (A) : K2SO4 is soluble in water but BaSO4 is not
Reason (R) : Lattice energy of BaSO4 exceeds its hydration energy
..
Q.86 Assertion (A) : Hybridization on 'N' is sp3 in CH2 = CH– NH2
Reason (R) : Lone pair of electron present on nitrogen undergoes resonance
Chapter 8 : Miscellaneous Problems 137
Q.87 Assertion (A) : NaI will be more soluble in acetone in comparison to NaF
Reason (R) : NaI is more covalent than NaF
Q.88 Assertion (A) : In KMnO4 no unpaired electron is present in Mn but it has pink appearance
Reason (R) : O–2 ions transfer their charge to Mn+7
Q.89 Assertion (A) : XeF5(–) has planar geometry
Reason (R) : Xe is sp3d3 hybridized and non bonding electrons occupy equatorial positions
Q.90 Assertion (A) : BCl3 on hydrolysis forms HCl and H3BO3
Reason (R) : Water attacks on Cl atom of BCl3
Q.91 Assertion (A) : NCl3 on hydrolysis form NH3 and HOCl
Reason (R) : H2O attacks on Cl atom of NCl3
Q.92 Assertion (A) : (CH3)3N is a weaker base than (SiH3)3N
Reason (R) : In (SiH)3N back bonding takes place
(+) (–)
Q.93 Assertion (A) : NH3 + BF3 NH3 BF3 in this reaction hybrid state of nitrogen and B
does not change
Reason (R) : Dative bond will be considered as sigma bond

Cl Cl

Q.94 Assertion (A) : Cl Cl

m = x debye m = 3 x debye

Reason (R) : In 2nd case resulting dipole moment is found to be zero

Q.95 Assertion (A) : C3O2 is linear while SnCl2 is bent
Reason (R) : In SnCl2 lone pair of electron is present
Q.96 Assertion (A) : ICl is more reactive than Cl2
Reason (R) : Iodine has large size
Q.97 Assertion (A) : LiHCO3 is liquid while NaHCO3 is solid
Reason (R) : LiHCO3 has more lattice energy than NaHCO3
Q.98 Assertion (A) : BF3 does not undergo dimerisation to produce B2F6
Reason (R) : In BF3 back bonding occurs which reduces the electron deficiency of 'B' atom

MORE THAN ONE MAY CORRECT TYPE

Q.99 Molecules with zero dipole moments are:-
(a) CCl4 (b) NH4 (+)
(c) NH3 (d) BF3
Q.100 Inter molecular H – bonding will be present in:-
(a) CH3NH2 (b) N2O4
(c) NH4 (+) (d) H3BO3
 138 Chemical Bonding
Q.101 Which of the following has linear structure?
(a) KI3 (b) HgCl2
(c) C2H2 (d) H – F (gas)
Q.102 Which is not correct about ionic compounds?
(a) They are less soluble in benzene but more soluble in water
(b) They have directional bonds
(c) They have low melting points
(d) Their thermal stabilities are lesser than that of covalent compounds
Q.103 Pick out the correct statement about the following reactions
(1) SiCl4 + 4H2O Si(OH)4 + 4HCl
(2) CCl4 + 4H2O C(OH)4 + 4HCl
(a) 2nd reaction
is not possible while 1st reaction is possible
(b) 2nd reaction is possible while reaction is not possible
(c) 2nd reaction is not possible because 'C' can not receive electrons from water as it does not contain
empty'd' orbital
(d) 1st reaction is not possible because Si(OH)4 is an unstable compound and loose water to form
(OH)2 SiO
Q.104 Paramagnetic species are:-
(a) CN(+) (b) CN(–)
(c) NO(+) (d) NO(–)
Q.105 Thermally unstable oxides are:-
(a) HgO (b) AgO
(c) ZnO (d) Li2O
Q.106 The hybridization in which dz2 orbital is involved will be:-
(a) dsp 2 (b) sp 3 d
(c) sp 3 d 2 (d) d 2 sp 3
Q.107 The ion in present resonance takes is:-
(a) CO32– (b) HCO3(–)
(c) SO32– (d) ClO4(–)
Q.108 Compounds with µ = 0 are
(a) PF3Cl2 (b) PCl3F2
H Cl H Cl
(c) C=C=C=C (d) C=C=C
Cl H Cl H
Q.109 The type of bonds present in NH4Cl is:-
(a) Ionic (b) Covalent
(c) Dative bond (d) back bonding
Q.110 Which of the following has bond order 2.5?
(a) N2 (–) (b) N2 (+)
(c) NO(+) (d) O2 (+)
Chapter 8 : Miscellaneous Problems 139
Q.111 Which of the following has tetrahedral shape?
(a) SO42– (b) ClO4(–)
(c) SOF4 (d) NH4 (+)
Q.112 Pick out the correct statement:-
(a) NO(+) is more stable than NO towards dissociation in to its ions
(b) NO(–) is more stable than NO towards dissociation in to its ions
(c) CO(+) is more stable than CO
(d) O2(+) is more stable than O2(–)
Q.113 Peroxide linkages are present in:-
(a) CrO5 (b) H2SO5
(c) P2O5 (d) BaO2
Q.114 The compounds which have least solubility in water are:-
(a) BaSO4 (b) BaCl2
(c) CsNO3 (d) AgCl
Q.115 Which combination of the compounds and their geometry are correct?
(a) ICl4(–) - Square planar
(b) CHCl3 - Tetrahedral
(c) XeF5 (–) - Pentagonal planar
(d) H3 O(+) - Triangular planar
Q.116 In which case vacant orbital hybridization takes place:-
(a) B3N3H6 (b) B2O3
(c) B2H6 (d) Al2Cl6
Q.117 Which of the following is true about hybridized orbitals?
(a) Size of hybridized orbitals follow the order sp > sp2 > sp3
(b) Longitivity of sp2 hybridized orbitals is greater than sp3 hybridized orbital
(c) Angle between two sp3 hybridized orbitals is greater than that of sp2 and sp hybridized orbitals

(d) As we move from sp to sp3 hybridized orbitals % p character increases

Q.118 Correct order of boiling point is:-
(a) HF > HCl > HBr (b) H2O > H2Se > H2S
(c) HBr > HCl > HF (d) HF > HBr > HCl
Q.119 Correct order of reducing nature is:-
(a) HI > HBr > HCl > HF (b) H2S > H2Se > H2O
(c) HF > HCl > HBr > HI (d) H2Se > H2S > H2O
Q.120 Species in which central atom has two lone pair is / are:-
(a) XeF2 (b) SnCl2
(c) XeO3 (d) SO2
 140 Chemical Bonding
Q.121 The H –bond in solid HF can be best represented as?
H H H
(a) HF --------HF (b)
F F F
F H H
F
(c) H H H H (d) F F F F
F H
Q.122 Which of the following attraction are the types of van - der - waal's forces
(a) Ion - dipole (b) Ion - induces dipole
(c) Dipole - induces dipole (d) Dipole - dipole
Q.123 H - bonds are not present in:-
(a) KHF2 (b) CH3COCH3
COOH
(c) (d) DNA (double helix structure)

SINGLE INTEGER TYPE

The answer to each question of this section is a single digit integer, ranging from 0 to 9
Q.124 How many equatorial P –F bonds are there in PF3Cl2
Q.125 How many pp – dp bonds are present in XeO2F2
Q.126 How many - H – bonds are present in water in vapour state?
Q.127 How many S – S linkages are present in S3O9.
Q.128 How many resonating structures are possible for ClO4(–)
Q.129 How many nodal planes are present in s2pz
Q.130 Among the following compounds the number of compounds which are water soluble is…….
(CH3)2 NH, CH3OH, C6H6, C6H5NH2, CH3NH2, Na2SO4, BaSO4
2+
Q.131 Total number of electrons presents in BMO of N2 are……….
Q.132 Total numbers of p bonds in the given compound are…………
NC – CH = CHCOCOOH
Q.133 Total numbers of thermally unstable carbonates among the following are…………
Li2CO3, MgCO3, Na2CO3, Rb2CO3, CaCO3, K2CO3, FeCO3, ZnCO3,
PbCO3
Q.134 Total number of pairs in which 1st compound has higher boiling point than 2nd are………..
NH3 & HF, HF & HCl, H2S & H2Se, AlCl3 & BCl3, CH3OH & CH3COOH
Q.135 Total number of paramagnetic species is ………
NO, KO2, RbO2, O2(+), O2 (–), N2(+), O2, N2 (–), CN(–)
Q.136 Total number of molecules in which peroxide linkage is present is…….
Na2O2, BaO2, H2S2O8, H2S2O7, CrO5
Q.137 Total numbers of acidic hydrogens in H3PO2 are………..
Q.138 Total number of species in which back bonding takes place is……………
[CH2Cl] (–), S2Cl2, OCl2, SiH3NH2, BI3
Chapter 8 : Miscellaneous Problems 141
MATRIX MATCH TYPE
Q.139 Column - I Column - II
(A) H3 O(+) (p) µ= 0
(B) BF3 (q) Tetrahedral
(C) CO3 2(–) (r) Pyramidal
(D) NH4 (+) (s) Bond angle close to 120°
Q.140 Column - I Column - II
(A) Na2SO4 (p) Covalent bond
(B) CuSO4.5H2O (q) Coordinate bond
(C) Cu / Zn (r) Hydrogen bond
(D) H2O (s) Metallic bond
Q.141 Molecules No. of H - bonds formed by one molecule
(A) water (p) 1
(B) ice (q) 2
(C) H3BO3 (r) 3
(D) CH3COOH (s) 4
Q.142 Species Shape
(A) S8 (p) Crown
(B) NH2 (–) (q) Tetrahedral
..
(C) AB2 (r) V shape
..

(D) NCl2(–) (s) Linear

Q.143 Species Bond angle
(A) NO2 (+) (p) 180°
(B) NCl2 (–) (q) 120°
(C) NO3 (–) (r) 109°
(D) H2O (s) 104.5°
Q.144 Column - I Column - II
(Decreasing order) (Properties)
(A) CsCl > RbCl > KCl > NaCl (p) Bond order
(B) N2 > O2(+) > O2 (q) Magnetic moment
(C) AgI > AgBr > AgCl (r) Intensity of colour
(D) O2 > O2(+) > N2 (s) Solubility in water
Q.145 Column - I Column - II
(A) BrF2 (–) (p) sp 3
(B) ClF4(–) (q) sp 3 d
(C) ICl2(–) (r) sp 3 d 2
(D) IF5 (s) sp 3 d 3
 142 Chemical Bonding
Q.146 Column - I Column - II
(A) FeSO3 & MgSO4 (p) Isomorphours
(B) NaNO3 & NaClO3 (q) soluble in water
(C) K2SO4 & KMnO4 (r) same geometry of anion
(D) BaSO4 & BaCO3 (s) Water insoluble
Q.147 Species No. of axial bonds
(A) XeF5(–) (p) 0
(B) PCl3 (q) 1
(C) XeO2F2 (r) 2
(D) ClF3 (s) 3
Q.148 Column - I Column - II
(A) NO2(+) (p) 180°
(B) NO2(–) (q) 120°
(C) NO2 (r) 134°
(D) NO3(–) (s) 115°
(t) 109°

COMPREHENSION TYPE QUESTIONS

PASSAGE - I
The energy released in the formation of 1 g mole electrovalent compound from isolated gaseous ions is
called lattice energy (Uo)
M(+) + X(–) MX + Uo
The electric field of ions is uniformly distributed around the ion and so each ion is surrounded by
oppositely charged ions and thus crystal lattice is formed iva the release of energy called lattice energy.
It can be calculated by the help of Born - Lande equation

Uo = –NoAZ+Z–e2 / 4p e0 r0 (1 – 1/n)

Where ro = equilibrium distance between cation and anion.

Lattice energy affects the stability and melting point of ionic solids. If lattice energy of an ionic solid is
lesser than hydration energy compound is soluble in water.
Answer the question from 149 to 152
Q.149 Decreasing order of lattice energy of FeO, Fe2O3 & NaCl is
(a) NaCl > FeO > Fe2O3 (b) Fe2O3 > FeO > NaCl
(c) NaCl = FeO > < Fe2O3 (d) Fe2O3 > NaCl = FeO
Q.150 Correct order of solubility in water will be:-
(a) KI > RbI > CsI (b) RbI > KI > CsI
(c) CsI > RbI > KI (d) All are equally soluble in water
Chapter 8 : Miscellaneous Problems 143
Q.151 Correct order of solubility in water will be :
(a) Na2S > Rb2S > Cl2S > K2S (b) Cs2S > Rb2S > K2S > Na2S
(c) Na2S > K2S > Rb2S > Cs2S (d) Na2S > Cs2S > K2S > Rb2S
Q.152 Correct order of melting point will be:-
(a) MgF2 > Mg3N2 > MgO (b) Mg3N2 > MgO > MgF2
(c) Mg3N2 > MgF2 > MgO (d) MgF2 > MgO > Mg3N2

PASSAGE - II
The attraction together the constituent atoms or an ion of chemical species is called chemical bond. An
atom has tendency to occupy 8 electrons in its valence shell, which is stable arrangement. Thus, to
complete the octet, atom forms bonds with other atoms. But a number of molecules are known in which
either octet is not complete (Hypovalent molecules) or there are more than 8 electrons in the valence
shell of central atom (Hypervalent molecules)
Answer the questions from 153 to 155
Q.153 Impossible species is:-
(a) I3 (–) (b) AlH3(–)
(c) O2 2– (d) none of these
Q.154 Molecules with super octet are:-
(a) XeF2 (b) XeO3
(c) ClF3 (d) All of these
Q.155 For the formation of hypervalent molecules:-
(a) Central atom should have small size and low electronegativity
(b) Central atom should have empty d orbital
(c) Central atom should have small size and high electron affinity
(d) All of these

PASSAGE - III
According to Bent's rule in trigonal bipyramidal geometry lone pair prefers to stay at equatorial positions
while more electronegative element prefers to stay at axial position
Answer the questions from 156 to 158
Q.156 Correct representation of SF4 is:-

F .. F
F F F
F
(a) S (b) F S (c) F S F (d) S
..

..

F F
F .. F F
F F
 144 Chemical Bonding
Q.157 Shape of ICl4 (–) is:-

(a) Square Planar (b) Trigonal bi pyramidal

(c) Sea saw (d) Tetrahedral
Q.158 In sp3d hybridization % s character in axial bonds is:-
(a) 0% (b) 25%
(c) 33.33% (d) 20%
PASSAGE - IV
Elements of group 15, 16 & 17 form hydrides of the type MH3, MH2 & MH respectively. Their boiling
points depend upon the strength of intermolecular forces of attraction existing between them. Strength
of M – H bond decreases as the size of M increase.

Answer the questions from 159 to 163

Q.159 Compound with least boiling point is:-
(a) HI (b) H2S
(c) NH3 (d) HF
Q.160 Which among the following is highly volatile?
(a) HF (b) HBr
(c) HCl (d) HI
Q.161 Which among the following has highest boiling point?
(a) NH3 (b) BiH3
(c) PH3 (d) AsH3
Q.162 Strong reducing agent is:-
(a) H2O (b) H2S
(c) H2Se (d) H2Te
Q.163 Highly acidic compound is:-
(a) HF (b) NH3
(c) H2O (d) HI
TRUE AND FALSE TYPE QUESTIONS
Q.164 The size of negative ion decreases with increasing magnitude of negative charge.
Q.165 The presence of polar bonds in a poly-atomic molecule suggests that the molecule has non-zero dipole
moment.
Q.166 The higher the lattice energy of an ionic solid, the greater will be its stability.
Q.167 Linear overlap of two atomic p-orbitals leads to a s-bond.
Q.168 All molecules with polar bonds have dipole moment.
Q.169 The H – N – H bond angle in NH3 is greater than the H - As - H bond angle in AsH3
Q.170 Ca+2 is smaller in size than K+ because the effective nuclear charge is greater.
Q.171 sp2 hybrid orbitals have equal s and p - character.
Chapter 8 : Miscellaneous Problems 145
Q.172 Linear overlap of atomic p & s orbitals leads to a sigma bond.
Q.173 The tetrahedral geometry in SiF4 is due to sp3 hybridization of Si atom.
Q.174 In benzene, carbon uses all the three p-orbitals for hybridization.
Q.175 There are seven electron bond pairs in IF7 molecules.
Q.176 The dipole moment of CH3F is greater than that of CH3Cl.
Q.177 All molecules with polar bonds have dipole moment.
Q.178 Dipole of CHF3 is greater than CHCl3.
Q.179 Dipole moment of NF3 is lesser than NH3.
Q.180 SnCl2 is a non-linear molecule.
Q.181 Among HF, HCl, HBr and HI, HF has highest dipole moment.
Q.182 The presence of polar bonds in a polytomic molecule suggests that the molecule has non zero dipole
moment.
Q.183 Molten sodium chloride conducts electricity due to the presence of free ions.
Q.184 AgCl is more covalent than NaCl.
Q.185 MgCl2 is a non linear molecule.
Q.186 sp3d3 hybrid orbitals have equal 'd' and 'p' character.
 146 Chemical Bonding

MISCELLANEOUS EXERCISE

1. (a) 2. (a) 3. (c) 4. (d) 5. (a) 6. (d) 7. (d)

8. (b) 9. (a) 10. (b) 11. (a) 12. (c) 13. (b) 14. (a)
15. (a) 16. (c) 17. (a) 18. (a) 19. (b) 20. (a) 21. (a)
22. (b) 23. (a) 24. (b) 25. (b) 26. (a) 27. (a) 28. (d)
29. (d) 30. (d) 31. (b) 32. (a) 33. (b) 34. (c) 35. (d)
36. (a) 37. (a) 38. (c) 39. (c) 40. (a) 41. (d) 42. (a)
43. (a) 44. (d) 45. (c) 46. (a) 47. (b) 48. (a) 49. (d)
50. (b) 51. (a) 52. (b) 53. (c) 54. (b) 55. (b) 56. (d)
57. (a) 58. (a) 59. (d) 60. (d) 61. (b) 62. (b) 63. (a)
64. (c) 65. (c) 66. (d) 67. (a) 68. (b) 69. (c) 70. (c)
71. (c) 72. (b) 73. (c) 74. (a) 75. (d) 76. (a) 77. (c)
78. (d) 79. (a) 80. (a) 81. (a) 82. (d) 83. (a) 84. (b)
85. (a) 86. (d) 87. (a) 88. (a) 89. (c) 90. (c) 91. (a)
92. (d) 93. (d) 94. (a) 95. (a) 96. (b) 97. (b) 98. (b)

MORE THAN ONE, INTEGER TYPE & COMPREHENSIONS

99. (a,b,d) 100. (a,d) 101. (a,b,c,d) 102. (c,d) 103. (a,c) 104. (d) 105. (a,b)
106. (a,b,d) 107. (a,b,c,d) 108. (b,c) 109. (a,b,c) 110. (a,b,d) 111. (a,b,d) 112. (a,c,d)
113. (a,b,d) 114. (a,c,d) 115. (a,b,c) 116. (c,d) 117. (a,d) 118. (b,d) 119. (a,d)
120. (b,d) 121. (c) 122. (c,d) 123. (b) 124. 1 125. 2 126. 0
127. 0 128. 4 129. 2 130. 4 131. 8 132. 5 133. 6
134. 2 135. 8 136. 4 137. 1 138. 3
139. A – r B – p, s C – p, s D – p, q
140. A – p, q B – p, q, r C–s D – p, r
141. A – q B–s C– r D–q
142. A – p B– r C– r D–s
Chapter 8 : Miscellaneous Problems 147
143. A – r B–p C–q D–s
144. A – s B–p C– r D–q
145. A – q B– r C–q D– r
146. A – q B– q C – p, q, r D– s
147. A – p B– p C– r D– r
148. A – s B– t C–p D– r
149. (b) 150. (a) 151. (b) 152. (b) 153. (d) 154. (d) 155. (b)
156. (a) 157. (c) 158. (a) 159. (b) 160. (b) 161. (b) 162. (d)
163. (d)
TRUEAND FALSE

164. F 165. F 166. T 167. T 168. F 169. T 170. T

171. F 172. T 173. T 174. F 175. T 176. F 177. F
178. T 179. T 180. T 181. T 182. F 183. T 184.T
185 .F 186. F
 148 Chemical Bonding

ANSWERS TO MISCELLANEOUS PROBLEMS

1. (a) In sp2 & sp hybridization %p character is 66.67 & 50% respectively thus, mean of these values will
be (66.67 + 50) / 2 = 58.5%

CH2
2. (a)
x
q
H3C CH3 q = 109°28' = 54.75°
2
2.53 A° Sinq = 1.265
x
1.265 A° x = 1.265
Sin 54.75

x = 1.54 Å
3. (c)
4. (d) filled 2p of 'F' can easily overlap with empty 2p of 'B'
5. (a) 66.67 % of twelve electrons = 8e– A A
X
e– of bond pair = 8 thus, bond pair = 4
A A
e of lone pair = 12 – 8 = 4 thus, lone pair = 2
Thus central atom should have sp3d2 (4 + 2) hybridization & square planar shape.
6. (d)
7. (d) All are linear
8. (b) Extent of hydrogen bonding µ boiling point
9. (a) Due to more vander waal forces
10. (b) SrCl2 is an ionic compound
11. (a) 3pp – 2pp bond
12. (a) In 1st case C – C distance = 2 × 2.32 = 4.64Å

While in 2nd case C – C = (AC)2 + (AC) 2 = 3.28A°

13. (b) Calculate 'q' on atoms by q = µ / d

14. (a) 15. (a)

X
16. (c)
M sp2 m = 0

X X
Chapter 8 : Miscellaneous Problems 149
17. (a)
18. (a) In CH3CHO & CH3CH2OH bold carbons are sp2 and sp3 hybridized respectively, thus, change in
% 's' character will be (33.33 – 25) × 100 / 33.33
19. (b) 20. (a)
21. (a) 22. (b)
23. (a) SbH3 (almost 90°) CO32– (almost 120°), H2O (104.5°), I3(–) (180°)
24. (b) Except ZnCl2 rest all are ionic compounds
25. (b) Hg2Cl2 is called calomel Hg22+ ion possesses Hg – Hg bond
26. (a)
27. (a) KI + I2 KI3 & I3(–) has linear geometry
28. (d) 29. (d) 30. (d)
31. (b) N donates its lone pair to empty 'd' orbital of Si (back bonding) and makes double bond.

(+)
H3Si = N — SiH3 sp2

SiH3

32. (a) 33. (b)

34. (c) 35. (d)
36. (a) B.O. = No. of bonds participating in resonance / No. of resonating structure.

.. Cl
Sn
..

37. (a)
Cl
38. (c) ion are mobile

(+)
Xe O
..

39. (c)
O O H H
O H

40. (a) Net charge on molecule should be zero

41. (d)
42. (a) see q.n.– 11 in chapter – 05
43. (a)

s–
s– s+ Cl .. Cl (+) H
Cl — B H2O Cl — B —O
..

s– H
Cl Cl
2H2O Cl
H3BO3 + 2HCl B OH + HCl
Cl
 150 Chemical Bonding
44. (d) 45. (c) 46. (a)
47. (b) Because due to inert pair effect Bi forms Bi+ & not Bi+3
48. (a)
49. (d) 50. (b)
51. (a) LiHCO3 is liquid while rest are solid.
52. (d) Except Cs(HCO3)2 rest all exist in liquid state (see polarization in chapter – 05)
53. (c) See section - 6.2 54. (b)
(–) (+)
55. (b) Because of coordinate bond direction of dipole moment is from O to C
C O
56. (d) 57. (a)
58. (a) SO3 has zero dipole moment

59. (d) O O
O S
O
S O
O
O S
O O

60. (b)
61. (b) AlH3 (sp2) + H(–) AlH4(–)(sp3)
62. (b) Hydration µ 1 / size of ion µ size of hydrated ion.
63. (a) O = N(+) = O (sp hybridization an N, bond angle is 180°)
64. (c) 65. (c)
66. (d) N2O5 in solid state exists as NO2(+) & NO3(–).
67. (a) [Zn(H2O)6]+2
68. (b) Four pp – dp bonds are present in XeO4
69. (c) 70. (c)

Cl Cl
71. (c) Be Be Be
Cl Cl
72. (b)
73. (c) sp3d hybridization is present in PCl5
74. (a) See coordinate bond in chapter – 02
75. (d) See text in chapter – 06
76. (a)
77. (c) In NO2 unpaired electron is present on nitrogen which gets paired up on dimerisation
78. (d) 79. (a)
Chapter 8 : Miscellaneous Problems 151
80. (a) 81. (a)

82. (d) H
H H
B B
H H
H

Four B – H bonds are present on a plane and two – H – bonds are not present in plane, one is on
above plane & other is on below the plane. These two bonds are called banana bonds.
83. (a) See text chapter – 04, section – 4.8.
84. (b) Due to inert pair effect
85. (a)
86. (d) Delocalized electron pair (electron pair take part in resonance) are not considered in hybridization.
87. (a) Due to polarization NaI is covalent and thus, soluble in less polar solvent like acetone.
88. (a)
89. (c) See section
90. (c) See question – 43 91. (a)
92. (d) See question no. 28 93. (d)
94. (a) Resulting dipole moment will be zero. 95. (a)
96. (b) I – Cl bond is polar & needs less dissociation energy in comparison to Cl – Cl bond.
97. (b) See polarization
98. (b) 'B' Can not adjust more than 3 – fluorine around it self.

MORE THAN ONE MAY CORRECT

99. NH3 has pyramidal shape and hence it has non zero dipole moment.
100. In NH4+, N does not contains lone pair & hence can not form H – bond.
102. Ionic bonds are non directional bond.
103. Hydrolysis of CCl4 is not possible as 'C' does not contain empty 'd' orbitals.
105. Oxides of native metals like Pt, Ag, Hg, A4 are thermally unstable.
108. (d) is not planar while PF3Cl2 has following geometry.

F
Cl
Cl P µ ¹ 03
F
F
 152 Chemical Bonding

H
(+)
109. H N H Cl (–)
H

111. In a, b & d central atom has sp3 hybridization

115. H3O(+) has pyramidal shape
117. See section – 4.1
118. In H2O, H – bonding is present while in H2Se and H2S van– der– waal forces of attraction are present.
119. As length of M – H bond increases, stability decreases & M – H bond dissociates easily to produce H(+)
consequently reducing nature increases.

O HO
(+) (–)
123. Ph — C C — Ph K [ F–H F]
O— H O

COMPREHENSION TYPE QUESTIONS

Passage – I
149. (b) L.E. µ q1q2
150. (a) Check it by polarization
151. (b) Check it by L.E. & H.E
152. (b) M.P µ L.E. µ q1q2

Passage – II
153. (d)
154. (d) In all cases central atom possesses more than 8 e in outermost shell
155. (b)

Passage – III
156. (a) least bp – lp repulsions are present
157. (c) due to sp3d hybridization
158. (a) axial bonds have pd hybridization, thus, 0% 's' character

Passage – IV
159. (b) less extent of inter molecular forces are present
160. (b) same as previous
161. (b) More extent of London forces
162. (d) as it is least thermally stable
163. (d) same as previous