Chemical Bonding (ADV)

Chemical Bonding Rg-Chem.
XI
PREFACE
We know a great deal about the molecular structures of many thousands of compounds,
all based on reliable experiments. In our discussion of theories of covalent bonding, we must
keep in mind that the theories represent an attempt to explain and organize experimental
observations. For bonding theories to be valid, they must be consistent with the large body of
experimental observations about molecular structure. In this chapter we will study two theories
of covalent bonding, which usually allow us to predict correct structures and properties. Like
any simplified theories, they are not entirely satisfactory in describing every known structure;
however, their successful application to many thousands of structures justifies their continued
use.
Since the formation of chemical compounds takes place as a result of combination of
atoms of various elements in different ways, it raises many questions. Why do atoms combine?
Why are only certain combinations possible? Why do some atoms combine while certain
others do not? Why do molecules possess definite shapes? To answer such questions different
theories and concepts have been put forward from time to time. These are Kössel-Lewis
approach, Valence Shell Electron Pair Repulsion (VSEPR) Theory, Valence Bond (VB) Theory
and Molecular Orbital (MO) Theory. The evolution of various theories of valence and the
interpretation of the nature of chemical bonds have closely been related to the developments
in the understanding of the structure of atom, the electronic configuration of elements and the
periodic table. Every system tends to be more stable and bonding is nature’s way of lowering
the energy of the system to attain stability.
This booklet is divided into various sections. The first section deals with detailed theory
about the chapter. This is followed by some interesting solved examples which will help in
further understanding of the concepts. Students are advised to kindly go through these two
sections before jumping on to solving problems. Next, we have, a FOUNDATION BUILDER
EXERCISE, which will help the students in revision of the concepts taught in class and
application of these concepts. These exercises are to be done on a daily basis after the lecture
by the student.
To enhance your skills after you have grasped the basic concepts, you have the ‘‘Get
Equipped to JEE Mains & Get Equipped to JEE Advance “
A glance at the previous year questions of AIEEE has been provided in the section as
“Window to JEE Mains”
A glance at the previous year questions of IIT-JEE has been provided in the last section as
“Window to JEE Advance”
We are sure; you will have fun while you go through this journey.
Best of Luck!!
Team Chemistry @ IIT-ian’s PACE

COLLEGES: ANDHERI / BORIVALI / CHEMBUR / DADAR / KALYAN / KHARGHAR / NERUL / POWAI / THANE 1
Chemical Bonding Rg-Chem. XI
IIT–JEE SYLLABUS
Orbital overlap and covalent bond; Hybridisation involving s, p and d orbitals only; Orbital energy
diagrams for homonuclear diatomic species; Hydrogen bond; Polarity in molecules, dipole moment
(qualitative aspects only); VSEPR model and shapes of molecules (linear, angular, triangular, square
planar, pyramidal, square pyramidal, trigonal bipyramidal, tetrahedral and octahedral).
CONTENTS
1. Theory 2 – 38
2. Solved Problems (Subjective) 39 – 44
3. Solved Problems (Objective) 44 – 48
4. Foundation Builders (Objective) 49 – 59
5. Get Equipped for JEE (MAIN) 59 – 63
6. Get Equipped for JEE (ADVANCED) 63 – 72
7. Window To IIT-JEE (MAIN) 73 – 75
8. Window To IIT-JEE (ADVANCED) 75 – 80
9. Answer Keys 81 – 83
CHEMICAL BONDING : Tentative Lecture Flow

(Board Syllabus & Booklet Discussion Included)
Lecture –1 Ionic Bond, Lattice energy, Hydration, lattice & Solubilty, Octet Theory
Lecture – 2 Valance bond theory, Sigma& Pi bond, Lone pair, Coordinate bond
Lecture – 3 VSEPR Theory & Hybridisation

Lecture – 4 Fajan’s Rule amd Dipole Moment
Lecture – 5 Bond length, Energy and Bond Angle
Lecture – 6 MOT and Hydrogen Bond
1. INTRODUCTION
Chemical Bond is the physical process responsible for the attractive interactions between atoms and
molecules, and that which confers stability to diatomic and polyatomic chemical compounds. The
explanation of the attractive forces is a complex area that is described by the laws of quantum
electrodynamics. In general, strong chemical bonding is associated with the sharing or transfer of electrons
between the participating atoms.
The study on the “nature of forces that hold or bind atoms together to form a molecule” is required to gain
knowledge of the following
 To know about how atoms of same element form different compounds combining with different
elements.
 To know why particular shapes are adopted by molecules.
 To understand the specific properties of molecules or ions and the relation between the specific type of
bonding in the molecules.
2. LEWIS THEORY
The Lewis theory gave the first explanation of a covalent bond in terms of electrons that was generally
accepted. If two electrons are shared between two atoms, this constitutes a bond and binds the atoms
together. For many light atoms, a stable arrangement is attained when the atom is surrounded by eight
electrons.
The octet can be made up from some electrons which are totally owned and some electrons which are
‘shared’. Thus atoms continue to form bonds until they have made up an octet of electrons. This is called the
‘octet rule’. The octet rule explains the observed valences in a large number of cases. There are exceptions to
the octet rule; for example, hydrogen is stable with only two electrons.
The conventional Lewis structure representation of a pair of bonded electrons is by means of a ‘dash’ (-)
usually called a ‘bond’. Lone pairs or ‘non-bonded’ electrons are represented by ‘dots’. Some structures are
represented below:
.. H
(NH3) H : N : H
or H N H
..
..
H
H H
.. .. ..
(CO2) : O C O : (CH3CHO) H C C O :
H
Such representations of organic molecules are not usually problematic. However, ‘hit-and-trial’ is generally
the method (obviously not very efficient) used by most students in figuring out the structures of inorganic
molecules.
3. LEWIS DOT STRUCTURES

The formula of a molecule shows the number of atoms of each element but does not show the bonding
arrangement of the atoms. To represent the bonding pattern in a molecule, the electron dot symbols of the
elements are arranged such that the shared pairs and unshared pairs (called lone pairs) are shown and the
.. ..
octet rule (or duet for hydrogen) is satisfied. For example, a molecule of fluorine is shown as : F.. : F
.. : or
.. .. .. ..
:F
.. F
.. : and a molecule of hydrogen fluoride is shown as H:F
.. : or H F.. : .
Arrangement of dot symbols used to represent molecules are called Lewis structures. Lewis structures do
not convey any information regarding the shape of the molecule. Usually, the shared pairs of electrons are
represented by lines between atoms and any unshared pairs are shown as dot pairs.
Lewis structures are written by fitting the element dot symbols together to show shared electron pairs and
to satisfy the octet rule. For example,
..
. .. :O H
(i) In water (H2O), one H and two . O
. : complete their duet and octet respectively
H
. .. ..
(ii) In ammonia (NH3), three H and one . N. . fit together and satisfy their duet and octet H N H
respectively as H
..
:Cl:
.. .
(iii) In carbon tetrachloride (CCl4), four : Cl . and one . C . complete their octet as .. ..
.. . :Cl C Cl
.. .. :
:Cl
.. :
For the given molecules, we have adopted hit & trial method to fit the dot symbols together and satisfy the
octet rule. But remember that hydrogen form one bond, oxygen forms two bonds, nitrogen three bonds and
carbon forms four bonds. For simpler molecules, the hit & trial method works perfectly but for slightly
complicated polyatomic species, this may give us more than one possible structure. Thus, a systematic
approach is needed to design the Lewis structures of such polyatomic species. But before proceeding
further, let us understand the limitation of this approach.
LIMITATIONS OF LEWIS THEORY OF DRAWING STRUCTURE
This method would be applicable to only those molecules/species, which follow octet rule except hydrogen.
There are three kinds of molecules/species, which do not follow octet rule.
(a) Molecules, which have contraction of octet. Such molecules are electron deficient. For example,
BH3, BF3, BCl3, AlCl3, GaCl3 etc.
(b) Molecules, which have expansion of octet. Such species have more than eight electrons in their
outermost shell. This is possible in those molecules, which have vacant dorbitals, thus they can
expand their octet. For example, PCl5, SF6 etc.
(c) Molecules containing odd number of electrons (in total) cannot satisfy octet rule. Such species are
called odd electron species and are paramagnetic in nature due to presence of unpaired electron.
For example, NO, NO2 and ClO2.
METHOD OF DRAWING LEWIS STRCUTURES

To draw the Lewis structures of polyatomic species, follow the given sequence.
(i) First calculate n1.
n1 = Sum of valence electron of all the atoms of the species  net charge on the species.
For a negatively charged species, electrons are added while for positively charged species, the
electrons are subtracted. For anuninegatively charged species, add 1 to the sum of valence
electrons and for a dinegatively charged species, add 2 and so on.
(ii) Then calculate n2.
n2 =( 8 number of atoms other than H) + (2  number of H atoms)
(iii) Subtract n1 from n2, which gives n3.

n3 = n2 n1 = number of electrons shared between atoms = number of bonding electrons.
n3 n2  n1
 = number of shared (bonding) electron pairs = number of bonds.
2 2
(iv) Subtracting n3 from n1 gives n4.
n4 = n1 n3 = number of unshared electrons or nonbonding electrons.
n4 n  n3
= 1 = number of unshared electron pairs = number of lone pairs.
2 2
(v) Identify the central atom. Generally, the central atom is the one, which is least electronegative of all
the atoms, when the other atoms do not contain hydrogen. When the other atoms are hydrogen
only, then the central atom would be the more electronegative atom. Here, you are required to know
a bit of chemistry, physics or mathematics won’t help.
(vi) Now around the central atom, place the other atoms and distribute the required number of bonds
(as calculated in step (iii))& required number of lone pairs (as calculated in step (iv) ), keeping in
mind that every atom gets an octet of electrons except hydrogen.
(vii) Then calculate the formal charge on each atom of the species.Formal charge is the difference
between the valence electrons in an isolated atom and the number of electrons assigned to that
atom in a Lewis Structure.
Formal charge on an atom = number of valence electrons of the atom  (number of shared electrons
of that atom + number of unshared electrons of that atom).
Formal charge on an atom = number of valence electrons of the atom  number of bonds formed by
that atom  number of unshared electrons (2  lone pairs) of that atom.
For every electron of an atom that is shared in a bond, the “number of bonds formed by the atom” is
one. Therefore if an atom forms only one bond (AB), one electron of the bond is that of A and other
is that of B. So the “number of bonds” of A and B each is one. But if the bond were a coordinate
bond (AB), then two electrons of A are involved in it. This makes the number of bonds of A to be 2
and that of B to be zero.
(viii) When two adjacent atoms get opposite formal charges, then charges can be removed by replacing
the covalent bond between the atoms by a dative (coordinate) bond. This bond will have the
arrowhead pointing towards the atom with positive formal charge. It is not mandatory to show the
dative bonds unless required to do so.
(ix) The given Lewis structure should account for the factual aspects of the molecule like resonance
(delocalization), bond length, pd back bonding etc.
Sometimes, there are more than one acceptable Lewis structure for a given species. In such cases,
we select the most plausible Lewis structure by using formal charges and the following guidelines:
 For neutral molecules, a Lewis structure in which there are no formal charges is preferable to one in
which formal charges are present.
 Lewis structures with large formal charges (+2, +3 and/ or 2, 3 and so on) are less plausible than
those with small formal charges.
 Among Lewis structures having similar distributions of formal charges, the most plausible structure
is the one in which negative formal charges are placed on the more electronegative atoms.
Question: Determine Lewis structure of NO 3 ion.

Solution:
(i) n1 = 5 + (6  3) + 1 = 24
(ii) n2 = ( 4  8) = 32
(iii) n3 = n2  n1 = 32  24 = 8
8
 Number of bonds = =4
2
(iv) n4 = n1 n3 = 24  8 = 16
16
 Number of lone pairs = =8
2
(v) Nitrogen is the central atom (as it is less electronegative than O). Arranging three O atoms
around it and distributing 4 bonds and 8 lone pairs as
.. ..
:O N O
.. :
(a)
(b)
:O
.. : (c)
(vi) Calculating formal change on each atom.
Formal charge on N = 5  4  0 = + 1
Formal charge on O (a) = 6  2  4 = 0
Formal charge on O (b) = 6  1  6 = 1
Formal charge on O (c) = 6  1  6 = 1
Thus, the structures can now be shown as

1 1 +1 1 1 +1 0
0.. +1 .. .. .. .. ..
:O N O
.. : :O
.. N O
.. : :O
.. N O:
1
:O
.. : :O: 0 .. : 1
:O
Final structure of NO3 is therefore shown as

.. ..
:O N O
.. :
:O
.. :
which even accounts for resonance in NO3 ion.
4. IONIC BOND (OR ELECTROVALENT LINKAGE)

An ion is an atom or group of atoms which has acquired charge due to the loss or gain of one or more
electrons. When an atom gains an electron to form a negative ion (anion), it will increase in size. On the
other hand, when an atom loses an electron to give positive ion (cation), it will contract. The electron lost or
gained is always from the outermost shell.
When two atoms, one of which can lose one or more electrons to attain a noble gas configuration and the
other can receive these electrons and thereby acquire a noble gas configuration, they are said to be
bonded by an ionic bond. Since the loss and gain of electrons by atoms results in the formation of ions,
ionic bond is formed when two ions interact with each other and are thus held together by electrostatic
attraction.
The formation of an ionic compound is obviously related to the ease of formation of the cations and anions
from the neutral atom, which depends on two main factors:
Ionization energy: Lower the value of ionization energy of an atom, greater will be the ease of formation
of the cation from it.
Electron affinity: Higher the electron affinity of an atom, greater the ease of formation of the anion from
it.
The formation of an ionic compound is favoured by:
 low ionization energy (IE) of the metal.
 high electron affinity (EA) of the other element.
 higher lattice energy (U) of the resulting compound.
PROPERTIES OF IONIC COMPOUNDS

 Ionic compounds cannot show electrical conductivity as solids but conduct electricity quite well when
molten.
 Ionic compounds tend to have high melting points.
 Ionic compounds usually are very hard but brittle substances
 Ionic compounds are often soluble in polar solvents with high dielectric constants.
LATTICE ENERGY
“Lattice energy is the amount of energy released when one mole of an ionic solid is formed from its
constituent gaseous ions”. This amount of energy released is due to electrostatic force of attraction
produced by the 3 D rearrangement of the constituent ions.
Na+(g) + Cl-(g) Na+Cl-(s) + U; where U is the lattice energy.
The electrostatic attraction in the ionic bond is always follows coulomb’s law, which is given by
q q
F  12 2 where r is the interionic distance and q1& q2 are magnitude of charges.
r
Hence, the magnitude of lattice energy depends on two factors:
5. COVALENT BOND
A covalent bond is formed by the sharing of a pair of electrons between two atoms, each atom contributing
one electron to the shared pair. The shared pair of electrons should have opposite spins and they are
localized between the two nuclei concerned. A covalent bond is usually represented by a short line (i.e., a
dash) between the two atoms. Note that the covalent bond consists of a pair of electrons shared between
two atoms, and occupying a combination of two stable orbitals, one of each atom; the shared electrons of
each covalent bond are counted for each of the two atoms connected by the covalent bond.
Properties of covalent compounds
a) Under normal conditions of temperature and pressure, these exist as gases (or) liquid of low boiling
points. This is due to the fact that very weak forces of attraction (Vander Waal's forces) exist
between discrete molecules. Some exist as soft solids if their molecular masses are high.
b) With the exception of few, which have giant three-dimensional structure such as diamond,
carborundum (SiC), silica (SiO2), others have relatively low melting and boiling points. This is due to
the presence of weak attractive forces between the molecules. On supplying heat energy, the
molecules are readily pulled out from these forces and move freely having high kinetic energy.
c) In general, covalent substances are bad conductors of electricity. Substances, which have polar
character like HCl in solution, can conduct electricity. Covalent solids having giant molecules are
bad conductors since they do not contain charged particles or free electrons.
d) In general, covalent substances are insoluble in polar solvents like H2O, but soluble in non-polar
solvents like benzene, CCl4, ether etc. This is based on the principle, like dissolves like. Some of
the covalent compounds like alcohols; amines dissolve in water due to hydrogen bonding. Covalent
solids having giant molecules are practically insoluble in all solvents.
e) Covalent substances show molecular reactions. The reaction rates are usually low as it involves
breaking and establishing of covalent bonds.
6. CO-ORDINATE OR DATIVE BOND

It is a special type of covalent bond in which both the shared electrons are contributed by one atom only. It
may be defined as “a covalent bond in which both electrons of the shared pair are contributed by
one of the two atoms”. Such a bond is also called as dative bond. A coordinate or a dative bond is
established between two such atoms, one of which has a complete octet and possesses a pair of valence
electrons while the other is short of a pair of electrons.
The atom, which contributes electron pair is called the donor while the atom, which accepts, is called
acceptor. Co-ordinate bond after formation is indistinguishable from a covalent bond. This bond is
represented by an arrow ( → ) pointing towards acceptor atom.
For Example : Ammonium ion

The ammonia molecule has a lone pair of electrons i.e., an unshared pair. The hydrogen ion H+, has an
empty s orbital. The lone pair comes to be shared between the nitrogen and hydrogen atoms:

H  H   H 
..  ..   | 

H : N :  H  H : N : H or H  N  H
..  ..   | 
H  H   
   H 
Nitrogen atom is called the donor and H+, the acceptor. The arrowhead in N  H shows the acceptor.
NH is a neutral molecule. H+ carries a unit positive charge; so NH  ion carries a unit positive charge. Once
3 4

the NH ion is formed, all the NH bonds become identical to each other.
4
CHARACTERISTICS OF COORDINATE COMPOUNDS:

 They exist as gases, liquids and solids under ordinary conditions
 Their melting and boiling points are higher than purely covalent compounds and lower than purely ionic
compounds
 They are sparingly soluble in polar solvents like water but readily soluble in non-polar solvents
 They are as stable as the covalent compounds. The addition compounds are however not very stable.
It is also a strong bond because the paired electrons cannot be separated easily.
 Like covalent compounds, these are also bad conductors of electricity. The solutions or fused mass do
not allow the passage of electricity.
 They undergo molecular reactions. The reactions are slow
 The bond is rigid and directional. Thus co-ordinate compounds show isomerism.
 The compounds containing co-ordinate bond possess high values of dielectric constants.
7. VALENCE BOND THEORY

According to this theory proposed by Heitler and London and developed by Linus Pauling and Slater.
 For the formation of a covalent bond, a half – filled atomic orbital of one atom overlaps with the half
– filled atomic orbitals of another atom. These atomic orbitals belong to the outermost shell of the
atoms.
 A covalent bond is formed by the overlapping of atomic orbitals having electrons with opposite
spins.
 The atomic orbitals containing paired electrons do not participate in the processes of overlapping.
These electrons are called non – bonding electrons.
 Due to the directional nature of most of the orbitals, overlapping is possible only when orbitals are
properly oriented.
7.1 Sigma and Pi Bonding
When two hydrogen atoms form a bond, their atomic orbitals overlap to produce a greater density of
electron cloud along the line connecting the two nuclei. In the simplified representations of the
formation of H2O and NH3 molecules, the O—H and N—H bonds are also formed in a similar
manner, the bonding electron cloud having its maximum density on the lines connecting the two
nuclei. Such bonds are called sigma bonds (-bond).
A covalent bond established between two atoms having the maximum density of the electron cloud
on the line connecting the centre of the bonded atoms is called a -bond. A -bond is thus said to
possess a cylindrical symmetry along the inter-nuclear axis.
Let us now consider the combination of two nitrogen atoms. Of the three singly occupied p-orbitals
in each, only one p-orbital from each nitrogen (say, the px may undergo “head–on” overlap to form a
-bond. The other two p-orbitals on each can no longer enter into a direct overlap. But each p-
orbital may undergo lateral overlap with the corresponding p-orbital on the neighbour atom. Thus we
have two additional overlaps, one by the two py orbitals, and the other by the two pz orbitals. These
overlaps are different from the type of overlap in a -bond. For each set of p-orbitals, the overlap
results in accumulation of charge cloud on two sides of the inter-nuclear axis. The bonding electron
cloud does no more posses an axial symmetry as with the -bond; instead, it possesses a plane of
symmetry. For the overlap of the pz atomic orbital, the xy plane provides this plane of symmetry; for
the overlap of the py atomic orbitals, the zx plane serves the purpose. Bonds arising out of such
orientation of the bonding electron cloud are designated as -bonds. The bond formed by lateral
overlap of two atomic orbitals having maximum overlapping on both sides of the line connecting the
centres of the atoms is called a -bond. A -bond possesses a plane of symmetry, often referred to
as the nodal plane.
+ + +  + +
s s s-s  bond
+ + + -  + + -
s px s-px  bond
- + + + -  - + + -
px px px–px  - bond
+ + + +
+ 
- - - -
p - p bond
7.2 Limitation of Valance Bond Theory

Limitation1:
When the bonding scheme of certain polyatomic molecules is discussed, our simple valence bond theory
fails to accurately describe what is going on. Methane is one of these molecules where we must expand
upon our valence bond theory. The 2s orbital is filled with two electrons and the 2py orbital has no electrons
for use in bonding. This leaves only the 2px and the2pz orbitals as the orbitals that can participate in
bonding. We know however, that in CH4, four hydrogen atoms must make four bonds with the central
carbon atom.
What happens is that the carbon atom promotes one of its 2s electrons to the 2pyoribital. This leaves one
electron in the 2s orbital and one electron in the 2py orbital. All together, the central carbon now has four
unpaired valence electrons to bond to each of the four hydrogen atoms. Thus out of four C-H bonds one
should be different from remaining three C-H bonds. But experimentally it is found that all four C – H in
methane are identical in all aspect.
Limitation 2:
Another one of the shortcomings of the Valence Bond Theory is the inability to predict molecular
geometries. If we take a look at the bonding orbitals of H2O, only two of the p orbitals of sulphur bond with
a 1s orbital from H. The molecular geometry predicted by these two bonding orbitals is 90 o. This is
obviously incorrect because the valence bond theory does not take into account the lone pair electrons on
the central O atom. The two lone pair electrons create a angle of 104.5o between the two hydrogen atoms.
8. VSEPR THEORY
In 1957 Gillespie and Nyhom gave this theory to predict and explain molecular shapes and bond angles
more exactly. The theory was developed extensively by Gillespie as the Valence Shell Electron Pair
Repulsion (VSEPR) theory. This may be summarized as:
 The shape of the molecule is determined by repulsions between all of the electron pairs present in the
valence shell.
 A lone pair of electrons takes up more space round the central atom than a bond pair, since the lone
pair is attracted to one nucleus whilst the bond pair is shared by two nuclei. It follows that repulsion
between two lone pairs is greater than repulsion between a lone pair and a bond pair, which in turn is
greater than the repulsion between two bond pairs. Thus the presence of lone pairs on the central
atom causes slight distortion of the bond angles from the ideal shape. If the angle between a lone pair,
the central atom and a bond pair is increased, it follows that the actual bond angles between the atoms
must be decreased. The order of repulsion between lone pairs and bond pairs of electrons follows the
order as:
Lone pair - lone pair > lone pair – bond pair > bond pair – bond pair
 The magnitude of repulsions between bonding pairs of electrons depends on the electronegativity
difference between the central atom and the other atoms.
 Double bonds cause more repulsion than single bonds, and triple bonds cause more repulsion than a
double bond.
8.1 Geometry of Molecules
For the prediction of geometrical shapes of molecules with the help of VSEPR theory, it is convenient to
divide molecules into two categories as
(i) Molecules in which the central atom has no lone pair and
(ii) Molecules in which the central atom has one or more lone pairs.
Two Charge Clouds: When there are only two charge clouds, as occurs on the carbon atoms of (two
double bonds) and HCN (one single bond and one triple bond), the clouds are farthest apart when they
point in opposite directions. Thus, CO2 and HCN are linear molecules with bond angles of 180°.
Three Charge Clouds: When there are three charge clouds, as occurs on the carbon atom of
formaldehyde (two single bonds and one double bond) and the sulfur atom of SO2(one single bond, one
double bond, and one lone pair), the clouds are farthest apartwhen they lie in the same plane and point to
the corners of an equilateral triangle. Thus, a formaldehyde molecule has a trigonal planar shape, with H–
C–H and H-C=O bond angles near 120°. Similarly, an SO2 molecule has a trigonal planar arrangement of
its three charge clouds on sulfur, but one point of the triangle is occupied by a lone pair and two points by
oxygen atoms. The molecule therefore has a bent rather than linear shape, with an O–S–O bond angle of
approximately120° rather than 180°.
Four Charge Clouds: When there are four charge clouds, as occurs on the central atoms in CH4 (four
single bonds), NH3 (three single bonds and one lone pair), and H2O (two single bonds and two lone pairs),
the clouds are farthest apart if they extend toward the corners of a regular tetrahedron. The central atom
lies in the center of the tetrahedron, the charge clouds point toward the four corners, and the angle
between two lines drawn from thecenter to any two corners is 109.5°.
Five Charge Clouds: Five charge clouds, such as are found on the central atoms in PCl5, SF4 and ClF3
are oriented toward the corners of a geometric figure called a trigonalbipyramid. Three clouds lie in a plane
and point toward the corners of an equilateral triangle, the fourth cloud points directly up, and the fifth cloud
points down:
Six Charge Clouds: Six charge clouds around an atom orient toward the six corners of a regular
octahedron, a geometric solid whose eight faces are equilateral triangles. All six positions are equivalent,
and the angle between any two adjacent positions is 90°.
SF6 has six bond pairs in the outer shell and is a regular octahedron with bond angles of exactly 90°. In
BrF5, the Br also has six outer pairs of electrons, made up of five bond pairs and one lone pair. The lone
pair reduces the bond angles to 84°30’.
8.2 Geometry of Molecules
9. HYBRIDIZATION
The intermixing of two or more pure atomic orbitals of an atom with almost same energy to give same
number of identical and degenerate new type of orbitals is known as hybridization. The new orbitals formed
are also known as hybrid orbitals. The intermixing or hybridization of atomic orbitals is a mathematical
concept based on quantum mechanics. During this process, the wavefunctions, Ψ of atomic orbitals of
same atom are combined to give new wavefunctions corresponding to hybrid orbitals.
Requirements for atomic orbitals to undergo hybridization:
 The atomic orbitals of same atom with almost same energy can only participate in the hybridization.
 The fully filled or half filled or even empty orbitals can undergo hybridization provided they have almost
equal energy.
 The hybridization is the mixing of orbitals of same atom only. The combination of orbitals belonging to
different atoms is called bonding.
9.1 Hybrid Orbitals
The new orbitals that are formed due to intermixing of atomic orbitals are also known as hybrid orbitals,
which have mixed characteristics of atomic orbitals. The shapes of hybrid orbitals are identical. Usually they
have one big lobe associated with a small lobe on the other side. The hybrid orbitals are degenerate i.e.,
they are associated with same energy. The hybrid orbitals participate in the σ bond formation with other
atoms.
+
+ + +  
p sp
The number of hybrid orbitals formed is equal to the number of pure atomic orbitals undergoing
hybridization. E.g. If three atomic orbitals intermix with each other, the number of hybrid orbitals formed will
be equal to 3.The hybrid orbitals are filled with those electrons which were present in the pure atomic
orbitals forming them. The filling up of electrons in them follows Pauli's exclusion principle and Hund's rule.
Why atomic orbitals in a given atom undergo hybridization?

The hybrid orbitals are oriented in space so as to minimize repulsions between them. This explains why the
atomic orbitals undergo hybridization before bond formation. The reason for hybridization is to minimize the
repulsions between the bonds that are going to be formed by the atoms by using hybrid orbitals.
Remember that the hybridization is the process that occurs before bond formation.
The bond angles in the molecule are equal to or almost equal to the angles between the hybrid orbitals
forming the σ bonds. The shape of the molecule is determined by the type of hybridization, number of
bonds formed by them and the number of lone pairs.
9.2 Types of Hybridisation
There are many different types of hybridisation depending upon the type of orbitals involved in mixing such
as sp3, sp2, sp, sp3d, sp3d2, etc.
Let us now discuss various types of hybridisation along with some examples with reference to the
compounds of carbon, boron and beryllium.
(i)sp3 hybridisation. The type of hybridisation involves the mixing of one orbital of s-sub-level and three
orbitals of p-sub-level of the valence shell to form four sp3 hybrid orbitals of equivalent energies and shape.
Each sp3 hybrid orbital has 25% s-character and 75% p-character. These hybridised orbitals tend to lie as
far apart in space as possible so that the repulsive interactions between them are minimum. The four sp3
hybrid orbitals are directed towards the four corners of a tetrahedron. The angle between the sp3 hybrid
orbitals is 109.5° (Figure below).
sp3 hybridisation is also known as tetrahedral hybridisation. The molecules in which central atom is sp3
hybridised and is linked to four other atoms directly, have tetrahedral shape. Let us study some examples
of molecules where the atoms assume sp3 hybrid state.
Formation of methane (CH4). In methane carbon atom acquires sp3 hybrid states as described below :
Here, one orbital of 2s-sub-shell and three orbitals of 2p-sub-shell of excited carbon atom undergo
hybridisation to form four sp3 hybrid orbitals. The process involving promotion of 2s-electron followed by
hybridisation is shown in figure below.
As pointed out earlier the sp3 hybrid orbitals of carbon atom are directed towards the corners of regular
tetrahedron. Each of the sp3 hybrid orbitals overlaps axially with half-filled 1s-orbital of hydrogen atom
constituting a sigma bond figure below.
Because of sp3hybridisation of carbon atom, CH4 molecule has tetrahedral shape.
Formation of ethane (CH3—CH3). In ethane both the carbon atoms assume sp3 hybrid state as shown in
figure below. One of the hybrid orbitals of carbon atom overlaps axially with similar orbitals of the other
carbon atom to form sp3-sp3 sigma bond. The other three hybrid orbitals of each carbon atom are used in
forming sp3-s sigma bonds with hydrogen atoms as described below :
(ii) sp2 hybridisation. This type of hybridisation involves the mixing of one orbital of s-sub-level and two
orbitals of p-sub-level of the valence shell to form three sp2 hybrid orbitals. These sp2 hybrid orbitals lie in a
plane and are directed towards the corners of equilateral triangle (Figure below). Each sp2 hybrid orbital has
one-third s-character and two-third p-character. sp2 hybridisation is also called trigonal hybridisation. The
molecules in which central is sp2 hybridised and is linked to three other atoms directly have triangular planar
shape.
Let us study some examples of the molecules which involve sp2 hybridisation.
1. Formation of boron trifluoride (BF3). Boron (5B) atom has ground state configuration as 1s2 2s2, 2p1.
But in the excited state its configuration is 1s2, 2s1, 2px1, 2py1. One 2s-orbital of boron intermixes with two 2p-
orbitals of excited boron atom to form three sp2 hybrid orbitals as shown in figure below.
The sp2 hybrid orbitals of boron are directed towards the corners of equilateral triangle and lie in a plane.
Each of the sp2 hybrid orbitals of boron overlaps axially with half-filled orbital of fluorine atom to form three
B-F sigma bonds as shown in figure below.
Because of sp2 hybridisation of boron, BF3 molecule has triangular planar shape.
2. Formation of ethylene (C2H4). Both the carbon atoms in ethylene assume sp2 hybrid state. In acquiring
sp2 hybrid state, one 2s-orbital and two 2p-orbitals of excited carbon atom get hybridised to form three sp2
hybridised orbitals. However, one orbital of 2p-sub-shell of the excited carbon atom does not take part in
hybridisation. The promotion of electron and hybridisation in carbon atom is shown in figure below.
As already indicated, the three sp2 hybrid orbitals lie in one plane and are oriented in space at an angle of
120° to one another. The unhybridised 2p-orbital is perpendicular to the plane of sp2 hybrid orbitals as
shown in figure below.
In the formation of ethylene, one of the sp2 hybrid orbital of carbon atom overlaps axially with similar orbital
of the other carbon atom to form C—C sigma bond. The other two sp2 hybrid orbitals of each carbon atom
are utilised for forming sp2-s sigma bond with two hydrogen atoms.
The unhybridisedp-orbitals of the two carbon atoms overlap sidewise each other to form two p clouds
distributed above and below the plane of carbon and hydrogen atoms figure below.
Thus, in ethylene, the six atoms (bonded by sigma bonds) lie in one plane while the p bond is projected
perpendicular to the plane of six atoms (two C atoms and four H atoms). In ethylene molecule, the C = C
bond consists of one sp2-sp2 sigma bond and one p bond. Its bond length is134 pm.C—Hbond is sp2-ssigma bond
with bond length108 pm.The H—C—H angle is117.5°while H—C—C angle is121°.
(iii) sp-hybridisation. This type of hybridisation involves the mixing of one orbital of s-sub-level and one
orbital of p-sub-level of the valence shell of the atom to form two sp-hybridised orbitals of equivalent shapes
and energies. These sp-hybridised orbitals are oriented in space at an angle of 180° figure below. This
hybridisation is also called diagonal hybridisation.
Each sp hybrid orbital has equal s and p character, i.e., 50% s-character and 50% p-character. The
molecules in which the central atom is sp-hybridised and is linked to two other atoms directly have linear
shape.
Let us study some examples of molecules involving sp hybridisation.
Formation of beryllium fluoride (BeF2). Beryllium (4Be) atom has a ground state configuration as 1s2, 2s2.
In the excited state one of the 2s-electron is promoted to 2p-orbitals. One 2s-orbital and one 2p-orbitals of
excited beryllium atom undergo hybridisation to form two sp-hybridised orbitals as described in figure below.
(iv) sp3d -hybridisation

In this type of hybridization, one ‘s’, three ‘p’ and one ‘d’ orbitals of the same shell mix to give five
sp3d hybrid orbitals. These five sp3d hybrid orbitals orient themselves towards the corners of a
trigonalbipyramidal.
Cl Cl
P
Cl
Cl
Cl
(iv) sp3d2-hybridisation
In this type of hybridization, one ‘s’, three ‘p’ and two ‘d’ orbitals of the same/different shell mix to
give six sp3d2 hybrid orbitals. These six sp3d2 hybrid orbitals orient themselves towards the corners
of an octahedron. This type of hybridization is exhibited by SF6, SCl6 etc.
F
F F
F F
F
9.3 Method of Predicting the hybridization state

The hybrid state of the central atom in simple covalent molecule or polyatomic ion can be predicted by
using the generalized formula as described below:
Simple Molecule Polyatomic Anion Poyatomic Cation

1 1 1
X  [V  G ] X  [V  G  a ] X  [V  G  c]
2 2 2
In the above formulae,

V = Number of monovalent atoms or groups attached to the central atom
G = Number of outer shell electrons in ground state of the central atom
a = Magnitude of charge on anion
c = Magnitude of charge on cation
Calculate the value of X and decide the hybrid state of central atom as follows :
X 2 3 4 5 6 7
Hybrid state sp sp2 Sp3 sp3d sp3d2 sp3d3
For Example:
9.4HYBRIDISATION AND SHAPE OF DIFFERENT MOLECULES:
Types of No. of No. of
Shape of Molecule/
Molecule bond lone Hybrid Orbitals Examples
Ion
/ Ion pairs pairs
2 0 sp Linear BeCl2, HgCl2
2 1 sp2 bent (V-shape) SnCl2, PbCl2

AX2
2 2 sp3 bent (V-shape) H2O, OF2
2 3 sp3d Linear I3–, XeF2
3 0 sp2 Trigonal planar BF3, BCl3
AX3 3 1 sp3 Pyramidal NH3, H3O+
3 2 sp3d T-shape ClF3, BrF3
4 0 sp3 Tetrahedral CH4, NH4+
Distorted tetrahedral
AX4 4 1 sp3d SF4
(See Saw)
4 2 sp3d2 Square planar XeF4
5 0 sp3d Trigonalbipyramidal PCl5

AX5
5 1 sp3d2 Square pyramidal IF5
6 0 sp3d2 Octahedral SF6

AX6
6 1 sp3d3 Distorted Octahedral XeF6
AX7 7 0 sp3d3 Pentagonal bipyramidal IF7
10.BONDING PARAMETERS
10.1 Bond Energy
It has already been pointed out that the formation of a bond occurs as a result of decrease of energy.
Therefore, same amount of energy is required to break the bond between the two atoms. For example, the
energy released during the formation of bonds between the gaseous hydrogen atoms to form one mole of
hydrogen molecules is 433 kJmol-1. This energy involved in making or breaking of bonds is referred to as
bond energy. Thus, bondenergy may be defined as the amount of energy required to break one mole of
bonds of same kind so as to separate the bonded atoms in the gaseous state.
The magnitude of bond energy reflects the strength of the bond. Its magnitude depends upon the following
factors:
1. Size of the participating atoms:
Larger the size of the atoms involved in bond formation, lesser is the extent of overlapping and
consequently, smaller is the value of bond energy.
For example, bond energy of Cl—Cl bond is 237 kJmol-1 whereas that of H—H bond is 433 kJmol-1.
2. Multiplicity of bonds:
The magnitude of bond energy increases with the multiplicity of bonds even though the atoms involved
in the bond formation are same. It is because of the fact that with the multiplicity of bonds the number of
shared electrons between the atoms increases. As a result, the attractive force between nuclei and
electrons also increases and consequently, the magnitude of bond energy increases. For example, bond
energy of C — C bond is 348 kJ/mol-1 but that of C = C bond is 619 kJ mol-1. The average bond
energies of some bonds are given in Table below.
Bond Energies of Some Common Bonds
3. Number of lone pairs of electrons:

Greater the number of lone pair of electrons present on the bonded atoms, greater is the repulsive
interactions between them and smaller is the bond energy
10.2 BOND LENGTH

It has already been discussed that two bonded atoms in a molecule remain held up at a certain distance
from each other. They cannot approach too close because it leads to repulsive interactions and potential
energy of system increases. This minimum distance between the bonded atoms is referred to as bond
length. Thus, bond length may be defined as the average distance between the centers of nuclei of the two
bonded atoms in a molecule. Bond length is usually expressed in Angstrom units (Å) or Pico meters (pm)
and it can be determined experimentally by X-ray diffraction and other spectroscopic techniques.
1. Bond length increases with the increase in the size of the atoms:
Bond length between hydrogen and chlorine atoms in HCl molecule is 127 pm whereas bond length
between carbon and chlorine atoms is C—Cl bond 177 pm.
2. Bond length decreases with the multiplicity of bonds:

It is because of the fact that larger the number of electrons shared by the two atoms greater will be
attractive force between electrons and the nuclei and consequently, lesser is the bond length. For
example, bond length of C—C bond is 154 pm whereas that of C = C bond is 134 pm. Bond lengths of
some common bonds are given in Table below.
Table below. Bond Lengths of Some Common Bonds
10.3BOND ANGLE
We know that overlapping of atomic orbitals forms covalent bonds. Due to directional character of atomic
orbitals, the covalent bonds in a molecule are oriented in specified directions. The bond angle is defined as
the average angle between the lines representing the orbitals containing the bonding electrons.
Bond angle is expressed in degree/minute/seconds. For example, H—C—H bond angle in CH4 molecule is
109° 28'. Similarly, F—B—F bond angle in BF3 is 120° and H—N—H bond angle in NH3 molecule is 107°.
The bond angles in CH4, NH3, H2O and BF3 molecules are shown below in Figure below.
Following factors can affect bond angle:
1.Hybridisation of central atom:

sp 180°
sp2 120°
sp3 109.5°
sp3d 90°, 120°, 180°
sp3d2 90°, 180°
3 3
sp d 72°, 90°, 144°, 180°
2. Presence of lone pair: lp─bp repulsion is more than bp─bp
3. Electronegativity of central atom: Due to more electronegativity of central atom bond pair get shifted
toward it and distance between them decrease thus further bp─bprepulsion increases.
4. Multiple bonds: Due to more electron density for double bond than that of single bond, repulsion due to
double bond is more than single bond.
11. Resonance
Carbon dioxide may be represented by Lewis dot formula as
.. ..
: O :: C :: O : or O=C=O … (i)
The bond length of C=O is 1.22 Å, but the actual measured value is 1.15 Å. Further CO 2 is quite stable and
does not show the characteristic reactions of the carbonyl group, as shown by aldehydes and ketones.
Without shifting, the relative positions of atoms of CO2 can be represented by two more Lewis formulae:
O C O O C O
(ii) (iii)
In (ii) and (iii), the two bonds between C and O are different, one being a triple bond and the other a
single bond. Both the CO bonds in CO2 are identical. It is now obvious that none of these structures
actually represents CO2. To explain this difficulty the concept of resonance was introduced, according to
which CO2 cannot be accurately depicted by any Lewis formula. The actual structure of CO 2 is a resonance
hybrid of the three structures:
O = C = O O C  O O C O.
These different structures are called the canonical or contributing structures. The actual structure of
CO2 is different from the canonical structures and although it is closely related to them, the actual
structure cannot be represented on paper using the accepted symbols. All the molecules of CO2 have
the same structure. Usually, a doubleheaded arrow  is used between the canonical structures.
Imagine that you are trying to describe to a friend what a rhinoceros looks like. You might tell your friend
that a rhinoceros looks like a cross between a unicorn and a dragon.
Unicorn Dragon Rhinoceros

resonance contributor resonance contributor resonance hybrid
The unicorn and the dragon don’t really exist, so they are like the resonance contributors. They are not in
equilibrium: A rhinoceros does not jump back and forth between the two resonance contributors, looking
like a unicorn one minute and a dragon the next. The rhinoceros is real, so it is like the resonance hybrid.
11.1 Conditions for Resonance

Resonance can occur when the canonical structures
(i) have the constituent atoms in the same relative positions;
(ii) have nearly the same energy;
(iii) have the same number of unpaired electrons (to allow for continuous change from one type of bond
to another);
(iv) differ in the distribution of electrons around the constituent atoms;
(v) (molecules or ions) are planar.
11.2 Resonance Energy
The resonance hybrid is a more stable structure than any of the contributing structures. This means that
resonance hybrid has less energy than any of the contributing structures. The difference in energy
between the actual observed energy of the resonance hybrid and the most stable of the
contributing structures is called resonance energy.
OTHER EXAMPLES OF RESONANCE
(i) Sulphur dioxide SO2

.. ..
S S
.. O :

:O :
:O
.. .. .. : O
..
(ii) Nitrous oxide (dinitrogen oxide), N2O

N = N = O  N N O
(iii) Nitric oxide, NO

. .. .. .
: N  O :  : N  O :
(iv) Carbonate ion, CO  (planar, triangular)

3
O O O

O C O C O C
 
O O O
(v) Benzene, C6H6. It is a resonance hybrid of the following structures (hexagonal, planar).
I II III IV V
Kekule Structures Dewar Structures
C–C bond length is 1.54 Å; C=C bond length is 1.34 Å. In benzene, all the
C–C bonds are identical in length, 1.39 Å, i.e., intermediate between those of single and double
bonds. Note that shortening of bond length and therefore increased stability is an indication of the
existence of resonance [Decrease in dipole moment also indicates resonance]. Resonance energy of
benzene is 152 kJ/mol.
12. TRANSITION FROM IONIC TO COVALENT BOND – FAJANS’ RULE

Just as a covalent bond may have partial ionic character an ionic bond may also show a certain degree of
covalent character. When two oppositely charged ions approach each other closely, the cation would
attract the electrons in the outer shell of the anion and simultaneously repel its nucleus. This produces
distortion or polarization of the anion, which is accompanied by some sharing of electrons between the
ions, i.e., the bond acquires a certain covalent character. The formation of a covalent bond between two
ions may be illustrated with reference to formation of AgI.
Ag+ I Ag+ I Ag+ ... I
separate ions distorted ions covalent bond

The polarising power of a cation is expressed by an index,  defined as
Cationic charge
 (where is called ionic potential)
Cationic radius
Again the extent to which an anion is polarized is given by its polarisability. This is governed by the charge
and size of the anion.
FACTORS EFFECTING POLARIZATION AND POLARISABILITY (FAJAN’S RULE)

1.Cation Size:
Smaller is the cation more is the value of  and hence more its polarising power. As a result more
covalent character will develop. Let us take the example of the chlorides of the alkaline earth metals. As
we go down from Be to Ba the cation size increases and the value of  decreases which indicates that
BaCl2 is less covalent i.e. more ionic. This is well reflected in their melting points. Melting points of
BeCl2 = 405°C and BaCl2 = 960°C.
2. Cationic Charge:
More is the charge on the cation, the higher is the value of  and higher is the polarising power. This can
be well illustrated by the e.g. already given, NaBr and AlBr3. Here the charge on Na is +1 while that of Al
is +3, hence polarising power of Al is higher which in turn means a higher degree of covalency resulting
in a lowering of melting point of AlBr3 as compared to NaBr.
3. Noble Gas vs Pseudo Noble Gas Cation:

A pseudo noble gas cation consist of a noble gas core surrounded by electron cloud due to filled d-
subshell. Since d-electrons provide inadequate shielding from the nuclei charge due to relatively less
penetration of orbitals into the inner electron core, the effective nuclear charge (ENC) is relatively larger
than that of a noble gas cation of the same period. KCl has got a melting point of 776°C while CuCl has
got melting point of 425°C. This is a classic example of what we gave in this paragraph. The
configuration of Cu+ = [Ar] 3d10 while that K+ = [Ar]. Due to presence of d-electrons Effective Nuclear
Charge is more and therefore Cl– is more polarised in CuCl leading to a higher degree of covalency and
lower melting point.
4.Anion Size:
Larger is the anion, more is the polarisability and hence more covalent character is expected. An e.g. of
this is CaF2 and CaI2, the former has melting point of 1400°C and latter has 575°C. The larger size of I –
ion compared to F– causes more polarization of the molecule leading to a lowering of covalency and
melting point.
5. Anionic Charge:
Larger is the anionic charge, the more is the polarisability. A well illustrated example is the much higher
degree of covalency in magnesium nitride (Mg++ N3–) compared to magnesium fluoride (Mg++ F—). This is
due to higher charge of nitride compared to fluoride.
13. Polar Covalent Bond
Sharing of electrons between two atoms sets up a covalent bond. It is further classified as polar or non-
polar depending upon the fact whether the electron pair is shared unequally between the atoms or shared
equally. For example, the covalent bonds in H2 and Cl2 are called non-polar as the electron pair is equally
shared between the two atoms.
.. ..
H:H :Cl:Cl:  
.. ..
(Both formed by equal sharing
of electrons between the atoms
H ------ Cl
i.e. by non-polar bonds )
In the case of hydrogen Chloride the bond is polar as the electron pair is unequally shared. Chlorine has a
greater attraction for electrons or has higher electronegativity than hydrogen and the shared pair of
electrons is nearer to the fluorine atom than hydrogen atom. The hydrogen end of the molecule, therefore,
appears positive with respect to Chlorine. Such covalent bonds are said to be polar.
13.1 Dipole Moment

The electronegativities of the two atoms which form the covalent bond are not the same. The atom having
higher electronegativity will draw the bonded electron pair more towards itself resulting in a partial charge
separation. The distribution of the electron cloud in the bond does not remain uniform and shifts towards
the more electronegative one. Such bonds are called polar covalent bonds. For example the bond formed
between hydrogen and chlorine or between hydrogen and oxygen in water is of this type.
    
H Cl H O  H
Molecules like HCl, H2O, NH3 i.e. molecules of the type H – X having two polar ends (positive and
negative) are known as polar molecules. The extent of polar character or the degree of polarity in a
compound is given by it’s dipole moment which is defined as the product of the net positive or negative
charge and the distance of separation of the charges i.e. the bond length. The symbol of dipole moment is
. It is vector quantity and is defined as the product of the magnitude of charge on any of the atom and the
distance between the atoms.
Electric pole Electric pole
+ 
μ = q  d
The unit of dipole moment is Debye (D)
1D = 3.33  10–30 Cm = 10–18esu cm
Dipole moment is indicated by an arrow having a symbol ( ) pointing towards the negative end.
Dipole moment has both magnitude and direction and therefore it is a vector quantity.
Examples of Covalent compounds having diapole moment:
O S
O=C=O S=C=S Cl  Hg  Cl
H H O O
1.84D 1.63D 0D 0D 0D
Let us study an interesting case of NH3 and NF3 molecule. Both the molecules have pyramidal shape with
a lone pair of electrons on nitrogen atom. Although fluorine is more electronegative than nitrogen, the
resultant dipole moment of NH3(4.90 × 10─30 Cm ) is greater than that of NF3 (0.8 × 10─30 Cm). This is
because, in case of NH3 the orbital dipole due to lone pair is in the same direction as the resultant dipole
moment of the N – H bonds, whereas in NF3 the orbital dipole is in the direction opposite to the resultant
dipole moment of the three N–F bonds.
The dipole moments of the aromatic compounds present a very good illustration of dipole moment. We all
know when a substituted benzene is treated with a reagent different products namely ortho, meta and para
products are formed. The dipole moments of these products are different since the orientation of the
groups are different at ortho, meta and para position. Let us take an example which will make it easily
digestive for you. Suppose we have three isomers of o-nitrophenol, m-nitrophenol and p-nitrophenol. We
have also the e.g. o-aminophenol, m-aminophenol and p-aminophenol.
X X X
Y Para
Meta
Ortho Y
ortho = 12  22  212 cos 60 o
meta = 12   22  21 2 cos 120 
para = 12   22  21 2 cos 180 
13.2 Percentage Ionic Character

The measured dipole moment of a substance may be used to calculate the percentage ionic character of
a covalent bond in simple molecules.
Percent ionic character = Observed dipole moment
× 100
Calculated dipole moment assuming 100% ionic bond
14.MOLECULAR ORBITAL THEORY

Because arguments based on atomic orbitals focus on the bonds formed between valence electrons on an
atom, they are often said to involve a valence-bond theory.The valence-bond model can't adequately
explain the fact that some molecules contains two equivalent bonds with a bond order between that of a
single bond and a double bond. The best it can do is suggest that these molecules are mixtures, or hybrids,
of the two Lewis structures that can be written for these molecules.
This problem, and many others, can be overcome by using a more sophisticated model of bonding based
on molecular orbitals. Molecular orbital theory is more powerful than valence-bond theory because the
orbitals reflect the geometry of the molecule to which they are applied. But this power carries a significant
cost in terms of the ease with which the model can be visualized.
14.1 Formation of Molecular Orbitals

Molecular orbitals are obtained by combining the atomic orbitals of the atoms in the molecule. Consider the
H2 molecule, for example. One of the molecular orbitals in this molecule is constructed by adding the
mathematical functions for the two 1s atomic orbitals that come together to form this molecule. Another
orbital is formed by subtracting one of these functions from the other, as shown in the figure below.
One of these orbitals is called a bonding molecular orbital because electrons in this orbital spend most of
their time in the region directly between the two nuclei. It is called a sigma ( ) molecular orbital because it
looks like an s orbital when viewed along the H-H bond. Electrons placed in the other orbital spend most of
their time away from the region between the two nuclei. This orbital is therefore an antibonding, or sigma
star ( *), molecular orbital.
The bonding molecular orbital concentrates electrons in the region directly between the two nuclei.
Placing an electron in this orbital therefore stabilizes the H2 molecule. Since the * antibonding molecular
orbital forces the electron to spend most of its time away from the area between the nuclei, placing an
electron in this orbital makes the molecule less stable.
Electrons are added to molecular orbitals, one at a time, starting with the lowest energy molecular orbital.
The two electrons associated with a pair of hydrogen atoms are placed in the lowest energy, or bonding,
molecular orbital, as shown in the figure below. This diagram suggests that the energy of an H2 molecule is
lower than that of a pair of isolated atoms. As a result, the H2 molecule is more stable than a pair of isolated
atoms.
If we arbitrarily define the Z axis of the coordinate system for the O2 molecule as the axis along which the
bond forms, the 2pz orbitals on the adjacent atoms will meet head-on to form a 2P bonding and a 2P *
antibonding molecular orbital, as shown in the figure below.
The 2px orbitals on one atom interact with the 2px orbitals on the other to form molecular orbitals that have
a different shape. These molecular orbitals are called pi

   orbitals because they look like p orbitals when
viewed along the bond. Whereas  and  * orbitals concentrate the electrons along the axis on which the
nuclei of the atoms lie,  and  * orbitals concentrate the electrons either above or below this axis.
The 2px atomic orbitals combine to form a

x bonding molecular orbital and a  x * antibonding molecular
y y *
orbital. The same thing happens when the 2py orbitals interact, only in this case we get a and a
antibonding molecular orbital. Because there is no difference between the energies of the 2px and
2py atomic orbitals, there is no difference between the energies of the

x and y or the  x * and  y *
molecular orbitals.
The number of molecular orbitals produced must always be equal to the number of atomic orbitals
involved. Electron density is increased for the bonding MO’s in the inter-nuclear region but decreased
for the anti-bonding MO’s, Shielding of the nuclei by increased electron density in bonding MO’s
reduces inter nuclei repulsion and thus stabilizes the molecule whereas lower electron density even as
compared to the individual atom in anti-bonding MO’s increases the repulsion and destabilizes the
system.
Anti-bonding MO
Energy
O
Bonding MO
Distance between atoms
In denotion of MO’s, indicates head on overlap and  represents side ways overlap of orbitals. In
simple homo-nuclear diatomic molecules the order of MO’s based on increasing energy is
2p    
*

1s1*s2 s *2 s2px  y   2py *2px
 2 p z  
*
 2 p z 

Note that the 2py atomic orbitals gives  bonding and * anti-bonding MOs and the 2pzatomic orbital gives 
bonding and * anti-bonding MO’s.The bonding 2py. MOs have exactly the same energy and are said to
be double degenerate and in a similar way *2py and 2pz are also doubly degenerate.
This order is true except B2, C2& N2. For them 2py and 2pz are probably lower than 2px.
no. of es occupying bonding MO' s  no. of es occupying anti  bonding MO' s
Bond order =
2
Atoms or molecules in which the electrons are paired are diamagnetic repelled by both poles of a
magnetic. Those that have one or more unpaired electrons are paramagnetic attracted to a magnetic
field. Liquid oxygen is attracted to a magnetic field and can actually bridge the gap between the poles of a
horseshoe magnet. The molecular orbital model of O2 is therefore superior to the valence-bond model,
which cannot explain this property of oxygen.
Application of MOT to homonuclei diatomic molecules

H2 molecule : Total no. of electrons = 2
Arrangement :  12s
Bond order : ½ (2 – 0) = 1
H 2 molecule : Total no. of electrons = 1

Arrangement :  1s1
Bond order : ½ (1 – 0) = 1/2
He2 molecule : Total no. of electrons = 4
Arrangement :  1s2 1*s 2
Bond order : ½ (2 – 2) = 0
He2 molecule does not exist.
He 2 molecule : Total no. of electrons = 3
Arrangement :  1s2 1*s1

Bond order : ½ (2 – 1) = 1/2
So He 2 exists and has been detected in discharge tubes.
Li2 molecule : Total no. of electrons = 6

Arrangement :  1s2 1*s 2  2 2s
Bond order : ½ (4 – 2) = 1
No unpaired e’s so diamagnetic
Be2 molecule : Total no. of electrons = 8

Arrangement :  1s2 1*s 2  2 2s *2 s2
Bond order : ½ (4 – 4) = 0
No unpaired e–s so diamagnetic
B2 molecule : Total no. of electrons = 10
 2 p 
1
Arrangement :  12s 1*s2  22s *2 s2  1 y 

 2 pz 
Bond order : ½ (6 – 4) = 1
It is paramagnetic
C2 molecule : Total no. of electrons = 12
 2 p y 
2
2
 *2  2s
 2 
2
 *2
 2 p z 
1s 2s
Bond order : ½ (4 – 0) = 2
It is diamagnetic
N2 molecule : Total no. of electrons = 14

*2 2 *2 2py  2
2
Arrangement :  1s 1s  2 s  2 s  2  2px
2

2pz 
Bond order : ½ (6 – 0) = 3
 It is diamagnetic
O2 molecule : Total no. of electrons = 16

 22p   
*1

Arrangement :  12s 1*s2  2 2s *2 s2 22px  2 y   2 p y 
 2 pz  
*
 2 pz 
1

Bond order : ½ (6 – 2) = 2
It is paramagnetic
F2 molecule : Total no. of electrons = 18
 22py  *2 
2
 *2  2s
2
* 2 2px
2
 2 
2 py *
 *2   2 px
 2 pz   2pz 
1s 2s
Bond order : ½ (6 – 4) = 1
Ex. Arrange the species O2, O2–,O22– and O2+ in the decreasing order of bond order and stability and also
indicate their magnetic properties.
Sol: The molecular orbital configuration of O2, O2–,O22– and O2+ are as follows:
O2 = 1s2, *1s2, 2s2, *2s2, 2px2, 2py2, 2pz2, *2py1 = *2pz1 Bond order =2 ,
No. of unpaired electrons = 2  paramagnetic
O2– = 1s2, *1s2, 2s2, *2s2, 2px2, 2py2, 2pz2, *2py2 = *2pz1 Bond order =1.5 ,
No. of unpaired electrons = 1  paramagnetic
O2 = 1s , *1s , 2s , *2s , 2px , 2py , 2pz2, *2py2 = *2pz2
2– 2 2 2 2 2 2 Bond order =1,
No. of unpaired electrons = 0  diamagnetic
O2 = 1s , *1s , 2s , *2s , 2px , 2py , 2pz2, *2py1 = *2pz0
+ 2 2 2 2 2 2
Bond order =2.5, No. of unpaired electrons = 1  paramagnetic
Now as the bond order decreases in the order O2+ O2 O2– O22–
Ex: Compare the stabilities of H2, H2+ and H2–.

1
Sol: Configuration of H2 will be 1s2, *1s0 => B.O. = (2 – 0) = 1
2
1 1
H2+ means removal of an electron from the bonding M.O. => B.O. = (1 – 0) =
2 2
1 1
H2– means addition of an electron in the anti-bonding M.O. (*1s). => B.O. = (2 – 1) =
2 2
So from the bond order it may be seen that both H2 & H2 may have the same bond energy. But
removal of an electron from a diatomic species tend to decrease the inter electronic repulsion and
thereby shorter the bond length. So the bond energy becomes more than that compared to H2 .
Higher the bond order the greater will be the bond energies and hence greater the stability.
14.2Intermixing of orbital
The 2s and 2p energy levels of O and F are very far apart. The combination of the 2s orbitals from the two
atoms form a sigma bonding and sigma antibonding orbitals in a way very similar to the case of the
hydrogen molecules, because the 2p orbitals have little to do with the 2s orbitals.
On the other hand, the three 2p orbitals of each O (or F) atom can form one sigma and two pi bonds and
their corresponding antibonding molecular orbitals. The interaction of the 2p orbitals for the sigma bond is
stronger, and the levels of sigma and anti sigma bonds are farther apart than those of pi and anti pi bonds.
Atomic energy levels E in kJ mol-1
of second group elements
Element E2s E2p E2p-E2s
Li -521
Be -897
B -1350 -801 549
C -1871 -1022 849
N -2470 -1274 1196
O -3116 -1524 1592
F -3879 -1795 2084
Ne -4680 -2084 2596
Recently, the study of the energies of electrons in molecules revealed that the relative energy levels of
molecular orbitals of Li2 to N2 are different from those of O2 and F2. The explanation for the difference
comes from the consideration of hybrid atomic orbitals. Because the 2s energy levels and 2p energy levels
for Li to N are relatively close, the 2s orbitals are influenced by the 2p orbitals. This influence makes the
bonding orbitals stronger than, and the antibonding orbitals weaker than those formed by pure 2s orbitals.
This process is called s p mixing
Due to s p mixing, the 2p orbital is weakened, and the *2pis also affected. These effects cause the relative
order to change.
15. HYDROGEN BONDING

A hydrogen bond is a type of attractive intermolecular force that exists between two partial electric charges
of opposite polarity. Although stronger than most other intermolecular forces, the hydrogen bond is much
weaker than both the ionic bond and the covalent bond. Within macromolecules such as proteins and
nucleic acids, it can exist between two parts of the same molecule, and figures as an important constraint
on such molecules' overall shape.
As the name "hydrogen bond" implies, one part of the bond involves a hydrogen atom. The hydrogen must
be attached to a strongly electronegative heteroatom, such as oxygen, nitrogen or fluorine, which is called
the hydrogen-bond donor. This electronegative element attracts the electron cloud from around the
hydrogen nucleus and, by decentralizing the cloud, leaves the atom with a positive partial charge. Because
of the small size of hydrogen relative to other atoms and molecules, the resulting charge, though only
partial, nevertheless represents a large charge density. A hydrogen bond results when this strong positive
charge density attracts a lone pair of electrons on another heteroatom, which becomes the hydrogen-
bond acceptor.
The hydrogen bond is not like a simple attraction between point charges, however. It possesses some
degree of orientational preference, and can be shown to have some of the characteristics of a covalent
bond. This covalency tends to be more extreme when acceptors bind hydrogens from more electronegative
donors.
In the species X—H----X, as the electronegativity of X increases the strength of hydrogen bond (H- - - X)
also increases. Thus the order of increases of the and (F—H- - - - F) is shown below
N — H - - - - N O — H - - - - O  F — H - - - - F
[The electronegativity of N = 3.0, O = 3.5, F = 4.0 in Pauling scale]
CONDITIONS FOR HYDROGEN BONDING

 Hydrogen should be linked to a highly electronegative element.
 The size of the electronegative element must be small.
These two criteria’s are fulfilled by F, O, and N in the periodic table. Greater the electronegativity and
smaller the size, the stronger is the hydrogen bond which is evident from the relative order of energies of
hydrogen bonds.
Although the electronegativities of nitrogen and chlorine are same (3.0) , nitrogen can form hydrogen bond
but Cl does not form effective hydrogen bond due to its larger size.
TYPES OF HYDROGEN BONDING
1. INTERMOLECULAR HYDROGEN BONDING:

This type of bonding takes place between two molecules of the same or different types. For example,
H H H
O—H----- O — H ------ O — H ------
Inter molecular hydrogen bonding leads to molecular association in liquids like water etc. Thus in water
only a few percent of the water molecules appear not to be hydrogen bonded even at 90°C. Breaking of
those hydrogen bonds throughout the entire liquid requires appreciable heat energy. This is indicated in the
relatively higher boiling points of hydrogen bonded liquids.
Crystalline hydrogen fluoride consists of the polymer (HF)n. This has a zig-zag chain structure involving H-
bond.
F F
H H
H H H
F F F
2. INTRAMOLECULAR HYDROGEN BONDING:

This type of bonding occurs between atoms of the same molecule present on different sites. Intramolecular
hydrogen bonding gives rise to a closed ring structure for which the term chelation is sometimes used.
Examples are, o-nitrophenol, salicylaldehyde.
H H
O O O
O
N C
O H
Salicaldehyde
o-nitrophenol
Ex: o-hydroxybenzaldehyde is less soluble in water than p-hydroxybenzaldehyde. Explain.

Sol: A substance is said to be soluble in water if it is capable of forming H-bonding with water molecule.
In o-hydroxybenzaldehyde due to intra-molecular chelation the –OH group is not available to form
hydrogen bond with water hence it is sparingly soluble in water. On the other hand the –OH group is
available in p-hydroxybenzaldehyde to form H-bond with water and hence it is more soluble
compared to the o-isomer.
O H O H O H
H
O
C
H
o-Isomer H C O p-isomer
Ex: HF forms stronger H-bonds than H2O, still Hvap of HF is lower than that of pure water.
Explain?
Sol: The number of H–bonds broken per mole of HF on vaporization is much less than in the case of
H2O. Each HF forms two bonds, while each H2O molecule forms 4 bonds. In case of water vapour
at boiling pt. contains essentially monomers while HF contains polymers i.e., all H–bonds are not
broken on vaporization whereas all 4-H bonds are broken per molecule of water.
Importance of Hydrogen Bonding in Biological Systems

Hydrogen bonding plays a vital role in physiological systems. Proteins contain chains of amino acids. The
amino acid units are arranged in a spiral form somewhat like a stretched coil spring (forming a helix). The
N-H group of each amino acid unit and the fourth C=O group following it along the chain, establishes the
N–H---O hydrogen bonds. These bonds are partly responsible for the stability of the spiral structure.
16. INTERMOLECULAR FORCES

Intermolecular forces are forces of attraction or repulsion which act between neighboring particles: atoms,
molecules or ions. They are weak compared to the intramolecular forces, the forces which keep a molecule
together. For example, the covalent bond present within HCl molecules is much stronger than the forces
present between the neighbouring molecules, which exist when the molecules are sufficiently close to each
other. These forces are also known as Vander Waal’s Forces.
Attractive intermolecular forces consist of four types:
1. Dipole–dipole forces
Dipole–dipole interactions are electrostatic interactions of permanent dipoles in molecules. These
interactions tend to align the molecules to increase the attraction (reducing potential energy). An
example of a dipole–dipole interaction can be seen in hydrogen chloride (HCl): The positive end of a
polar molecule will attract the negative end of the other molecule and cause them to be arranged in a
specific arrangement. Polar molecules have a net attraction between them. For example HCl and
chloroform (CHCl3)
2. Ion–dipole forces
Ion-dipole and induced-dipole forces operate much like dipole-dipole and induced-dipole interactions.
However, instead of only polar and non-polar molecules being involved, ion interactions involve ions (as
the name suggests). Ion-dipole and ion-induced dipole forces are stronger than dipole interactions
because the charge of any ion is much greater than the charge of a dipole moment. Ion-dipole is
greater than Hydrogen bonding.
An ion-dipole force consists of an ion and a polar molecule interacting. They align so that the positive
and negative forces are next to one another, allowing for maximum attraction. An ion-induced dipole
force consists of an ion and a non-polar molecule interacting. Like a dipole-induced dipole force, the
charge of the ion causes a distortion of the electron cloud on the non-polar molecule.
3. Dipole-induced dipole force or Debye forces
The induced dipole forces appear from the induction (also known as polarization), which is the attractive
interaction between a permanent multipole on one molecule with an induced (by the former di/multi-
pole) multipole on another molecule. This interaction is called Debye force after Peter J.W. Debye.
The example of an induction-interaction between permanent dipole and induced dipole is HCl and Ar. In
this system, Ar experiences a dipole as its electrons are attracted (to H side) or repelled (from Cl side)
by HCl. This kind of interaction can be expected between any polar molecule and non-
polar/symmetrical molecule. The induction-interaction force is far weaker than dipole-dipole interaction,
but stronger than the London dispersion force.
4. Instantaneous dipole-induced dipole forces or London dispersion forces.
Otherwise known as quantum-induced instantaneous polarization or instantaneous dipole-induced
dipole forces, the London dispersion force is caused by correlated movements of the electrons in
interacting molecules. The electrons, which belong to different molecules, start "fleeing" and avoiding
each other at the short intermolecular distances, which is frequently described as formation of
"instantaneous dipoles" that attract each other.
17. ODD ELECTRON SPECIES

It has been observed that almost all the compounds of non-transition elements contain an even number of
bonding electrons. Very few exceptions like NO, NO2 etc. possess odd number of bonding electrons. Such
type of compounds are called Odd Molecules. The odd molecules are classified into following two
categories
1.One electron bond molecules and ions:

H2+ ion is an example in which one electron bond is formed. H2+ ion is considered to be resonance hybrid of
the two resonating structures (i) and (ii) i) +
H H ii) H H+
H2+ ion has its bond energy equal to 61 kcal/mol. These two forms are of equal stability. H 2 molecules has
its bond energy equal to 109 kcal/mol. Inter nuclear distance between the H-atoms in H2+ is 1.06Å and in
H2 molecule it is 0.74Å.
Other examples having 1 electron bond are Li2+, Na2+, K2+ ions and B2H6 (diborone) molecule.
2. Three electron bond molecules and ions:

Examples of some molecules and ions are given below.
x x
He2+ ion: This ion is represented as a resonance hybrid of (a) and (b) He x He++He  x He
Resonance between the two forms (a) and (b) leads to the formation of a three-electron bond between He
and He+. It is only one electron that plays part in resonance. Thus, 1- and 3-electron bonds have
approximately the same energy. The binding energy of He2+ is 58 kcal/mol.
O2 molecule: Normal VBT structure for O2 molecules
O Oxx
xx
This structure however, does not represent the paramagnetic property of O 2 molecule. It is therefore
assumed that two O-atoms in O2 molecule are linked by a normal covalent bond and two 3-electron bonds.
Thus O2molecule is O O
Properties of Odd-electron Bonds

 One and three electron bonds are approximately half as strong as an ordinary electron pair bond
(normal covalent bond)
 Such bonds are not stable if the electronegativity difference between the atoms involved is large.
Formation of 1-electron bond generally occurs between like atoms while its formation between unlike
atoms is rare.
 Molecules containing a 3-electron bond in addition to an electron pair bond sometimes shows a
tendency to dimerise. Since the three electron bond is half as strong as an electron pair bond, the
energy of dimer will be close to that of two monomeric molecules.
18. SOLVED PROBLEMS
18.1 Subjective
Problem 1:The bond angle of NF3 is less than that of NH3. Explain.
Solution: Both NH3 and NF3 have a lone pair of electrons. But fluorine being highly electronegative, the
bond pair electrons are drawn more towards F in NF3, whereas in NH3 it is drawn towards N. So in
NF3 the bond pairs being displaced away from the central atom has very little tendency to open up
the angle. But in NH3 this opening up is more as the bond pair electrons are closer to each other.
So bond angle of NF3 is less than NH3.
N N
Repulsion more
H
H H F F F
Repulsion less
Problem 2:Why is that Lithium salts have a greater degree of covalent character than other halides
of the group?
Solution: The small size of Li+ gives it a large polarising power, hence covalent nature of its compound
increases. It can be viewed in terms of Fajan's rule
 Smaller the cation
 Larger the anion
 Greater the charge density as the surface causes greater polarising power of Li+
Hence, greater the covalent nature.
Problem3:The solubility of the hydroxides of the alkaline earth metals increases i.e. Ba(OH)2 has
got a higher solubility in water compared to Mg(OH)2-. Why?
Solution: Here both the cations Ba2+ and Mg2+ have the same charge, but as the radius of Ba2+ is more
therefore  of Ba2+ is less which implies that Ba(OH)2 having higher degree of ionic character is
more soluble in polar solvents like water.
But now if I ask to predict the solubility of MgSO4& BaSO4. The answer seems to be quite
similar to the earlier one and BaSO4 turns out to be the one having higher solubility. But
contrary to our expectation the trend is reversed here. BaSO4 is sparingly soluble in water. The
question comes why? In case of hydroxide it is something. In case of sulfate it’s the other way
around. Is there any way by which we can a predict the solubility trend? The answer is yes.
When a lattice is dissolved in water, the ions became solvated and the solvated ions are more
stable than a free ion and due to this stability energy is released. This energy released is called
solvation energy and if this overcomes the lattice energy then it is soluble. The lattice energy of
NaCl is 778 kJ mol–1 and the heats of hydration of Na+ and Cl– is –787 kJ mol–1. As it is more
than the lattice energy of NaCl therefore it is soluble.
Now we should focus our attention to the solubility trend in a given series. For a comparison of
the solubility both the lattice energy and hydration energy factors have to be taken into account.
If in a series the decrease of lattice energy is more compared to the decrease in hydration
energy then the substance becomes soluble.
Now the hydration enthalpy of a salt is given by
k1 k 2
Hhydration  
r r
where k1 and k2 are constants
k3
& lattice energy U  k3 = constant
r  r
Case (i): When r+<< r– the contribution of the anion to the hydration enthalpy is small so the
total Hhydration would be dominated by the cation alone. In a series of salts of a large anion, the
hydrational enthalpy will decrease in magnitude with increasing cation size. Now how does the
lattice energy respond to this changing cation radius? The lattice energy is inversely proportional to
(r+ + r–). Since r–>> r+, the sum will not change significantly as r+ increases. Consequently the lattice
energy will not decrease as fast as the hydration energy with increasing cationic size. The more
quickly diminishing hydration energy results in a decrease in solubility.
E.g. Solubility of LiI>NaI> KI…
MgSO4> CaSO4> SrSo4> BaSO4
Case (ii): r+  r–
Here the lattice energy decreases with increasing cationic size more rapidly than the hydration
energy which therefore results in an enhanced solubility in a series.
E.g. Solubility of LiF<NaF< KF
Mg(OH)2<Ca(OH)2< Ba(OH)2
Problem 4:The melting point of NaCl is higher than that of AgCl. Explain
Solution: Now whenever any comparison is asked about the melting point of the compounds which are
fully ionic from the electron transfer concept it means that the compound having lower melting point
has got lesser amount of ionic character than the other one. To analyse such a question first find
out the difference between the 2 given compounds. Here in both the compounds the anion is the
same. So the deciding factor would be the cation. Now if the anion is different, then the answer
should be from the variation of the anion. Now in the above example, the difference of the cation is
their electronic configuration. Na+ = [Ne]; Ag+ = [Kr] 4d10. This is now a comparison between a noble
gas core and pseudo noble gas core, the analysis of which we have already done. So try to finish
off this answer.
Problem 5:Which of the following molecules are polar: H2O, NH3,CO2,SO2,CHCl3,BF3?

Solution: Cl F
O C B
O N O F
S H H F
H H H O=C=O
H H H
Non-polar (Polar) Polar Non-polar
(Polar) (Polar)
 = 1.84D  = 1.86D =0  = 1.60D  = 1.86D =0
Problem 6:CH4 has zero dipole moment but CH2Cl2 has an appreciable dipole moment. Why?
Solution: Both CH4& CH2Cl2 have tetrahedral structure but CH4 is symmetrical while CH2Cl2 is
unsymmetrical.
H H
C
C
H H
H Cl
H Cl
Symmetrical Unsymmetrical
Due to the symmetrical structure of CCl4 the resultant of bond dipoles comes out to be zero.
But in case of CH2Cl2 it is not possible as the presence of hydrogen introduces some
dissymmetry.
Problem 7:Compare the dipole moment of Cis 1,2dichloroethylene and trans 1,2 dichloroethylene.
Solution: Cl Cl Cl H
C C C C
H H Cl
H
Cis Trans
In the trans compound the C-Cl bond dipoles are equal and at the same time acting in
opposition cancel each other while Cis compound the dipoles do not cancel each other
resulting in a higher value.
Generally all trans compounds have a lower dipole moment compared to the corresponding
cis isomers, when both the substituents attached to carbon atom are either electron
releasing or electron withdrawing.
Problem 8: Explain why ethyl alcohol (C2H5OH) has got a higher boiling point than dimethyl ether
(CH3-O-CH3) although the molecular weight of both are same?
Solution: Though ethyl alcohol and dimethyl ether have the same molecular weight but in ethyl
alcohol the hydrogen of the O-H groups forms intermolecular hydrogen bonding with the OH
group in another molecule. But in case of ether the hydrogen is linked to C is not so
electronegative to encourage the hydrogen to from hydrogen bonding.
C2H5 C2H5
O H O H
Due to intermolecular H-bonding, ethyl alcohol remains in the associated form and
therefore boils at a higher temperature compared to dimethyl ether.
Problem 9: Explain why O-nitrophenol is more volatile than p-nitrophenol?

Solution: More volatility means it has got lower boiling point. Now p-nitrophenol remains associated
through intermolecular hydrogen bonding. But in o-nitrophenol only intramolecular H-
bonding formation takes places, as a result of which there is no association. So p-
nitrophenol which remains as an associated species has got higher boiling point and so less
volatile.
O H O H O H
H
O
N
O
o-Isomer O N O
p-isomer
Problem 10: Draw the structure of the following
(i) SOF4 (ii) XeO3 (iii) POCl3
Solution: F ii) iii) O

F
Xe
i) O S P
O O
F F O
Cl Cl
Cl
Problem 11: In o-dichlorobenzene the observed value of dipole moment is 6.00 D while it
theoretical value is 6.30 D why?
Solution: o-dichlorobenzene due to dipole-dipole repulsion Cl

bond angle increase. Therefore dipole moment
Cl
decreases.
Problem 12: Dipole moment of o-chlorphenol is less than o-fluoro-phenol. Explain
Solution: Cl F H
OH O
no H-bonding
Due to H-bonding on o-fluorophenol bond angle decrease ( 60°) hence dipole moment is
increased.
Problem 13: BiCl5 does not exist. Explain

Solution: Due to inert pair effect, stability of Bi3+ Sb3+ As3+ and Bi5+ Sb5+ As5+
Hence Bi5+ salts are least stable; so BiCl5 does not exist.
Problem 14: Dipole moment of BF3 is zero. Explain

Solution:BF3 is a planar molecule with the bond angles being 120°. In
each B-F bond the bond dipole is projected towards Fluorine. Now F
the direction of the resultant bond dipoles of these two bonds is
shown in the diagram as R. If R is equal to the dipole of the 3rd B-F R
bond then R and B-F dipole will neutralize each other as equal B
dipoles acting in opposite direction cancel each other. Now let’s see
the magnitude of R. As dipole moment is a vector quantity, so the 120°
F F
resultant of two dipoles can be obtained from the law of vector
addition. Suppose the bond dipole is 1.
R = a2  b2  2abcos a & b are the individual vectors
12  12  211 cos 120 

=  = angle between vectors
 1
212  212   
=  2
 1
cos120° =   
 2
= 212  12 = 1 = B–F
 R is equal in magnitude to B-F bond dipole. Similar is the case with the other two
resultants. So the net dipole of BF3 is zero.
Problem 15: Carbon has a co-ordination number of four while other elements of this group have
co-ordination number of six. Why?
Solution: The normal valency of the elements is four, but apart from carbon, the elements can make
more than four bonds. This because they make use of a set of d-orbitals in bonding. The
availability of d-orbitals empty but electrons of ns2 and np2 can be excited into this is
responsible for the ability of the elements, except carbon, to make complex ions such as
SiF62 
Example16: KHF2 exists but KHCl2 does not explain

Solution: Due to inability of H – Cl to from H – bond with Cl- , the formation of HCl2 is not possible.
On the other hand , H – F can easily form H – bond with F- resulting in the formation of
HF2 .
Example17: ClF3 exists but FCl3 does not. Explain

Solution: Chlorine can expand its octet due to the presence of vacant d – orbitals which are not
available in fluorine.
Example18: N (CH3)3 is pyramidal whereas N (SiH)3 is planar. Explain

Solution: Lone pair of electron is localized on nitrogen in N (CH3)3 lone pair delocalised in vacant d –
orbitals of silicon.
Example19: Water has maximum density at 4°C. Explain:

Solution: At 0° there is sufficient H – bonding in water molecules and thus open cage – like structure
exists which has larger volume and makes the density low. On heating, to increases in
density. This is the case up to 4°C . After this, the increase in volume due to expansion of
the liquid water dominates over the decrease in volume due to cleavage of H – bonds.
Example20: Discuss the shape of XeF5 ion. How many different F—Xe—F bond angles are there in
the ion?
Solution: The Lewis dot formula of this ion is:
Geometry:
Bond angle: Due to presence of one lone pair, the ion is slightly distorted. Due to greater lp – bp
repulsion, four Xe—F bonds will be pushed slightly away from lp giving axial – equatorial bond
angle slightly less than 900. However, the bond angles between the adjacent bonds in the plane of
square are all identical.
18.2 Objective
Problem 1 Which of the following molecules has the smallest bond angle between its atoms?
(A) H2O (B) NH3 (C) SO3 (D) XeF4
Solution: XeF4: All bonds angles are 900. In others, bond angles are close to 1200 and 1090.
 (D)
Problem 2: In which of the following molecules the Vander Waal’s forces is likely to be most
important in determining the melting and boiling point?
(A)CO (B)H2S (C)Br2 (D)HCl
Solution: Br2 is non-polar molecules and hence its melting and boiling points depend only on Vander
Waal’s forces while all other molecules are having dipole moments hence their melting and
boiling points depends upon dipole-dipole interactions.
 (C)
Problem 3: Which of the following has highest viscosity?

(A)Glycerol (B)Glycol (C)Ethanol (D)Water
Solution: Due to 3 O–H groups, glycerol shows extensive intramolecular H-bonding and hence it has
highviscosity.
 (A)
Problem 4: Which of the statement are correct?

(1) The N atoms are close together in N2 than in N22
(2) It would be easier to separate the atoms in N22 than in N2.
(3) There is a triple bond between the nitrogen atoms in N2.
(4) There is a single bond between the nitrogen atoms in N22 .
(A) 1, 2 and 3 (B) 1 and 3 (C) 2 and 4 (D) 4 only
2
Solution: Bond order of N2 is 3 while bond order of N 2 is 2. Hence, N2 has shorter bonds (closer N
atoms) than N22 . Therefore, bond energy of N22 is smaller than N2.
 (A)
Problem 5: Indicate the type of bond angles present in IF5
(A) 90° (B) 90°,120° (C) 90°, 180° (D) 90°, 120°, 180°
3 2
Solution: Iodine undergoes sp d hybridisation with 5 bond pairs and one lone pair having square
pyramidal structure. (C)
Problem 6: The compound in which all carbon atoms make use of sp3 hybrid orbitals for bond
formation is
(A)HCOOH (B)(H2N)2CO (C)(CH3)3COH (D)CH3CHO
C O
Solution: (A), (B), (D) contains group where carbon is sp2hybridised
 (C)
Problem 7: The correct increasing bond angle among BF3, PF3 and ClF3 follow the order
(A)BF3 PF3 ClF3 (B)PF3 BF3 ClF3
(C)ClF3 PF3 BF3 (D)All have equal bond angle
Solution: In BF3, B is sp2hybridised with bond angle 120°C. In PF3, P is sp3hybridised but bond angle
is less than 109°28 due to lone pair bond pair repulsion. In ClF3, Cl is sp3d hybridised having
T-shape with bond angle 90°C.
(C)
Problem 8: The molecular size of ICl and Br2 is approximately same, but boiling point of ICl is
about 40° higher than that of Br2. It is because
(A) ICl bond is stronger than Br – Br bond
(B) I.E. of I  I.E. of Br
(C) ICl is polar while Br2 is non-polar
(D) I has larger size than Br
Solution: Polar molecule also have dipole-dipole interactions which increase the boiling point
 (C)
Problem 9: Which of the following has highest percentage of ionic character?

(A)HF (B)HCl (C)HBr (D)HI
Solution: The electronegativity difference in HF is highest and hence HF has high percentage of ionic
character.
 (A)
Problem 10: On the basis of VSEPR theory, the best description of the structure of H3S is
(A) The hydrogen atoms are at the corners of an equilateral triangle with the sulphur
at the centre of the triangle
(B) the hydrogen atoms are at the corners of an equilateral triangle with sulphur
above the plane of the H atoms at the top of the trigonal pyramid, the ion forms
(C) The H atoms are at corners of triangle with sulphur at the tetrahedral centre that
the molecule forms
(D) the H atoms are at the corners of a triangle with the sulphur placed so that the
molecule forms a “T” shape
Solution: Hybridization of S in H3S+ in sp3 with one lone pair, hence trigonal pyramidal shape like
ammonia.
 (B)
Problem 11: The bond energies in NO, NO+ and NO– follow the order
(A)NO+ NO  NO– (B)NO NO+ NO–
(C)NO– NO NO+ (D)NO+ NO– NO
1
Solution: Bond order NO = (10 – 5) = 2.5
2
1
Bond order in NO+ = (10 – 4) = 3.0
2
1
Bond order in NO– = (10 – 6) = 2.0
2
Since bond energies are directly related to bond order. Therefore correct order of increasing
bond energies is NO+ NO  NO–
 (A)
Problem 12: The molecule which has zero dipole moment is

(A)CH2Cl2 (B)BF3 (C)NF3 (D)ClO2
Solution: BF3 is trigonal planar and hence has zero dipole moment.
(B)
Problem 13: H2O has higher boiling point than H2S because
(A) H2S is a smaller molecule and hence more closely packed
(B) the bond angle of H2O is more than H2S and hence H2O molecule are more tightly
packed
(C) the intermolecular hydrogen bonding in liquid H2O
(D) the latent heat of vapourisation is higher for H2O than for H2S.
Solution: (C)
Problem 14: Among the following species, identify the isostructural pairs
NF3, NO3–, BF3, H3O+, HN3
(A) [NF3, NO3–] and [BF3, H3+O] (B) [NF3, HN3], [NO3–, BF3]
+ –
(C) [NF3, H3 O] and [NO3 , BF3] (D) [NF3, H3+O] and [HN3, BF3]
+ –
Solution: [NF3 and H3 O] are pyramidal while [NO3 and BF3] are trigonal planar
 (C)
Problem 15: Among the following compounds, the one that is polar and has central atom with
sp2hybridisation is
(A)H2CO3 (B)SiF4 (C)BF3 (D)HClO2
Solution: H2CO3 and BF3have sp2 hybridisation while SiF4 and HClO2 have sp3hybridisation. But in
BF3 it is symmetrical so dipole moment is zero while in H2CO3 resultant dipole is not zero so
it is also polar.
 (A)
Problem 16: N2 and O2 are converted into monocations, N2+ and O2+ respectively. Which of the
following is wrong
(A) In N2+, N – N bond weakens (B)In O2+, the O – O bond order increases
(C) In O2 , paramagnetism decreases (D)N2+ becomes diamagnetic
+
Solution: B.O. in N2 = (10 – 4)/2 = 3 B.O. in N2+ = (9 – 4) /2 = 2.5

B.O. in O2 = (10 – 6)/2 = 2 B.O. in O2+ = (10 – 5)/2 = 2.5
+
N2 contains one unpaired electron and hence it is paramagnetic. Thus option (D) is wrong.
 (D)
Problem 17: The correct order of increasing C–O bond length of CO, CO32– and CO2
(A)CO32– CO2 CO (B)CO2 CO32– CO
(C)CO  CO3  CO2
2–
(D)CO CO2 CO32–
Solution: B.O. of C - O in CO is 3, that of O = C = O is 2 while that of CO 32– ion is 1.33. Since the
bond length increases as the bond order decreases i.e.
CO  CO2 CO32– order is correct  (D)
Problem 18: A diatomic molecule has dipole moment of 1.2 D. If the bond distance is 1Å what
percentage of electronic charge exists on each atom?
(A) 12% of e (B) 19% of e
(C) 25% of e (D) 29% of e
Dipole moment 1.2D
Solution: Fraction charge of electron = 
Dis tan ce 1A
1.2 1018 esu cm
= = 1.2  10–10esu
110 cm
8
1.2 1010
% of electronic charge = 100 = 25%
4.8 1010
 (C)
Problem 19: The true statements from the following are

1. PH5 and BiCl5 do not exist 2.p – d bond is present in SO2
3. Electrons travel at the speed of light 4.SeF4 and CH4 have same shape
5. I3+ has bent geometry
(A) 1, 3 (B) 1, 2, 5
(C) 1, 3, 5 (D) 1, 2, 4
Solution: The statement 3 i.e. electron travel at the speed of light and statement 4, i.e. SeF 4 and CH4
have same shape are incorrect. SeF4 has distorted tetrahedral shape (sp3d hybridisation)
while methane tetrahedral shape (sp3hybridisation)
 (B)
Problem 20: The atomic orbitals used by As atom in the formation of AsF5 are
(A) d x 2 - y 2 , d z 2 , px , py, pz (B) dxy , s , px , py , pz
(C) s , px , py , pz , d z 2 (D) d x 2 - y 2 , d z 2 , px , py, s

Solution: Hybridisation and shape of AsF5 are sp3d and trigonalbipyramidal respectively. Three hybrid
orbitals should be in equatorial plane and two hybrid orbitals will orient themselves along
axial positions.
 (C)
Problem 21: NCl3 molecules is pyramidal and BCl3 molecules is planar because
(A) B – Cl bond is more polar than N – Cl bond
(B) BCl3 does not contain unused electron pair while NCl3 does.
(C) Boron atom is smaller than nitrogen atom
(D) N – Cl bond is more covalent than B – Cl bond.
Solution: BCl3 does not contain any lone – pair, so it is trigonal planar. NCl3 has one lone pair of
electrons. Due to lp – bp repulsion, it acuries pyramidal shape.
(B)
Problem 22: Among LiCl, BeCl2 , BCl3 and CCl4 , the covalent character follows the order
(A) LiCl> BeCl2> BCl3> CCl4 (B) LiCl> BeCl2> BCl3> CCl4
(C) LiCl< BeCl2< BCl3< CCl4 (D) LiCl> CCl4 > BeCl2> BCl3
Solution: Electropositive character decreases in the order Li > Be > B > C. hence covalent character
increases from LiCl to CCl4
 (C)
Problem 23: The correct order of decreasing bond angles is

+ +
(A) NH3> NH 2 > N H4 (B) N H4 > NH3 > NH 2
+ +
(C) NH 2 > NH3 > N H4 (D) N H4 > NH 2 > NH3
+
Solution: As the number of lone pair of electrons of N increases, bond angle decreases. N H4 , NH3
and NH 2 contain 0, 1 and 2 lone pairs respectively.
(B)
Problem 24: An atom of an element ‘X’ has three electrons in its outermost shell and that of ‘Y’
has six electrons in the outermost shell. The formula of compound between these two
elements would be
(A) X2Y4 (B) X2Y3 (C) X3Y2 (D) X2Y
Solution: Since ‘X’ has 3 valence electrons, it will lose three electrons to acquire noble gas
configuration. Similarly ‘Y’ will gain 2 electrons to acquire octet in its outermost shell.
 (B)
Problem 25: In which of the following compounds, all the bond angles are same.
(A) CCl4 (B) CHCl3 (C) CH3Cl (D) CH2Cl2
Solution: Since all 4 C – Cl bonds are at equivalent position
 (A)
Problem 26: When the substance CCl4, CH4 and CF4 are arranged in order to increasing boiling
point, what is the correct order?
(A) CCl4, CF4, CH4 (B) CH4, CF4, CCl4
(C) CF4, CCl4, CH4 (D) CF4, CH4, CCl4
Solution: All are non–polar, molar mass follows the boiling point
 (B)
Problem 27: The following compounds have been arranged in order of their increasing thermal
stability. Identify the correct order :
K2CO3(I) MgCO3(II) CaCO3(III) BeCO3(IV)
(A) I < II < III <IV (B) IV < II < III < I
(C) IV < II < I < III (D) II < IV < III < I
Solution: The stability of carbonates increases with increasing electropositive character of the metal.
 (B)
Problem 28: The molecules with zero dipole moment is:

(A) SO2 (B) ClO2 (C) NO2 (D) HgCl2
Solution: HgCl2 is sp hybridized and linear
 (D)
Problem 29: The bond order of C2 is

(A) 1 (B) 2 (C) 3/2 (D) ½
Solution: Molecular orbital configuration of
74

=       
2 *2 2 *2 1 2
C2 1a 2s 2s 2s 2p y 2p x B.O = 2 = 3/2
 (C)
Problem 30: Which does not use sp3hybride orbitals in its bonding
(A) BeF3 (B) OH 3

(C) NH 4

(D) NF3

Solution: (A) BeF3 involves sp2 hybridization
Foundation Builder (Objective)
BASIC CONCEPTS
IONIC BONDING
1. An ionic compound A+ B is most likely to be formed when.3

(A) The ionization energy of A is high and electron affinity of B is low
(B) The ionization energy of A is low and electron affinity of B is high
(C) Both, the ionization energy of A and electron affinity of B are high
(D) Both, the ionization energy of A and electron affinity of B are low
2. Which of the following is an ionic compound?
(A) SO3 (B) ICl (C) KI (D) CHCl3
3. The compound which does not contain ionic bond is

(A) NaOH (B) HCl (C) K2S (D) LiH
4. The magnitude of the lattice energy of a solid increase if

(A) the ions are large (B) the ions are small
(C) the ions are of equal size (D) charges on the ions are small
5. In which of the following species the bonds are nondirectional?

(A) NCl3 (B) RbCl (C) BeCl2 (D) BCl3
COVALENT BONDING
6. Which of the following compound does not follow octet rule?
(A) CO2 (B) PCl3 (C) ICl (D) ClF3

7. In NO3 ion, the number of bond pairs and lone pairs of electrons on nitrogen atom are
(A) 2, 2 (B) 3 , 1 (C) 1 , 3 (D) 4 , 0
8. Which of the following statements concerning a covalent bond is false?
(A) The electrons are shared between atoms
(B) The bond is nondirectional
(C) The strength of the bond depends upon the extent of overlapping
(D) The bond formed may be polar or nonpolar.
9. Which one of the following statements is incorrect?
(A) Sodium hydride is ionic
(B) Beryllium chloride is covalent
(C) CCl4 gives a white ppt. with AgNO3 solution
(D) Bonds in NaCl are nondirectional
10. The compound which contains ionic as well as covalent bonds is
(A) C2H4Cl2 (B) CH3l (C) KCN (D) H2O2
11. In the electronic structure of acetic acid, there are
(A) 16 shared and 8 unshared electrons (B) 8 shared and 16 unshared electrons
(C) 12 shared and 12 unshared electrons (D) 18 shared and 6 unshared electrons
12. Which of the following is an example of super octet molecule?
(A) ClF3 (B) PCl5 (C) IF7 (D) all the three
13. Which of the following has one lone pair of electrons on the central atom?
(A) H2 (B) CH4 (C) NH 4 (D) NCl3
VALENCE BOND THEORY
14. A covalent bond may be formed by

(A) ssoverlap (B) spoverlap (C) ppoverlap (D) all these three
15. Lateral overlap of porbitals leads to the formation of

(A)  bond (B) metallic bond (C)  bond (D) Ionic bond
16. The number of sigma  and pi   bonds present in a molecule of tetracyanoethylene
CN2 C  CCN2 are
(A) 5 and 9 (B) 5 and 8 (C) 9 and 9 (D) 9 and 7
17. If Zaxis is the molecular axis, then  molecular orbitals are formed by the overlap of
(A) s + pz (B) px + py (C) pz + pz (D) px + px
18. Which of the following combinations is not allowed (assumed Zaxis is internuclear axis)?
(A) 2s and 2s (B) 2px and 2px (C) 2s and 2pz (D) 2px and 2py
COORDINATE BONDING
19. Which of the following is best explained by co-ordinate bond?

1
(A)H2 + I2 (B) Mg + O2 (C)H+ + H2O (D) Cl + Cl
2
20. NH3 and BF3 form an adduct readily because they form
(A) An ionic bond (B) A covalent bond
(C) A coordinate bond (D) A hydrogen bond
21. The dative bond is present in

(A) NH3 (B) NH4Cl (C) PCl5 (D) BF3
VSEPR THEORY
1. Which of the following pair does not have same shape?

(A)NH4+, CH4 (B) H3O+, NH3 (C) I3–, XeF2 (D) PF5, BrF5
2. Which of the following does not have a tetrahedral structure?

(A) SO 24  (B) SF4 (C) SO 2Cl2 (D) SeO24

3. The geometrical arrangement and shape of I 3 are respectively
(A)Trigonal bipyramidal, T-shape (B)Octahedral, linear
(C)Trigonal planar, Angular (D)Trigonal bipyramidal, linear
4. Which of the following is octahedral?

3
(D) BF4
-
(A) PCl6 (B) SF4 (C) BO 3
5. Which of the following have linear shape?


(A)SnCl2 (B) NO2 (C) FNO (D) SO2
6. A molecule XY2 contains two , two  bonds and one lone pair of electrons in the valence shell
of X. The arrangement of lone pair as well as bond pairs is
(A)Square pyramidal (B)Linear
(C)Trigonal planar (D)Unpredictable
7. If the atomic number of M is 50. The shape of gaseous MCl2 is
Cl
M
M M
Cl
(A) Cl (B) Cl Cl (C) Cl (D) Cl M Cl
8. The shape of ClF3 molecules is

(A) Triangular planar (B) Pyramidal
(C) Tshape (D) Trigonal bipyramidal
9. C2 – C3 sigma single bond in vinyl acetylene CH2 = CH – C  CH is due to overlapping of

(A)sp – sp (B) sp2 – sp2 (C) sp – sp2 (D) sp2 – sp
10. Decreasing order of size of various orbitals is

(A) sp > sp2> sp3 (B) sp3> sp2> sp (C) sp2> sp > sp3 (D) sp > sp3> sp2
11. Atomic orbitals of carbon in carbon dioxide are

(A) sp – hybridised (B) sp3d – hybridised
(C) sp – hybridised
2
(D) sp3 – hybridised
12. Which one is not tetrahedral?

(A) BF 4 (B) NH 4 (C) CO 32 (D) SO 24
13. On hybridization of one s and p – orbitals , we get

(A) two mutually perpendicular orbitals (B) two orbitals at 180°
(C) four orbitals directed tetrahedrally (D) three orbitals in a plane.
14. The geometry and the type of hybrid orbitals present about the central atom in BF3 is
(A) linear, sp (B) trigonal planar , sp2
(C) tetrahedral , sp3 (D) pyramidal , sp3
15. Which of the following are isoelectonic and isostructural ?

NO 3 , CO 32 , SO3,ClO 3
(A)NO 3 , CO 32 (B) SO3 , NO 3 (C) ClO 3 , CO 32 (D) CO 32 , SO3
16. CO2 is isostructural with

(A) HgI 4 (B) SnCl2 (C) NCO (D) NO2
17. The linear structure is assumed by

(A) SnCl2 (B) C2H2 (C) NO2 (D) SO2
18. The fluorine molecule is formed by

(A) pp orbitals (sideways overlap) (B) pp orbitals (endtoend overlap)
(C) spsp orbitals (D) ss orbitals
19. Two hybrid orbitals have a bond angle of 120ºC. The percentage of s character in the hybrid
orbital is nearly
(A) 25% (B) 33% (C) 50% (D) 66%
20. Which carbon is more electronegative?

(A) sp3 hybridised carbon (B) sp hybridised carbon
(C) sp3 hybridised carbon
(D) the electron attracting power of C is always same irrespective is its hybrid state.
21. Compound in which central atom assumes sp3d hybridisation is
(A) SO3 (B) PCl5 (C) SO2 (D) PCl3
22. In OF2, oxygen has hybridisation of

(A) sp (B) sp2 (C) sp3 (D) none of these
23. C2H2 is isostructural with

(A) H2O2 (B) NO2 (C) SnCl2 (D) CO2
24. Pair of molecules having identical geometry is

(A) BF3, NH3 (B) BF3, AlF3 (C) BeF2, H2O (D) BCl3, PCl3
25. The pair of species with similar shape is

(A) PCl3, NH3 (B) CF4, SF4 (C) PbCl2, CO2 (D) PF5, IF5
26. The hybrid state of B in BF 4 is

(A) sp2 (B) sp (C) sp3 (D) no specific
27. The hybridization of phosphorus in POCl3 is the same as in

(A) P in PCl3 (B) S in SF4 (C) Cl in ClF3 (D) B in BCl3
28. The hybridization of the central atom in ICl 2 is

(A)sp3d (B) sp (C) sp2 (D) sp3
29. Out of CHCl3, CH4 and SF4 the molecules having regular geometry are
(A) CHCl3 only (B) CHCl3 and SF4 (C) CH4 only (D) CH4 and SF4
30. The molecule MLx is planar with six pairs of electrons around M in the valence shell. The value of x
is
(A) 6 (B) 2 (C) 4 (D) 3
BOND PARAMETERS & FAJAN’S RULE

1. The strongest bond is
(A) C—C (B) C—H (C) C—N (D) C—O
2. Which of the following is least soluble in H2O?
(A) BaF2 (B) SrF2 (C) CaF2 (D) MgF2
3. Amongst LiCl, RbCl, BeCl2 and MgCl2, the compounds with the greatest and least ionic
character respectively are
(A)LiCl and RbCl (B)RbCl and BeCl2
(C)RbCl and MgCl2 (D)MgCl2 and BeCl2
4. Which of the following is insoluble in water?

(A) AgF (B) AgI (C) KBr (D) CaCl2
5. Which of the following is least ionic?

(A) AgCl (B) KCl (C) BaCl2 (D) CaCl2
6. In which of the following, bond angle is maximum?

(A) NH3 (B) NH 4 (C) PCl3 (D) SCl2
7. Maximum bond angle is present in case of

(A) BBr3 (B) BCl3 (C) BF3 (D) Same in all
8. The correct order of increasing C – O bond length of CO, CO 32 , CO2 is
(A) CO 32 < CO2< CO (B) CO2< CO 32 < CO
(C) CO < CO 32 < CO2 (D) CO < CO2< CO 32
9. Which one is the highest melting point?

(A) NaCl (B) NaF (C) NaBr (D) NaI.
10. Which of the following statements about LiCl and NaCl is wrong?
(A) LiCl has lower melting point that NaCl
(B) LiCl dissolves more in organic solvents whereas NaCl does not
(C) LiCl is more soluble in water than NaCl
(D) Fused LiCl would be less conducting than fused NaCl
11. Which of the following has highest ionic character?

(A) MgCl2 (B) CaCl2 (C) BaCl2 (D) BeCl2
12. Covalent character is maximum in

(A) NaF (B) Na2O
(C) Na3N (D) all have equal covalent character
13. The bond angles of NH3, NH 4 and NH 2 are in the order

(A) NH 2 > NH3> NH 4 (B) NH 4 > NH3> NH 2
(C) NH3> NH 2 > NH 4 (D) NH3> NH 4 > NH 2
14. The correct order of bond angles is

(A) NO 2 > NO 2 > NO 2 (B) NO 2 > NO 2 > NO 2
(C) NO 2 > NO 2 > NO 2 (D) NO 2 > NO 2 > NO 2
15. The bond angle in H2S is

(A) > NH3 (B) Same as in BeCl2
(C) > H2Se &< H2O (D) Same as in CH4
16. Which of the following set contains species having same angle around the central atom?
(A) SF4, CH4, NH3 (B) NF3, BCl3, NH3
(C) BF3, NF3, AlCl3 (D) BF3, BCl3, BBr3
17. Which one of the following compounds has bond angle as nearly 90º?
(A) NH3 (B) H2S (C) H2O (D) CH4
18. The correct increasing bond angle among BF3, PF3 and ClF3 follows the order
(A) BF3< PF3< ClF3 (B) PF3< BF3< ClF3
(C) ClF3< PF3< BF3 (D) BF3 = PF3 = ClF3
19. The correct order of increasing covalent character of the following is

(A) SiCl4< AlCl3< CaCl2< KCl (B) KCl < CaCl2< AlCl3< SiCl4
(C) AlCl3< CaCl2< KCl < SiCl4 (D) none of these
20. Indicate the type of bond angles present in IF5

(A) 90° (B) 90°,120° (C) 90°, 180° (D) 90°, 120°, 180°
21. If Na+ is larger than Mg2+ ions and S2- ion is larger than Cl- ion, which of the following will be least
soluble in water.
(A) NaCl (B) Na2S (C) MgCl (D) MgS
22. The most covalent aluminium halide is
(A)AlF3 (B) AlCl3 (C) AlBr3 (D) AlI3
23. The threedimensional representation of H2N is

.. ..
H .. H . H .
(A) .. N (B) HNH (C) N (D) N
H .. .. H . .
H
24. The bond angle is minimum in

(A) NH 4 (B) NOCl (C)H2Se (D) SO3
25. F — Xe — F bond angle in XeO2F2 is approximately

(A)90º (B) 120º (C) 180º (D) 109º28
POLAR COVALENT BONDS & DIPOLE MOMENT
1. Which bond angle () would result in the maximum dipole moment for the triatomic molecule
XY2?
(A)  = 90° (B)  = 120° (C)  = 150° (D)  = 180°
2. Which of the following pair one which contains both polar and non – polar bonds?
(A) NH4Cl (B) HCN (C) H2O2 (D) CH4
3. Among the following bonds which has the most polar character?
(A) C – O (B) C – Br (C) C – F (D) C – S
4. The molecule which has zero dipole moment is
(A) CH2Cl2 (B) BF3 (C) NH3 (D) ClO2
5. Which one of the following arrangement of molecules is correct on the basis of their dipole
moments ?
(A) BF3> NF3> NH3 (B) NF3> BF3> NH3
(C) NH3> BF3> NF3 (D) NH3> NF3> BF3
6. Among the following compounds, the one that is polar and has the central atom with
sp2hybridization is
(A) H2CO3 (B) SiF4 (C) BF3 (D) HClO2
7. Arrange the following compounds in order of increasing dipole moment. Toluene (I), m –
dichlorobenzene (II), o – dichlorobenzene (III), p – dichlorobenzene (IV).
(A) I < IV < II < III (B) IV < I < II < III (C) IV < I < III < II (D) IV < II < I < III
8. Which one of the following has zero dipole moment ?

(A) ClF (B) PCl3 (C) SiF4 (D) CFCl3
9. Among the following, the molecule with highest dipole moment is

(A) CH3Cl (B) CH2Cl2 (C) CHCl3 (D) CCl4
10. Which of the following pair of molecules will have permanent dipole moment for both members
(A) NO2 and CO2 (B) NO2 and O3 (C) SiF4 and CO2 (D) SiF4 and NO2
11. Which of the following statements is correct?
(A) A  bond is weaker than a  bond
(B) There are four coordinate bonds in the NH 4 ion
(C) The covalent bond is directional in nature
(D) HF is less polar than HCl
12. Which of the following compounds is nonpolar?

(A) CH3Cl (B) CH2Cl2 (C) CHCl3 (D) CCl4
13. Which of the following will be least polar?

(A) NH (B) CH (C) OH (D) HF
14. Which of the following has zero value of dipole moment?

(A) Benzene (B) Naphthalene (C) pDichlorobenzene (D) All the three
15. Which of the following molecules has highest dipole moment?

(A) H2S (B) CO2 (C) CCl4 (D) BF3
16. Which of the following molecules has zero dipole moment?

(A) NH3 (B) CHCl3 (C) H2O (D) BF3
17. Which of the following molecules has a high dipole moment?

(A) CO2 (B) CCl4 (C) NH3 (D) BF3
18. Which of the following molecules has highest dipole moment?

(A) BF3 (B) NH3 (C) NF3 (D) B2H6
19. Which of the following molecules has nonzero dipole moment?

(A) PCl5 (B) BF3 (C) SO2 (D) CO2
20. The molecule that does not possess a permanent dipole moment is
(A) NF3 (B) BF3 (C) CH2Cl2 (D) NO2
21. Dipole moment of NF3 is smaller than

(A) NH3 (B) CO2 (C) BF3 (D) CCl4
22. The dipole moment of o, p and mdichlorobenzene will be in the order

(A) o>p>m (B) p>o>m (C) m>o>p (D) o>m>p
23. BF3 and NF3 both are covalent compounds but NF3 is polar whereas BF3 is non-polar. This is
because
(A) Nitrogen atom is smaller than boron atom
(B) NF bond is more polar than BF bond
(C) NF3 is pyramidal whereas BF3 is planar triangular
(D) BF3 is electron deficient whereas NF3 is not
24. Which of the following hydrogen halides has a high percentage of ionic character?
(A) HF (B) HCl (C) HBr (D) HI
MOLECULAR ORBITAL THEORY

1. The correct order of O—O bond length in O2, H2O2 and O3 is
(A) O2 O3 H2O2 (B) O3 H2O2 O2
(C) H2O2 O3 O2 (D) O2 H2O2 O3
2. When N2 goes N2 , the N—N bond distance …….. and when O2 goes to O 2 , the O—O bond
distance………..
(A) increases, decreases (B) decreases, increases
(C) increase in both case (D) decrease in both case
3. Which of the following diatomic molecules would be stabilized by the removal of an electron
(A) C2 (B) CN (C) N2 (D) O2
4. The energy of  2 s is greater than 1*s orbital because

(A)  2 s orbital is bigger than 1s orbital
(B)  2 s is a bonding orbital whereas 1*s is an antibonding orbital
(C)  2 s orbital has a greater value of n than 1*s orbital
(D)  2 s orbital is formed only after 1s
5. Which of the following statements is incorrect?

(A) He2 does not exist because its bond order is zero
(B) O2, O 2 and O 2 are all paramagnetic
(C) any two atomic orbitals can combine to form two molecular orbitals
(D) 2p x  and 2p y  are degenerate molecular orbitals
6.  
The bond order in peroxide ion O 22  is
(A) 2  5 (B) 1 5 (C) 2 (D) 1 0
7. The bond order in O 2 is the same as in

(A) N 2 (B) CN (C) NO+ (D) CO.
8. The bond length of H 2 , H 2 and H2 are in the order

(A) H 2 > H2> H 2 (B) H2> H 2 > H 2 (C) H 2 > H2> H 2 (D) H 2 > H 2 > H2
9. Which sequence correctly describes the relative bond strengths of oxygen molecule, superoxide ion,
peroxide ion and unipositive oxygen molecule?
(A) O 2 > O 2 > O 22  > O2 (B) O 2 > O2> O 2 > O 22 
(C) O 22  > O 2 > O2> O 2 (D) O 22  > O 2 > O 2 > O2
10. The bond energies in NO, NO+ and NO follow the order
(A) NO+> NO > NO (B) NO> NO+> NO
(C) NO> NO > NO+ (D) NO+> NO> NO
11. Which of the following contains maximum number of electrons in the antibonding molecular orbitals?
(A) O2 (B) O 22  (C) O 2 (D) O 2
12. Which of the following molecules have unpaired electrons in antibonding molecular orbitals?
(A) O2 (B) N2 (C) C2 (D) B2
13. Which of the following species is paramagnetic?

(A) O2 (B) N2 (C) O 22  (D) H2
14. In which set of molecules are all the species paramagnetic?

(A) B2, O2, N2 (B) B2, O2, NO (C) B2, F2, O2 (D) B2, O2, Li2
15. How many bonds (bond order) does B2 have?

(A) 0 (B) 1 (C) 2 (D) 3
16. The sequence of energy levels of MO’s formed from the outermost shells of C2 molecule is
(A) 2s  * 2s  2p x   2p y   2p z   * 2p x   * 2p y   * 2p z 
(B) 2s  * 2s  2p x   2p y   2p z   * 2p z   * 2p y   * 2p z 
(C) 2s  * 2s  2p z   2p y   * 2p x   * 2p y   * 2p y   * 2p z 
(D) 2s  * 2s  2p z   2p x   2p y   * 2p z   * 2p x   * 2p y 
17. Which among the following molecules/ions is diamagnetic?

(A) Super oxide ion (B) Oxygen
(C) Carbon molecule (D) Unipositive ion of N2 molecule
18. Bond order of C-C bond in Calcium Carbide, CaC2

(A) 2 (B) 2.5 (C) 3 (D) 3.5
19. Which graph best represent the energy diagram of molecular orbitals vs distance between atoms
Anti-bonding MO Anti-bonding MO
Energy Energy
O O
(A) (B)
Bonding MO Bonding MO
Distance between atoms Distance between atoms
Anti-bonding MO
Bonding MO
Energy
Energy
O
O
(C) (D)
Anti-bonding MO
Bonding MO
Distance between atoms Distance between atoms
HYDROGEN BONDING
1. Among HF, CH4, CH3OH and N2O4, intermolecular hydrogen bonding is expected
(A) in all (B) in all expect one (C) in two (D) in none
2. The high boiling point of water is due to

(A) Weak dissociation of water
(B) Hydrogen bonding among water molecules
(C) Its high specific heat
(D) Its high dielectric constant
3. Hydrogen bonding is absent in

(A) H2O (B) NH3 (C) C2H5OH (D) C2H5OC2H5
4. What is the maximum number of hydrogen bonds in which a water molecule can participate
(A) 1 (B) 2 (C) 3 (D) 4
5. Which of the following hydrogen halides is most volatile?

(A) HF (B) HCl (C) HBr (D) HI
6. Amongst H2O, H2S , H2Se and H2Te, the one with the highest boiling point is
(A) H2O because of hydrogen bonding (B) H2 Te because of higher molecular weight
(C) H2S because of hydrogen bonding (D) H2Se because of lower molecular weight
7. The boiling point is not affected due to hydrogen bonding in
(A) Water (B) ammonia (C) methyl alcohol (D) hydrogen chloride
8. The correct order of the strength of Hbonds is
(A) H…..F > H…..O > H…..N (B) H…..N > H…..O > H…..F
(C) H…..O > H…..N > H…..F (D) H…..F > H…..N > H…..O
9. In ice, the length of Hbonds

(A) is less than that of covalent bonds
(B) is greater than that of covalent bonds
(C) is same as that of covalent bonds
(D) can be less, greater or same as that of covalent bonds
10. The boiling points of methanol, water and dimethyl ether are respectively 65ºC, 100ºC and 34.5ºC.
Which of the following best explains these wide variations in b.p.
(A) the molecular mass increases from water (18) to methanol (32) to diethyl ether (74)
(B) the extent of Hbonding decreases from water to methanol while it is absent in ether
(C) the extent of intramolecular Hbonding decreases from ether to methanol to water
(D) the density of water is 1.00g ml1, methanol 0.7914g ml1 and that of diethyl ether is0.7137g ml1
11. Intramolecular Hbonding is present in

(A) oNitrophenol (B) Salicylaldehyde (C) mNitrophenol (D) both (A) and (B)
12. Which of the following compounds has the least tendency to form hydrogen bonds between
molecules?
(A) NH3 (B) NH2OH (C) HF (D) CH3F
13. The weakest bond among the following is

(A) ionic (B) covalent (C) metallic (D) hydrogen bond
14. Incorrect order of decreasing boiling points is
(A) HF > HI > HBr > HCl (B) H2O > H2Te > H2Se > H2S
(C) Br2> Cl2> F2 (D) CH4> GeH4> SiH4
15. Which of the following does not contain any coordinate bond?
(A) H3O+ (B) BF 4 (C) HF 2 (D) NH 4
16. Which of the following has highest viscosity?

(A) Glycerol (B) Glycol (C) Ethanol (D) Water
17. Which of the following has a 3 centered 2 electron bond?
(A) BF3 (B) NH3 (C) CO2 (D) B2H6
18. Out of the following which has highest dipole moment?
(A)2,2-dimethyl propane (B)trans-2-pentene
(C)cis-3-hexene (D)2,2,3,3-tetramethyl butane
19. Identify the false statement
(A) Anhyd. FeCl3 cannot exist in dimeric form
(B) Maximum polarisation is brought about by a cation of high charge
(C) The bond dissociation energy of a metallic bond is greater than that of a hydrogen bond.
(D) The conversion of Na to Na+ is an endothermic process
20. In which of the following set of molecules is the order of boiling points incorrect?
(A) Xe > Ar > He (B) HF > HCl > HBr
(C) H2O > H2Se > H2S (D) C3H8> C2H6> CH4
21. 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
22. The electronegativity difference between two atoms A and B is 2 then percentage of covalent
character in the molecule is
(A) 54% (B) 46% (C) 23% (D) 72%
23. For resonance structure a molecule may not have

(A)Identical arrangement of atoms (B)Nearly same energy contents
(C)The same number of paired electrons (D) Identical bonding
24. Which is paramagnetic?

(A) Cl2O6 (B) Cl2O7 (C) Cl2O (D) ClO2
25. Which of the following statements concerning elements with atomic number 10 is true?
(A) it forms a covalent net work of solids
(B) its molecules are monoatomic
(C) it has a very high value of electron affinity
(D) it has extremely low value of ionisation energy.
26. Which of the following is solid with highest melting point?
(A) CO2 (B) H2O (C) SiO2 (D) He
27. Which one has least O-O bond length?
(A) O2 (B) Na2O2 (C) KO2 (D) O3
Get Equipped for JEE MAIN
1. Which ion below has a noble gas electron configuration?

(A) Li 2  (B) Be 2  (C) B2 (D) C2
2. Of the ions below, only __________ has a noble gas electron configuration.
(A) S3 (B) O 2  (C) I  (D) Cl
3. Which of the following has eight valence electrons?
(A) Ti 4 (B) Kr (C) Cl (D) all of the above
4. Which of the following does not have eight valence electrons?

(A) Ca  (B) Rb (C) Xe (D) Br 
5. The chloride of which of the following metals should have the greatest lattice energy?
(A) potassium (B) rubidium (C) sodium (D) lithium
6. Lattice energy is __________.

(A) the energy required to convert a mole of ionic solid into its constituent ions in the gas phase
(B) the energy given off when gaseous ions combine to form one mole of an ionic solid
(C) the energy required to produce one mole of an ionic compound from its constituent elements in
their standard states
(D) the sum of ionization energies of the components in an ionic solid
7. In ionic bond formation, the lattice energy of ions ________ as the magnitude of the ion charges
_______ and the radii __________.
(A) increases, decrease, increase (B) increases, increase, increase
(C) decreases, increase, increase (D) increases, increase, decrease
The diagram below is the Born-Haber cycle for the formation of crystalline potassium fluoride.
8. Which energy change corresponds to the electron affinity of fluorine?

(A) 2 (B) 5 (C) 4 (D) 1
9. Which energy change corresponds to the first ionization energy of potassium?

(A) 2 (B) 5 (C) 4 (D) 3
10. The electron configuration [Kr]4d10 represents __________.

(A) Sr+2 (B) Sn+2 (C) Te+2 (D) Ag+1
11. Fe+2 ions are represented by __________.

(A) [Ar]3d1 (B) [Ar]3d4 (C) [Ar]3d6 (D) [Ar]3d104s1
12. Using the Born-Haber cycle, the Hf  of KBr is equal to __________.
(A) Hf °[K (g)]  Hf °[Br (g)]  I1 (K)  E(Br)  H
lattice
(B) Hf °[K (g)]  Hf °[Br (g)]  I1 (K)  E(Br)  H
lattice
(C) Hf °[K (g)]  Hf °[Br (g)]  I1 (K)  E(Br)  H
lattice
(D) Hf °[K (g)]  Hf °[Br (g)]  I1  E(Br)  H
lattice
13. The type of compound that is most likely to contain a covalent bond is __________.
(A) one that is composed of a metal from the far left of the periodic table and a nonmetal from the far
right of the periodic table
(B) a solid metal
(C) one that is composed of only nonmetals
(D) held together by the electrostatic forces between oppositely charged ions
14. In which of the molecules below is the carbon-carbon distance the shortest?
(A) H2C  CH2 (B) C2 H2 (C) H3C  CH3 (D) H2C  C  CH2
15. Of the atoms below, __________ is the most electronegative.

(A) Si (B) Cl (C) Rb (D) Ca
16. Of the atoms below, __________ is the least electronegative.

(A) Rb (B) F (C) Si (D) Cl
17. Which of the elements below has the largest electronegativity?

(A) Si (B) Mg (C) P (D) S
18. Of the molecules below, the bond in __________ is the most polar.
(A) HBr (B) HI (C) HCl (D) HF
19. Of the bonds below, __________ is the least polar.
(A) Na, S (B) P, S (C) C, F (D) Na, Cl
20. Which of the following has the bonds correctly arranged in order of increasing polarity?
(A) Be  F, Mg  F, N  F, O  F (B) O  F, N  F, Be  F, Mg  F
(C) O  F, Be  F, Mg  F, N  F (D) N  F, Be  F, Mg  F, O  F
21. Which two bonds are most similar in polarity?

(A) O  F and Cl  F (B) B  F and Cl  F
(C) Al  Cl and I  Br (D) I  Br and Si  Cl
22. The bond length in an HI molecule is 1.61 Å and the measured dipole moment is 0.44 D. What is the
magnitude (in units of e) of the negative charge on I in HI?
( 1 debye = 3.34  1030 coulomb-meters ; e=1.6 1019 coulombs )
(A) 1.6  1019 (B) 0.057 (C) 9.1 (D) 1
23. Which of the following names is/are correct for the compound TiO 2 ?
(A) titanium dioxide and titanium (IV) oxide (B) titanium (IV) dioxide
(C) titanium oxide (D) titanium oxide and titanium (IV) dioxide
24. Which of the following names is/are correct for the compound SnCl 4 ?
(A) tin (II) chloride and tin (IV) chloride (B) tin tetrachloride and tin (IV) chloride
(C) tin (IV) tetrachloride (D) tin chloride
25. The structure of N2 H2 shows __________.

(A) a nitrogen-nitrogen triple bond
(B) a nitrogen-nitrogen single bond
(C) each nitrogen has one nonbonding electron pair
(D) each nitrogen has two nonbonding electron pairs
26. There are __________ valence electrons in CH3CH2Cl.
(A) 14 (B) 12 (C) 18 (D) 20
27. In the Lewis symbol for a sulfur atom, there are __________ paired and __________ unpaired
electrons.
(A) 2, 2 (B) 4, 2 (C) 2, 4 (D) 0, 6
28. Compare C–O bond strength amongst

(A) CO > CO2 > CO32– (B)CO > CO32–>CO2
(C) CO32–> CO2> CO (D) CO < CO32–< CO2
29. In the nitrite ion (NO 2- ) , __________.

(A) both bonds are single bonds
(B) both bonds are double bonds
(C) one bond is a double bond and the other is a single bond
(D) both bonds are the same
30. Resonance structures differ by __________.

(A) placement of electrons only (B) number of electrons only
(C) placement of atoms only (D) number of atoms only
31. The oxidation number of phosphorus in PF3 is __________.
(A) -2 (B) +1 (C) +3 (D) +2
32. To convert from one resonance structure to another, __________.
(A) only atoms can be moved (B) electrons and atoms can both be moved
(C) only electrons can be moved (D) neither electrons nor atoms can be moved
33. For resonance forms of a molecule or ion, __________.
(A) one always corresponds to the observed structure
(B) all the resonance structures are observed in various proportions
(C) the observed structure is an average of the resonance forms
(D) the same atoms need not be bonded to each other in all resonance forms
For the questions that follow, consider following oxyanions:
(i) NO 2  (ii) NO3 (iii) SO32 (iv) SO42 (v) BrO 3 
34. There can be four equivalent best resonance structures of __________.

(A) (ii) (B) (iii) (C) (i) (D) (iv)
35. In which of the ions do all X-O bonds (X indicates the central atom) have the same length?
(A) none (B) all (C) (i) and (ii) (D) (iii) and (v)
36. Of the following, __________ cannot accommodate more than an octet of electrons.
(A) P (B) As (C) O (D) S
37. Based on the octet rule, boron will most likely form a __________ ion.
(A) B3- (B) B1+ (C) B3+ (D) B2+
38. Which of the following does not have eight valence electrons?
(A)Xe (B) Ti+4 (C) Rb+1 (D) Sr+1
39. A valid Lewis structure of __________ cannot be drawn without violating the octet rule.
(A) PO43 (B) SiF4 (C) CF4 (D) SeF4
40. The central atom in __________ does not violate the octet rule.
(A) SF4 (B) KrF2 (C) CF4 (D) XeF4
41. The central atom in __________ violates the octet rule.

(A) NH3 (B) SeF2 (C) BF3 (D) AsF3
(A) ClF3 (B) PCl3 (C) SO3 (D) CCl 4
(A) NI3 (B) SO2 (C) ICl5 (D) SiF4
(A) NF3 (B) BeH2 (C) SO2 (D) CF4
45. Which atom can form compounds having incomplete octet according to Lewis theory?
(A) N (B) C (C) B (D) H
46. Bond enthalpy is __________.
(A) always positive (B) always negative
(C) sometimes positive, sometimes negative (D) always zero
47. Given that the average bond energies for C-H and C-Br bonds are 413 and 276 kJ/mol, respectively,
the heat of atomization of bromoform (CHBr3 ) is __________ kJ/mol.
(A) 1241 (B) 689 (C) -689 (D) 1378
48. Of the bonds C-N,C  N , and C  N , the C-N bond is __________.
(A) strongest/shortest (B) strongest/longest
(C) weakest/shortest (D) weakest/longest
49. As the number of covalent bonds between two atoms increases, the distance between the atoms
__________ and the strength of the bond between them __________.
(A) increases, increases (B) decreases, decreases
(C) increases, decreases (D) decreases, increases
50. Of the possible bonds between carbon atoms (single, double, and triple), __________.
(A) a triple bond is longer than a single bond
(B) a double bond is stronger than a triple bond
(C) a single bond is stronger than a triple bond
(D) a double bond is longer than a triple bond
51. The molecule which possesses both sp3 and sp3d2 hybridisation is
(A) solid PCl5 (B) gaseous PCl5 (C) PCl4 (D) PCl6
Get Equipped for JEE ADVANCED
Only one option correct
1. Out of the three molecules XeF4, SF4, SiF4 one which has tetrahedral structures is
(A) all the three (B)only SiF4
(C) both SF4 and XeF4 (D)only SF4 and XeF4
2. Which of the following molecules or ions is not linear?

(A)BeCl2 (B)ICl2– (C)CS2 (D)ICl2+
3. Which of the following is non–polar but contains polar bonds?

(A)HCl (B)H2O (C)SO3 (D)NO2
4. The number of 90° angles between bond pairbond pair of electrons in BrF5 is
(A)4 (B)5 (C)6 (D) 8
5. The shape of ClO4– is

(A)Square planar (B)Square pyramidal (C)Tetrahedral (D)Trigonal bipyramidal
6. The 2s orbital has a higher energy than *1s orbital, 2s, orbital is bonding while 1*s orbital is
antibonding because
(A)2s is planar while 1*s is nonplanar.
(B)2s is symmetrical while 1*s is unsymmetrical.
(C)2s is nearer to the nuclei than 1*s .
(D)none of these
7. A molecule of chloral hydrate contains two OH groups attached to a single carbon atom as shown
below
Cl OH
ClC CH
Cl OH
Its extra stability is due to the presence of
(A)intramolecular hydrogen bonding. (B)its planar structure.
(C)its symmetrical structure. (D)none of these.
8. The stability of O2, O 22  , O 2 and O 2 in their respective dissociation reaction is in the order
(A) O 2 < O2< O 2 < O 22  (B) O 22  < O 2 < O2< O 2
(C) O 2 < O 2 < O2< O 22  (D) O 2 < O 22  > O2< O 22 
9. Homolytic fission of CC bonding ethane (CH3CH3) gives an intermediate in which carbon atom is
(A)sp3 hybridised (B)sp2 hybridised (C)sp hybridised (D)sp2d hybridised
10. Which of the following is paramagnetic O 22  and BN?

(A)Both (B)None (C) O 22  (D)BN
11. Pick out the incorrect statement?

(A)N2 has greater dissociation energy than N 2 .
(B)O2 has lower dissociation energy than O 2 .
(C)Bond length in N 2 is less than in N2.
(D)Bond length in NO+ is less than in NO.
12. KF combines with HF to form KHF2. The compound contains the species
(A)K+, F and H+ (B)K+, F and HF (C)K+ and [HF2] (D)[KHF]+ and F2
13. The hybridisation of P in PO 34 is same as in

(A)I in ICl4 (B)S in SO3 (C)N in NO 3 (D)S in SO 24
14. The most acidic among the following oxide

(A)MnO (B)MnO2 (C)MnO2 (D)Mn2O7
15. Which of the following molecule involves sp2 hybridisation?

(A)CO2 (B)SO2 (C)N2O (D)CO
16. Which of the following have identical bond order :

(i)CN– (ii) O 2 (iii) NO+ (iv) CN+
(A)(i) and (iii) (B)(ii) and (iv) (C)(i) and (iv) (D)(ii) and (iii)
17. The hybridisation of atomic orbitals of nitrogen in NO 2 , NO 3 and NH 4 are

(A)sp2, sp3 and sp2 respectively. (B)sp, sp2 and sp3 respectively.
2 3
(C)sp , sp and sp respectively. (D)sp2, sp3 and sp respectively.
18. The correct order of hybridisation of the central atom in the following species, NH 3, [PtCl4]2, PCl5
and BCl3 is respectively
(A)dsp2, sp3d, sp2, sp3 (B)sp3, dsp2, sp3d, sp2
2 2 3 3
(C)dsp , sp , sp , sp d (D)dsp2, sp3, sp2, sp3d
19. The common features among the species CN, CO and NO+ are
(A)Bond order three and isoelectronic. (B)Bond order three and weak field ligands.
(C)Bond order three and acceptors. (D)Isoelectronic and weak filed ligands.
20. The nodal plane in the bond of ethene 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
right angles.
(D)a plane perpendicular to the molecular plane which contains the carboncarbon bond.
21. Which of the following hydrocarbons has the lowest dipole moment?
H3C CH3
(A) C (B)CH3CC.CH3
H H
(C)CH3CH2CCH (D)CH2=CHCCH
22. Which of the following molecular species has unpaired electron(s)?

(A)N2 (B)F2 (C) O 2 (D) O 22 
23. Arrange the following in the increasing order of melting points

(A)NH3 (B)CH3NH2 (C)(CH3)2NH (D)(CH3)3N
(A)(A)<(B)<(C)<(D) (B)(D)<(C)<(B)<(A)
(C)(A)<(D)<(C)<(B) (D)None of these
24. The species that does not contain peroxide ions are
(A) PbO2 (B)H2O2 (C)SrO2 (D)BaO2
25. The number of sp2 – sp2 sigma bonds in the compound given below is:
H3C CH3
H3C OH N
OH
NH2
OH
OH O OH O O
(A)8 (B) 10 (C) 11 (D) 12
26. The H bond in solid HF can be best represented as:

H H H H
(A) H  F ....H  F ....H  F (B) F F F
F F H H
H H H H F F F F
(C) F (D) H
27. The dipole moment of

Cl Cl
Cl Cl Cl
Cl Cl is 1.5 D. The dipole moment of Cl is

(A) Zero (B) 1.5 D (C) 2.60 D (D) 2.12 D
28. Consider the following sets of H─bonds
O H N
O H O
P: Q:
N H N N H O
R: S:
The correct order of H─bond strength is

(A) Q  P  S  R (B) R  Q  S  P
(C) R  S  P  Q (D) P  Q  R  S
29. In hydrocarbon C3Hm, X-ray diffraction (which does not “see” H’s) finds a C─C─C bond angle of
about 120o. The value of m must be__________
(A) 4 (B) 5 (C) 6 (D) 8
More than one option correct

1. Among the following, the diamagnetic compounds is/are
(A) Na2O2 (B) O3 (C) N2O (D) KO2
2. The species having same bond order as in CO

(A) NO (B) NO (C) CN (D) N2
3. The molecule(s) with some finite positive dipole moment is(are):

(A) OH (B) Cl
OH Cl
(C) PF3Cl2 (D) PCl3F2
4. The molecule(s) with zero dipole moment is(are):

OH CN Cl NH2
OH CN Cl NH2
(A) (B) (C) (D)
3
5. Compound which do have sp d hybridization
(A)ICl2 (B) ClF3 (C) XeO2F2 (D) XeF4
6. The molecules that will have dipole moment:

(A) 2, 2-dimethylpropane (B) Trans-2-pentene
(C) Cis-3-hexene (D) 2, 2, 3, 3-tetramethylbutane
7. Species having same bond order are:
(A) N2 (B) N 2 (C) N 2 (D) N 22
8. Which of the following species are paramagnetic?

2
(A) O2 (B) N 22 (C) N2 (D) O2
9. Molecules having distorted geometry are:
(A) H2O (B) NH3 (C) N3H (D) XeF2
10. The linear structure s assumed by:

(A) SnCl2 (B) NCO― (C) NO2 (D) CS2
11. Which of the following hybridization results in non-planar orbitals?

(A) sp3 (B) sp (C) sp2 (D) sp3d
12. Which statement(s) is/are correct?
(A) A sigma bond is stronger than   bond
(B) A sigma bond is weaker than   bond
(C) Hydrogen bonding is weaker than covalent bonding
(D) A triple bond is weaker than double bond
13. Which combination of the compounds and their geometry are correct?
(A) HgCl2 – linear (B) ClF3 – V- shaped
(C) ClF3 – T- shaped (D) ICl4 - square planar
14. In the following case(s), hybridization of the underlined atom is affected:

(A) PCl5 (solid) dissociates into PCl4 andPCl6
(B) LiH reacts with AlH3 forming LiAlH4
(C) NH3 is protonated
(D) H3PO2 is heated forming PH3 and H3PO3
COMPREHENSION TYPE
Passage 1
In gaseous phase PCl5 molecule exist and having Trigonal bipyramidal geometry, such
as it has three equatorial positions and two axial positions as
The electron pairs in the "axial" bonds have three 90° repulsions with electron pairs in
the "equatorial" bonds, whilst the electron pairs in the equatorial bonds have only two 90°
repulsions. It would therefore be predicted that repulsions involving the axial bonds
would be stronger and that these bonds would therefore be longer.
Due to asymmetry in the structure in crystals of PCl5 are composed of [PCl4]+ and [PCl6] ions, having
symmetric tetrahedral and octahedral geometry respectively.
1. Bond angle FPF in PCl3F2 will be

(A) 90o (B) 120o (C) 150o (D) 180o
2. Molecular shape of ClF3 is
(A) T-shaped (B) Triangular Planar (C) See-Saw (D) Tetrahedral
3. Out of the following, which compound does exist?
(A) PI5 (B) [PBr6] (C) PH5 (D) None of these.
4. In solid state PBr5 exist as

(A) [PBr4]+ and [PBr6] (B) [PBr4]+ and Br
(C) PBr5 only (D) None of these.
5. In nature Phosphorus consists two isotopes 30P and 31P and Chlorine as 35
Cl and 37
Cl. Maximum
there is how many type of PCl5 molecule exist in nature?
(A) 8 (B) 12 (C) 16 (D) 24
6. Molecular shape of SF4 is
(A) T-shaped (B) Square Planar (C) See-Saw (D) Tetrahedral
7. Molecular shape of IF2 is

(A) T-shaped (B) Angular (C) linear (D) bent
8. PCl5 undergoes
(A) sp3d x2  y 2 (B) sp3d xy (C) sp3d z2 (D) sp3d yz
Passage 2
Lewis concept of covalency of an element involved octet rule. Later on it was found that many elements in
their in compounds e.g., BeF2 , BF3 etc. have incomplete octet whereas PCl 5 , SF6 etc. have expanded
octet. This classical concept also failed in predicting the geometry of molecules. Modern concept of
covalence was proposed in terms of valence bond theory proposed by Heitler and London and later on
modified by Pauling and Slater. Hybridization concept alongwith valence bond failed in many molecules.
The geometry of such molecules was explained by VSEPR concept. Finally molecular orbital theory was
proposed by Hund-Mulliken to explain many other anomalies.
1. Which are true statements among the following:
(1) I 3 has bent structure (2) p  d bonds are present in SO 2
(3) SeF4 and CH 4 has same shape (4) XeF2 and CO 2 has same shape
(5) SF4 is see-saw structure whereas ICl3 is T shaped
(A) 1,2,4,5 (B) 1,2,3,4 (C) 2,3,4,5 (D) 1,3,4,5
2. Ratio of lone pair-bond pair electrons on central atom in I 3 and XeF4 are respectively:
(A) 2.66, 0.5 (B) 0.5, 1.5 (C) 1.5, 0.5 (D) 0.5, 2
 
3. The bond angles NO 2 , NO 2 and NO 2 are respectively:
(A) 180 ,134 ,115 (B) 115 ,134 ,180 (C) 134 ,180 ,130 (D) 115 ,180 ,130
4. Which statements are correct:

(1) Bond angle of PF3  PCl3
(2) Bond angle of PCl3  PBr3
(3) (CH 3 ) 3 N is pyramidal whereas ( SiH 3 ) 3 N is planar.
(4) Multiple bonds also influence the geometry of molecule and thus HCHO has  HCH  116 and
HCO  122 
(5) PCl 5 is super octet molecule.
(A) 1,3,4,5 (B) 1,2,3,4,5 (C) 2,3,4,5 (D) 2,5
5. Which of the following statements are true:

(1) O2 , O2 andO2 are paramagnetic species
(2) Correct bond order is: O2  O2  O2
(3) Bond length is shortest for O2 among the species O2 , O2 , O22 , O2 and O22
(4) Bond length is maximum for O 22  among the species O2 , O2 , O22 , O2 and O22
(5) B 2 has two unpaired electron and thus paramagnetic
(A) 1,2,3,5 (B) 1,3,4,5 (C) 1,2,5 (D) 1,4,5
6. Select the correct statements:
(1) Bond order for N 2 and N 2 are same
(2) Bond energy of N 2  N 2
(3) Bond length of N 2  N 2
(4) C 3 F4 is a non-polar molecular
(5) XeF2 has two F atoms in axial position whereas XeF4 has four F atoms in equatorial position.
(A) 2,3,4,5 (b )1,4,5 (C) 1,5 (D) 1,2,4,5
7. Which statements are correct:

(1) C (CN ) 4 and C 2 (CN ) 4 have ratio of  and  bonds same
(2) Propanal and propanone have same ratio of  and  bonds
(3) CO 2 and BeF2 both are linear and possess sp hybridization
(4) XeF4 and SF4 both are square planar and possess sp 3 d hybridization
(5) Cl-Cl bond is stronger than Br-Br:
(A) 1,3,5 (B) 1,2,4,5 (C) 1,2,3,5 (D) 1,4,5
Passage 3
To explain the abnormality in some molecules, the concept of H-bonding was introduced. Hydrogen
bonding is defined as the phenomenon in which H-atom covalently lined with N, O or F in a molecule is
held up on other side with dipole-dipole attraction with same or other molecules of same or other
compound. H-bonding between two molecules is called intermolecular H-bonding favours for cluster
formation whereas intramolecular H-bonding prevents the cluster formation.
1. Which of the following statement is wrong:

(A) H-bonding never involves more than two atoms
(B) The H-bond order is : H  F    H  F  H  O   H  O  H  N    H  N
(C) All the three atoms (e.g., F  H    F) involved in H-bonding lie in one plane
(D) Bond energy of H-bonding is about ½ of covalent bond
2. HF2 exists in solid state and in liquid HF but not in aqueous solution because :
(A) HF2  H 2O  H 3O   2F  (B) HF  H 2O  H 2 F   OH 
(C) HF2  H 2O  H 2 F2  OH  (D) None of these
3. The correct representation of H-bonding between NH 3 and H 2 O is:

(A) H 2 N  H    OH 2 (B) H 3 N    H  OH
(C) H 2 N  H    H  OH (C) H 3 N    OH 2
Passage 4
When anions and cations approach each other, the valence shell of anions are pulled towards cation
nucleus and thus, shape of anion is deformed. The phenomenon of deformation of anion by a cation is
known as polarization and the ability of the cation to polarize the anion is called as polarizing power of
cation. Due to polarization, sharing of electrons occurs between two ions to some extent and the bond
shows some covalent character.
The magnitude of polarization depends upon a number of factors. These factors were suggested by Fajan
and are known as Fajan’s rules.
(i) Greater is the polarization in a molecule, more is covalent character.
(ii) As the charge on cation increases, its tendency to polarize the anion increases.
(iii) As the size of the cation decreases or size of the anion increases, the polarization increases.
(iv) The cations with 18 electrons in the outermost shell bring greater polarization of the anion than those
with inert gas configuration even both the cations have same size and same charge.
1. Considering BeCl2, MgCl2, CaCl2 and BaCl2, predict which of the following statement is true?
(A) BeCl2 is least ionic out of the given chlorides
(B) Covalent character increases as the atomic number of the metal atom increases
(C) BeCl2 has the highest melting point among the given chlorides
(D) All are highly ionic compounds
2. In which of the halides, there is maximum polarization?

(A) AlF3 (B) AlCl3 (C) AlBr3 (D) AlI3
3. Which is most covalent in nature?

(A) NaCl (B) MgCl2 (C) AlCl3 (D) CaCl2
4. Non-aqueous solvent like ether is added to the mixture of LiCl, NaCl and KCl. Which will be
extracted into ether?
(A) NaCl (B) LiCl (C) KCl (D) None
5. Which has the minimum melting point?

(A) CaF2 (B) CaCl2 (C) CaBr2 (D) CaI2
Passage 5
Covalent molecules formed by heteroatoms found to have some ionic character. The ionic character is due
to shifting of the electron pair towards A or B in the molecule AB. Hence, atoms acquire small and equal
charge but opposite in sign. Such a bond which has some ionic character is described as polar covalent
bond. Polar covalent molecules can exhibit dipole moment. Dipole moment is equal to the product of
charge separation, q and the bond length, d for the bond. The unit of dipole moment is Debye. One Debye
is equal to 10-18 esu cm.
Dipole moment is a vector quantity. It has both magnitude and direction. Hence, dipole moment of
molecules depends upon the relative orientation of the bond dipoles, but not on the polarity of bonds alone.
A symmetrical structure shows zero dipole moment. Thus, dipole moments help to predict the geometry of
the molecules. Dipole moment values can be used to distinguish between cis- and trans-isomers; ortho-,
meta- and para- forms of a substance, etc. The percentage of ionic character of a bond can be calculated
by the application of the following formula:
Experimental value of dipole moment
% ionic character   100
Theoretical value of dipole moment
1. Which are non-polar molecules?
(A) XeF4 (B) BF3 (C) NH3 (D) H2O
2. A diatomic molecule has a dipole moment of 1.2 D. If the bond length is 1.0  108 cm, what fraction
of charge does exits on each atom?
(A) 0.1 (B) 0.2 (C) 0.25 (D) 0.3
3. Arrange the following compounds in increasing order of dipole moments, toluene (I), o-
dichlorobenzene (II), m-dichlorobenzene (III) and p-dichlorobenzene (IV):
(A) IV < I < II < III (B) I < IV < II < III
(C) IV < I < III < II (D) IV < II < I < III
4. The dipole moment of NF3 is very much less that of NH3 because:
(A) number of lone pair in NF3 is much greater than in NH3
(B) unshared electron pair is not present in NF3 as in NH3
(C) both have different shapes
(D) of different directions of moments of N – H and N – F bonds
5. A covalent molecule, x-y, is found to have a dipole moment of 1.5  1029 cm and a bond length 150
pm. The percentage of ionic character of the bond will be:
(A) 50% (B) 62.5% (C) 75% (D) 90%
Passage 6
According to Molecular orbital theory, Bond order is equal to (Nb-Na)/2, where Nb and Na is the number of
electron present in Molecular bonding and Antibonding orbital respectively.
Generally bond order is same as the number of bonds between bonded atoms from the Valance bond
- + - - -
approach e.g. Bond order of N N,C O ,C N &C C is 3.
Bond Order for resonating molecule = Total Number of bonds between bonded atoms in all resonatingstructure
Number of resonatingstructure
2-
e.g. in carbonate ion CO3
- -
O O O
- - -
O -
O O O O O
Bond order of ‘C-O’ bond in CO32- ion is (1+2+1)/3=1.33

1. Bond order of ‘S-O’ bond in SO42
(A)1.25 (B) 1.5 (C) 1.75 (D) 1.6
2. Decreasing order of O-O bond strength following compound-

(A) O2 > O2= O3> O22 (B) O2 > O2> O22= O3
(C) O2 > O3 > O2> O22 (D) O2 > O2> O3 > O22
3. Comparison of carbon carbon bond length in ethane (I) and benzene (II)
(A) I>II (B) II>I (C) I=II (D) Can’t compare.
MATRIX MATCH
1. Column - I Column - II (Molecular Orbital Theory)

A. B22 p. Paramagnetic
B.C22 q. Diamagnetic
C.O2 r. Bond order =2
D.N22+ s. Bond order =3
2. Column - I Column - II (Bond Angle)

A. XeF2 p. 90o

B. BH 4 q. 109.5o
C.XeOF4 r. 120o
D.PF3Cl2 s. 180o
3. Column - I Column – II (Hybridisation & No. of -bond)

A. XeO2F2 p. sp3 d
B.XeOF4 q. sp3d 2
C.XeF4 r. 4 -bonds
D.PCl5 s. 5 -bonds
4. Column - I Column - II (Order of different compounds)

A. Bond Energy p. HI > HBr > HCl > HF
B.Bond Length q. HI < HBr < HCl < HF
C.Dipole Moment r. HF > HI > HBr > HCl
D.Boiling Point s. I2> Br2> F2> Cl2
5. Column - I Column - II (No. of ,  bonds & lp)
A. CO32 p. 4 -bonds
B. SO42 q. 2-bonds
C. C2O42 r. 8 lp
D. MnO42 s. 10 lp
6. Column - I Column - II
A. Linear shape p. CS2
B.sp hybridization q. XeF2
C.sp3d hybridization r. C2H2
D. CO2 is isostructural to s. NCO−
7. Column - I Column - II
A. One of the ions is tetrahedral p. (NH4)2CO3
in shape
B. Contains covalent, Co-ordinate q. KBF4
& ionic bonds
C. One of the ions is planar in shape r. KCN
D. Contains covalent and ionic bonds s. NaNO3
only
8. Column - I Column – II (IITJEE 2008)

A. B2 p.Paramagentic
B. N2 q.Undergoes oxidation
C. O2― r.Undergoes reduction
D. O2 s.Bond order ≥ 2
t. Mixing of ‘s’ and ‘p’ orbitals
9. Column-I Column-II
(Pair of species) (Identical Property in pairs of species)
A. PCl3F2, PCl2F3 p. Hybridisation of central atom
B. BF3 and BCl3 q. Shape of molecule/ion
C. CO2 and CN 2 2 r.  (dipole moment)
D. C6H6 and B3N3H6 s. Total number of electrons
10. Match the orbitals in List-II with the hybridization in List-I and shape in List-III:
List-I List-II List-III
3
(A)sp d (p) d xy , d yz , d zx (u) Octahedral
(B)sp3d2 (q) d x 2  y 2 , d z 2 (v) Pentagonal bipyramidal
(C)sp3d3 (r) d z 2 (w) Trigonal bipyramidal
Window to JEE MAIN
1. Which of the following is not paramagnetic (DCE 2000)

(a) O 2 (b) O22 (c) O 2 (d) O2
2. The pair of molecules forming strongest intermolecular hydrogen bonding are (DCE 2000)
(a) H 2 O and H 2 (b) HCOOH and Ch3COOH
(b) CH3COCH3 and CHCl3 (d) SiH4 and SiF6
3. The hybridisation state of central atom in PCl5 is (DCE 2000)

(a) dsp3 (b) sp 3 (c) sp3d 2 (d) sp3 d .
4. Which of the following has sp 3  hybridization? (DCE 2001)

(a) BBr3 (b) XeF4 (c) BCl3 (d) XeO3 .
5. Which of the following is not linear? (DCE 2001)


(a) I 3 (b) CO2 (c) ClO 2 (d) None of these.
6. Which of the following compounds, shows ionic, covalent and coordinate bonds?
(a) NaCl (b) HCl (c) CuSO4 ; 5H2O (d) CaSO4 ; 5H2O.
(DCE 2001)
7. Which of the following is polar? (DCE 2002)
(a) IF7 (b) SF6 (c) PCl3 (d) PCl5
8. Which of the following has no dipole moment? (DCE 2002)

(a) H 2 O (b) O 3 (c) SO 2 (d) CO2
9. Which of the following is non-linear molecule? (DCE 2003)

(a) BeCl 2 (b) CS2 (c) CO2 (d) SO3
10. Which one of the following is highest melting halide? (DCE 2003)
(a) Agl (b) AgF (c) AgBr (d) AgCl
11. The polarising ability of which one of the following is highest? (DCE 2003)
(a) large –ve ion (b) small, highly –ve ion(c) large +ve ion (d) small, highly +ve ion
12. In O2 , O2 and O22 molecular species, the total number of antibonding electrons respectively are
(DCE 2003)
(a) 8, 6, 8 (b) 6, 6, 6 (c) 1, 0, 2 (d) 7, 6, 8
13. Maximum number of hydrogen bonding in H 2 O is (DCE 2004)

(a) 3 (b) 2 (c) 1 (d) 4
14. Which of the following molecules has pyramidal shape? (DCE 2004)
(a) CO32  (b) SO3 (c) PCl3 (d) NO . 
3
15. Which of the following has covalent bond? (DCE 2004)

(a) NaH (b) AlCl3 (c) Na 2S (d) MgCl2
16. Increasing order of electronegativity of the hybrid orbitals is (DCE 2005)
(a) sp < sp 2  sp3 (b) sp 2  sp < sp3 (c) sp3  sp 2  sp (d) sp  sp  sp .
2 3
17. Among the following, shortest bond length is in (DCE 2005)

(a) N 2 (b) O 2 (c) F2 (d) Cl 2
18. How many C - C bonds are there in ? (DCE 2005)
(a) 14,8 (b) 18,8 (c) 9,4 (d) 14, 2
19. Pair of species having identical shapes for molecules is (DCE 2005)
(a) CF4 ,SF4 (b) BF3 , PCl3 (c) XeF2 ,CO2 (d) PF5 , IF5
20. Metalliclustre is explained by

(a) Diffusion of metal ions (b) Oscillation of loose electrons
(c) Excitation of free protons (c) Existence of bec lattice.
21. Which of the following represents isostructural pairs? (DCE 2006)

(a)  NF3 , NO3  and BF3 , H3O  (b)  NF3 , HN3  and  NO3 , BF3 
(c)  NF3 , H3O  and NO3 , BF3  (d)  NF3 , H3O  and HN3 , BF3 
22. Among the following, the pair in which the two species are notisostructural is (DCE 2007)
   
(a) IO3 and XeO3 (b) BH4 and NH4 (c) PF6 and SF6 (d) SiF4 and SF4
23. Which of the following compounds has the smallest bond angle in its molecule ? [AIEEE-2003]
(a) SO2 (b) H2O (c) H2S (d) NH3
24. An ether is more volatile than an alcohol having the same molecular formula. This is due to:
[AIEEE-2003]
(a) dipolar character of ethers.
(b) alcohols having resonance structures.
(c) inter-molecular hydrogen bonding in ethers.
(d) inter-molecular hydrogen bonding in alcohols.
25. The bond order in NO is 2.5 while that in NO+ is 3. Which of the following statements is true for
these two species? [AIEEE-2004]
(a) bond length in NO+ is greater than in NO (b) bond length in NO is greater than in NO+
(c) bond length in NO+ is equal to that in NO (d) bond length is unpredictable
26. The states of hybridization of boron and oxygen atoms in boric acid (H3BO3) are respectively :
[AIEEE-2004]
2
(a) sp and sp 2 2
(b) sp and sp 3 3
(c) sp and sp 2 3
(d) sp and sp3
27. Based on lattice energy and other considerations, which one of the following alkali metal chlorides is
expected to have the highest melting point ? [AIEEE-2005]
(a) LiCI (b) NaCl (c) KCl (d) RbCl
28. The molecular shapes of SF4 ,CF4 and XeF4 are (AIEEE 2005)
(a) The same with 2, 0 and 1 lone pairs of electrons on the central atoms respectively
(b) The same with 1, 1 and 1 lone pair of electrons on the central atoms respectively
(c) Different with 0, 1 and 2 lone pairs of electrons on the central atoms respectively.
(d) Different with 1, 0 and 2 lone pairs of electrons on the central atoms respectively.
29. Which of the following molecules/ions does not contain unpaired electrons? (AIEEE 2006)
(a) O22 (b) B 2 (c) N 2 (d) O 2
30. In which of the molecules/ions are all the bonds not equal? (AIEEE 2006)
(a) SF4 (b) Si F4 (c) XeF4 (d) BF4
31. Which of the following species exhibits the diamagnetic behavior? (AIEEE 2007)
(a) NO (b) O22 (c) O 2 (d) O 2 .
32. The charge/size ratio of a cation determines its polarizing power. Which one of the following
sequences represents the increasing order of the polarizing power of the cationic species,
K  , Ca 2 , Mg 2 , Be 2 ? (AIEEE 2007)
(a) Ca 2  Mg2  Be  K (b) Mg2  Be2  K  Ca 2
(c) Be2  K  Ca 2  Mg2 (d) K  Ca 2  Mg2  Be2
33. In which of the following ionization processers, the bond order has increased and the magnetic
behaviour has changed? (AIEEE 2007)

(a) N 2  N 2 (b) C2  C2 (c) NO  NO (d) O 2  O 2
34. Which of the following hydrogen bonds is the strongest? (AIEEE 2007)
(a) O  H    F (b) O  H  H (c) F  H    F (d)
35. Which one of the following constitutes a group of the isoelectronic species? (AIEEE 2008)
  2 
(a) N 2 , O , NO , CO
2 (b) C , O , CO, NO
2 2
 2   2 2
(c) NO , C2 , CN , N 2 (d) CN , N 2 , O 2 , C 2 .
36. Using MO theory predict which of the following species has the shortest bond length?
2   2
(a) O2 (b) O 2 (c) O 2 (d) O2 (AIEEE 2009)
37. Which of the following species is not paramagnetic?

(a) B 2 (b) NO (c) CO (d) O 2 (JEE 2016)
Window to JEE ADVANCED

A. Fill in the blanks:
1. The angle between two covalent bonds is maximum in …………… (CH4, H2O, CO2)
2. Pair of molecules which forms strongest intermolecular hydrogen bond is …………….

(SiH4 and SiF4, CH3—C—CH3 and CHCI3, HC –OH and CH3—C –OH)
O O O
3. There are ………..  bonds in a nitrogen molecule.

4. …………. hybrid orbitals of nitrogen atom are involved in the formation of ammonium ion.
5. The shape of CH 3  + is ……………..
6. The two types of bonds present in B2H6 are covalent and ……….
7. When N2 goes to N 2 , the N –N bond distance ….., and when O2 goes to O 2 the O-O
bonddistance……….
 
8. Among N2O, SO2, I 3 and I 3 , the linear species are ………. and ………
B. True / False :
1. Linear overlap of two atomic p – orbitals leads to a sigma bond.
2. All molecules with polar bonds have dipole moment
3. SnCl2 is a non – linear molecule.
4. In benzene, carbon uses all the three p – orbitals for hybridization.
5. sp3 hybrid orbitals have equal s and p character.
6. The presence of polar bonds in a poly – atomic molecule suggests that the molecule has non-zero
dipole moment.
7. The dipole moment of CH3F is greater than that of CH3Cl.
C. Multiple Choice Questions with ONE correct answer :

1. 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
2. The ion that is isoelectronic with CO is

( 1981 – 1 Mark )
(A) CN─ (B) O2+ (C) O2─ (D) N2+
3. Among the following , the molecule that is linear is
(A) CO2 (B) NO2 (C) SO2 (D)ClO2
4. The compound with no dipole moment is

(A) Methylchloride (B) carbontetrachloride
(C) methylenechloride (D) chloroform
5. Carbon tetrachloride has no net dipole moment because of

(A) its planar structure
(B) its regular tetrahedral structure
(C) similar sizes of carbon and chlorine
(D) similar electron affinities of carbon and chlorine
6. Which one among the following does not have the hydrogen bond?
(A) phenol (B) liquid NH3 (C) water (D) liquid HCl
7. The molecule having one unpaired electron is :

(A) NO (B) CO (C) CN─ (D) O2
8. The hydrogen bond is strongest in :

(A) O – H………S (B) S – H………...O (C) F- H………..F (D) F-H……..O
9. The hybridization of sulphur in sulphur dioxide is :

(A) sp (B) sp3 (C) sp2 (D) dsp2
10. Hydrogen bonding is maximum in

(A) Ethanol (B) Diethylether (C) Ethly chloride (D) Triethylamine
11. The species in which the central atom uses sp2 hybrid orbitals in its bonding is
(A) PH3 (B) NH3 (C) CH 3 (D) SbH3
12. The molecule that has linear structure is

(A)CO2 (B) NO2 (C) SO2 (D) SiO2
13. The molecule which has zero dipole moment is :
(A) CH2Cl2 (B) BF3 (C) NF3 (D) ClO2
14. The molecule which has pyramidal shape is :

(A) PCl3 (B) SO3 (C) CO 32  (D) NO 3
15. The compound in which ‘C’ uses its sp3 hybrid orbitals for bond formation is :
(A) HCOOH (B) (H2N)2CO (C) (CH3)3COH (D) CH3CHO
16. The type of hybrid orbitals used by the chlorine atom in ClO2 is
(A) sp3 (B)sp2 (C)sp (D) none of these
17. The maximum possible number of hydrogen bonds a water molecule can form is
(A) 2 (B) 4 (C) 3 (D) 1
18. Which one is most ionic :
(A) P2O5 (B) CrO3 (C) MnO (D) Mn2O7
19. Number of paired electrons in O2 molecule is :
(A) 7 (B) 8 (C) 16 (D) 14
20. Among the following species, identify the isostructural pairs.
NF3, NO3 , BF3 , H3O+ , HN3
 
(A) NF3 , NO3 and BF3 , H 3 O   
(B) NF3 , HN3  and NO3 , BF3 

(C) NF3 , H 3 O  and NO3 , BF3   
(D) NF3 , H 3 O  and HN 3, BF3 
21. The number and type of bonds between two carbon atoms in CaC2 are :
(A) one sigma (  ) and one pi (  ) bonds
(B) one sigma (  ) and two pi (  ) bonds
(C) one sigma (  ) and one and a half pi (  ) bonds
(D) one sigma (  ) bond.
22. Among KO2, AlO 2 , BaO2 and NO 2 , unpaired electron is present in

(A) NO 2 and BaO2 (B) KO2 and AlO 2 (C) KO2 only (D) BaO2 only
23. Among the following compounds the one that is polar and has the central atom with sp 2
hybridization is
(A) H2CO3 (B) SiF4 (C) BF3 (D) HClO2
24. Which contains polar and non – polar bonds?

(A) NH4CI (B) HCN (C) H2O2 (D) CH4
25. The critical temperature of water is higher than that of O2 because the H2O molecule has
(A) fewer electron than O2 (B) two covalent bonds
(C) V – shape (D) dipole moment
26. Which one of the following compounds has sp2 hybridization?
(A) CO2 (B) SO2 (C) N2O (D) CO
27. Read the following statement and explanation and answer as per the options given below :

Assertion: A lewis structure of O3 is O

O O O
Reason: structure is not allowed because octet around O cannot be expanded.
O O
(A) If both assertion and reason are correct, and reason is the correct explanation of the assertion.
(B) If both assertion and reason are correct, but reason is not the correct explanation of the reason
assertion.
(C) If assertion is correct but reason is incorrect.
(D) If assertion is incorrect but reason is correct.
28. Read the following statement and explanation and answer as per the options given below :-
Assertion: LiCl is predominantly a covalent compound.
Reason: Electronegativity difference between Li and Cl is too small.
(A) If both assertion and reason are correct, and reason is the correct explanation of the assertion .
(B) If both assertion and reason are correct, but reason is not the correct explanation of the assertion.
(C) If assertion is correct but reason is incorrect.
(D) If assertion is incorrect but reason is correct.
29. The correct order of increasing C – O bond length of CO, CO 32  , CO2 , is

(A) CO 32  < CO2< CO (B) CO2< CO 32  < CO (C) CO <CO 32  <CO2(D) CO<CO2<CO 32 
30. The geometry of H2S and its dipole moment are

(A) angular and non – zero (B) angular and zero
(C) linear and non – zero (D) linear and zero.
31. Molecular shapes of SF4, CF4 and XeF4 are

(A) the same, with 2, 0 and 1 lone pairs of electrons respectively
(B) the same, with 1,1 and 1 lone pairs of electrons respectively
(C) different, with 0,1 and 2 lone pairs of electrons respectively
(D) different, with 1, 0 and 2 lone pairs of electrons respectively
32. The hybridization of atomic orbitals of nitrogen in NO 2 , NO 3 and NH 4 are

(A) sp, sp3 and sp2 respectively (B) sp, sp2 and sp3 respectively
2 3
(C) sp , sp and sp respectively (D) sp2 , sp3 and sp respectively
33. Specify the coordination geometry around and hybridization of N and B atoms in a 1:1 complex of
BF3 and NH3
(A) N: tetrahedral, sp3; B: tetrahedral, sp3 (B) N: pyramidal, sp3; B: pyramidal, sp3
(C) N: pyramidal, sp3; B: planar, sp2 (D) N: pyramidal, sp3; B: tetrahedral, sp3
34. Which of the following molecular species has unpaired electron (s)?
(A) N2 (B) F2 (C) O─2 (D) O 22
35. According to molecular orbital theory which of the following statement about the magnetic character and
bond order is correct regarding O2+
(A) Paramagnetic and Bond order < O2 (B) Paramagnetic and Bond order > O2
(C) Diamagnetic and Bond order < O2 (D) Diamagnetic and Bond order > O2
36. Which species has the maximum number of lone pair of electrons on the central atom?
(A) CIO 3  (D) I 3 
 
(B) XeF4 (C) SF4
D. Multiple Choice Questions with ONE or MORE THAN ONE correct answer :
1. CO2 is isostructural with :
(A) HgCl2 (B) SnCl2 (C) C2H2 (D) NO2
2. The linear structure is assumed by :

(A) SnCl2 (B) NCO− (C) CS2 (D) NO+2 (E) SO2
3. Which of the following have identical bond order?
(A) CN− (B) O2− (C) NO+ (D) CN+
4. The molecules that will have dipole moment are

(A) 2,2- Dimethylpropane (B) trans -2 –pentene
(C) cis -3-Hexene (D) 2, 2, 3,3, - tetramethylbutane
5. Pick out the isoelectronic structures from the following ;

I. CH 3 II. H3O+ III. NH3 IV CH 3
(A) I and II (B) III and IV (C) I and III (D) II, III and IV
6. The geometry and the type of hybrid orbital present about the central atom in BF3 is
(A) linear, sp (B) trigonal planar, sp2
3
(C) tetrahedral, sp (D) pyramidal, sp3
7. Which of the following molecules has as O – O bond?
(A) H2S2O8 (B) H2S2O7 (C) H2SO5 (D) H2S2O6
8. Which of the following species is paramagnetic:

(A) CN (B) NO (C) O 22  (D) O2
9. CO2 molecule is not isostructural with:

(A) HgCl2 (B) SnCl2 (C) C2H2 (D) NO2
10. Ionic compounds in general do not posses:
(A) high melting points and non-directional bonds
(B) high melting points and low-boiling points
(C)directional bonds and low-boiling points
(D) high solubilities in polar and non-polar solvents
11. Which of the following statements is incorrect:

(A) A  bond is weaker than a  bond (B) There are four co-ordinate bonds in the NH 4 ions
(C) The covalent bond is directional in nature(D) HF is less polar than HCl
12. Correct order of decreasing boiling points is:

(A) HF > HI > HBr > HCl (B) H2O > H2Te > H2Se > H2S
(C) Br2> Cl2> F2 (D) CH4> GeH4> SiH4
13. Which of the following have a linear structure?

(A) HgCl2 (B) SnCl2 (C) ICl 2 (D) CS2
14. Which of the following compound is/are non-polar?

(A) NO2 (B) B2H6 (C) PF3Cl2 (D) B3N3H6
15. Which of the following statements is/are correct?
(A) All carbon-to-carbon bonds contain a sigma bond and one or more pi bonds
(B) All carbon to hydrogen bonds are pi bonds
(C) All oxygen to hydrogen bonds are hydrogen bonds
(D) All carbon to hydrogen bonds are sigma bonds
(E) All carbon to carbon bonds are sigma bonds
16. Non-polar molecules are:

(A) CH4 (B) C2F2 (C) C2F4 (D) OF2
17. In which of the following there is intermolecular hydrogen bonding?

(A) Water (B) Ethanol (C) Acetic acid (D) H – F
18. In which species the hybrid state of central atom is/are sp3d :
(A) I3+ (B) SF4 (C) PF5 (D) IF5
19. Which of the following statements are correct about sulphur hexafluoride?
(A) all – F bonds are equivalent
(B) SF6 is a planar molecule
(C) oxidation number of sulphur is the same as number of electrons involved in bonding
(D) sulphur has acquired the electronic structure of the gas argon.
20. Which of the following statement is incorrect:

(A) O2 is paramagnetic, O3 is also paramagnetic
(B) O2 is paramagnetic, O3 is diamagnetic
(C) B2 is paramagnetic C2 is also paramagnetic
(D) Different observation is found in their bond length when NO  NO and CO  CO
 
21. Which of the following statements are not correct?

(A) All C – O bonds in CO 32  are equal but not in H2CO3
(B) All C – O bonds in HCO 2 are equal but not in HCO2H
(C) C – O bond length in HCO 2 is longer than C – O bond length in CO 32 
(D) C – O bond length in HCO 2 and C – O bond length in CO 32  are equal
22. In the structure of H2CSF4, which of the following statement is/are correct?
(A) Two C – H bonds are in the same plane of axial S – F bonds
(B) Two C – H bonds are in the same plane of equatorial S – F bonds
(C) Total six atoms are in the same plane
(D)Equatorial S – F plane is perpendicular to plane of  -bond
23. In which compound vacant orbital take part in hybridization:
(A) B2H6 (B) Al2Cl6 (C) C2H5Cl (D) H3BO3
24. Which of the following is true for N2O?
(A) Its molecule is linear
(B) Symmetric N – O – N is a favored structure as compared to N – N – O skeleton
(C) Bond orders are fractional for N – N and N – O bonds
(D) It is a neutral oxide
25. Silane is more reactive than CH4 due to:
(A) larger size of Si compared to ‘C’ which facilitate the attack by nucleophile.
(B) Polarity of Si – H bond is opposite to that of C – H bond
(C) Availability of vacant 3d orbitals in case of Si to form the reaction intermediateeasily
(D) Si – H bond energy is lower than of C– H bond
26. Which of the following statements is/are not correct for following compounds?
(I) SCl2 (OCH3)2 and (II) SF2 (OCH3)2
(A) – OCH3 groups in both cases occupy the same position
(B) Cl-atoms occupy equatorial position in case of (I) and F-atoms occupy equatorialposition in case
of (II)
(C) Cl-atoms occupy axial position in case of (I) & F-atoms occupy equatorial position in case of (II)
(D)Cl and F-atoms occupy either axial or equatorial position in case of (I) and (II) respectively.
27. Among the following, the correct statement(s) is (are)

(A) Al  CH3 3 has three centre two-electron bonds in its dimeric structure
(B) AlCl3 has the three-cenre two-electron bond in its dimeric structure
(C) BH3 has the three-centre two-electron bonds in its dimeric structure
(D) The Lewis acidity of BCl3 is greater than that of AlCl3
ANSWER KEY
Foundation Builder (Objective)
BASIC CONCEPTS
1. B 2. C 3. B 4. B 5. B
6. D 7. D 8. B 9. C 10. C
11. A 12. D 13. D 14. D 15. A
16. C 17. D 18. D 19. C 20. C
21. B
VSEPR THEORY
1. D 2. B 3. D 4. A 5. B
6. C 7. B 8. C 9. D 10. B
11. A 12. C 13. B 14. B 15. A
16. C 17. B 18. B 19. B 20. B
21. B 22. C 23. D 24. B 25. A
26. C 27. A 28. D 29. C 30. C
BOND PARAMETERS & FAJAN’S RULE
1. B 2. D 3. B 4. B 5. A
6. B 7. D 8. D 9. B 10. C
11. C 12. C 13. B 14. D 15. C
16. D 17. B 18. C 19. B 20. C
21. D 22. D 23. C 24. C 25. C
POLAR COVALENT BONDS & DIPOLE MOMENT
1. A 2. C 3. C 4. B 5. D
6. A 7. B 8. C 9. A 10. B
11. C 12. D 13. B 14. D 15. A
16. D 17. C 18. B 19. C 20. B
21. A 22. D 23. C 24. A
MOLECULAR ORBITAL THEORY
1. C 2. A 3. D 4. C 5. C
6. D 7. A 8. D 9. B 10. A
11. B 12. A 13. A 14. B 15. B
16. A 17. C 18. C 19. B
HYDROGEN BONDING
1. C 2. B 3. D 4. D 5. B
6. A 7. D 8. A 9. B 10. B
11. D 12. D 13. D 14. D 15 C
16. A 17. D 18. C 19. A 20. B
21. C 22. A 23. D 24. D 25. B
26. C 27. A
Get Equipped for JEE MAIN
1. B 2. D 3. D 4. A 5. D
6. A 7. D 8. C 9. D 10. D
11. C 12. C 13. C 14. B 15. B
16. A 17. D 18. D 19. B 20. B
21. A 22. B 23. A 24. B 25. C
26. D 27. B 28. A 29. D 30. A
31. C 32. C 33. C 34. D 35. B
36. C 37. C 38. D 39. D 40. C
41. C 42. A 43. C 44. B 45. C
46. A 47. A 48. D 49. D 50. D
51. A
Get Equipped for JEE ADVANCED
ONLY ONE OPTION CORRECT
1. B 2. D 3. C 4. D 5. C
6. D 7. A 8. B 9. B 10. B
11. C 12. C 13. D 14. D 15. B
16. A 17. B 18. B 19. A 20. A
21. B 22. C 23. B 24. A 25. D
26. C 27. C 28. D 29. C
MORE THAN ONE OPTION CORRECT

1. A, B, C 2. B, C, D 3. A, C 4. B, C 5.A, B, C
6. B, C 7. B, C 8. A, B 9. A, B, C, D 10.B, C, D
11. A, D 12. A, C 13. A, C, D 14. A, B
COMPREHENSION TYPE
Passage-1 1. D 2. A 3. D 4. B 5. D 6. C
7. C 8. C
Passage-2 1. A 2. C 3. A 4. C 5. D 6. D
7. C
Passage-3 1. D 2. A 3. B
Passage-4 1. A 2. D 3. C 4. B 5. D
Passage-5 1. A, B 2. C 3. C 4. D 5. B
Passage-6 1. B 2. A 3. A
MATRIX MATCH
1. A  q, r; B  q, s; C  p, r; D  q, r
2. A  s; B  q; C  p, s; D  p, r, s
3. A  p, r; B  q, s; C  q, r; D  p, s
4. A  q; B  p, s; C  p; D  r
5. A  r; B  p, q, s; C  q, s; D  p, q, s
6. A  p, q, r, s; B  p, r, s; C  q; D  p
7. A  p, q; B  p, q, s; C  p, s; D  r
8. A  p, r, t; B  s, t; C  p, q; D  p, q, s
9. A  p, q; B  p, q, r; C  p, q, r, s; D  p, q, r, s;
10. A─r─w; B─q─u, C─p─v
WINDOW TO JEE MAIN
1. b 2. b 3. d 4. d 5. c 6. c 7. c
8. d 9. d 10. b 11. d 12. d 13. d 14. c
15. b 16. c 17. a 18. c 19. c 20. b 21. c
22. d 23. c 24. d 25. b 26. b 27. b 28.d
29. a 30. a 31. b 32. d 33. c 34. c 35. c
36. a 37. c
WINDOW TO JEE ADVANCED
A. 1.CO2 2. HCOOH and CH3COOH

3. 2 4. sp3
5.planar 6. three centred two electrons bond or banana bond
7. Increases, decreases 8. N2O, I 3
B. 1T 2F 3T 4F 5F 6F 7F
C. 1 C 2 A 3 A 4 B 5 B 6 D
7 A 8 C 9 C 10 A 11 C 12 A
13 B 14 A 15 C 16 A 17 B 18 C
19 D 20 C 21 B 22 C 23 A 24 C
25 D 26 B 27 A 28 C 29 D 30 A
31 D 32 B 33 A 34 B 35 A 36 C
37 B 38 D
D. 1 A,C 2 B,C,D 3 A,C 4 B,C

5 B,D 6 B 7. A,C 8. B, D
9. B, D 10. B,C,D 11. A,B,D 12. A,B,C
13. A,C,D 14. B,D 15. A,D 16. A,B,C
17. A,B,C,D 18. A,B,C 19. A,C 20. A,C,D
21. A,C 22. C,D 23. A,C 24. A,B
25. A,C,D 26. A,B,C,D 27. A,C,D

Chemical Bonding (ADV)

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Chemical Bonding Rg-Chem.

Team Chemistry @ IIT-ian’s PACE

2. Solved Problems (Subjective) 39 – 44

3. Solved Problems (Objective) 44 – 48

4. Foundation Builders (Objective) 49 – 59

5. Get Equipped for JEE (MAIN) 59 – 63

6. Get Equipped for JEE (ADVANCED) 63 – 72

7. Window To IIT-JEE (MAIN) 73 – 75

8. Window To IIT-JEE (ADVANCED) 75 – 80

CHEMICAL BONDING : Tentative Lecture Flow

Lecture – 3 VSEPR Theory & Hybridisation

3. LEWIS DOT STRUCTURES

LIMITATIONS OF LEWIS THEORY OF DRAWING STRUCTURE

METHOD OF DRAWING LEWIS STRCUTURES

(i) First calculate n1.

(iii) Subtract n1 from n2, which gives n3.

Question: Determine Lewis structure of NO 3 ion.

Thus, the structures can now be shown as

Final structure of NO3 is therefore shown as

4. IONIC BOND (OR ELECTROVALENT LINKAGE)

PROPERTIES OF IONIC COMPOUNDS

Na+(g) + Cl-(g) Na+Cl-(s) + U; where U is the lattice energy.

Hence, the magnitude of lattice energy depends on two factors:

6. CO-ORDINATE OR DATIVE BOND

For Example : Ammonium ion

CHARACTERISTICS OF COORDINATE COMPOUNDS:

7. VALENCE BOND THEORY

7.1 Sigma and Pi Bonding

7.2 Limitation of Valance Bond Theory

8.1 Geometry of Molecules

8.2 Geometry of Molecules

Why atomic orbitals in a given atom undergo hybridization?

9.2 Types of Hybridisation

Because of sp3hybridisation of carbon atom, CH4 molecule has tetrahedral shape.

Let us study some examples of molecules involving sp hybridisation.

(iv) sp3d -hybridisation

9.3 Method of Predicting the hybridization state

Simple Molecule Polyatomic Anion Poyatomic Cation

In the above formulae,

2 0 sp Linear BeCl2, HgCl2

2 1 sp2 bent (V-shape) SnCl2, PbCl2

2 3 sp3d Linear I3–, XeF2

3 0 sp2 Trigonal planar BF3, BCl3

AX3 3 1 sp3 Pyramidal NH3, H3O+

3 2 sp3d T-shape ClF3, BrF3

4 0 sp3 Tetrahedral CH4, NH4+

4 2 sp3d2 Square planar XeF4

5 0 sp3d Trigonalbipyramidal PCl5

6 0 sp3d2 Octahedral SF6

AX7 7 0 sp3d3 Pentagonal bipyramidal IF7

3. Number of lone pairs of electrons:

10.2 BOND LENGTH

2. Bond length decreases with the multiplicity of bonds:

Following factors can affect bond angle:

1.Hybridisation of central atom:

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11.1 Conditions for Resonance

(i) Sulphur dioxide SO2

(ii) Nitrous oxide (dinitrogen oxide), N2O

(iii) Nitric oxide, NO

(iv) Carbonate ion, CO  (planar, triangular)

Kekule Structures Dewar Structures

12. TRANSITION FROM IONIC TO COVALENT BOND – FAJANS’ RULE

Arrangement :  12s 1s2  22s 2 s2  1 y 