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 CHEMICAL BONDING
My name is Bond “Covalent Bond”

JEE SYLLABUS
Electrovalent (ionic bond ) and covalent (including coordinate ) bonds; polarity in molecules ;
dipole moments (qualitative aspects only ); conceptt of hybridization involving s and p
orbitals only; hydrogen bond.

Introduction

There are several different theories which explain the electronic structure and shapes of known
molecules ,and attempt to predict the shapes of molecules whose structures are so far unknown.
Each theory has its own virtues and shortcomings. None is rigorous . Theories change in the light
of new knowledge . If we Knew or could prove what a bond was, we would not need theories,
which by definition cannot be proved . The value of a theory lies more in its usefulness than in its truth.
Being able to predict the shape of a molecule is important . In many cases all the theoreis give the
correct answers.

The Lewis Theory

The octet rule : 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.

Thic 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 valencies in a large number of
cases . Thee are exceptions to the .. octet rule; for example hydrogen is stable with only two electrons.
Other exceptions are discussed later .Today,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 structure are represented below .
H

(NH3) H : N : H or H N H
..
H

H H
.. .. ..
(CO2) : O C O: (CH3CHO) H C C O:

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 struc-
tures of inorganic molecules.

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Exceptions to octat rule:

* Odd- elecron species like NO ,NO2 , O2 etc. Since it is impossible to distribute an odd
number of electrons into pairs , these species necessarily violate the octet rule.
The Valence Bond theory handles such species rather clumsily (odd-electron bond
etc.) the molecular orbital theory copes much better.

* Species in which the central atom ‘expands ‘ its octet (so to speak ) PCl5, SF6, many
transition metal compounds etc.

* Electron- defiicient species like BCl3, BeCl2, AlCl3, B2H6 etc. in which the central atom
has fewer than eight electrons.

ELECTROVALANCY
This type of valancy involver the transfer of leectrons from one atom to another , whereby each atom
may attain octat in their outermost shell. the resulting ions that are formed by gain or loss of electrons
ae held together by electrostatic forcesof attaraction due to opposite nature of their charges. The
reaction between potassium and chlorine to form potassium chloride is an example of this type of
valancy.

K. Cl K+Cl-

For an ionic bond one of the species must have low ionisation energy and the other should have high
electron affinity.Low ionisation energy is mainly exhibited by the alkali and alkaline earth metals , and
high electron affinity by the halogen and chalcogens.Therefore this group of elements are predominant
in the field of ionic bonding.

General properties of ionic compounds

1 An ionic compound is composed of positive and negative ions , the ion pairs of oppo-
site charges are held together by electrostatic attaraction.The ions arrange themselves
in a regular pattern in the crystal.. For example KCl crystal consists of two interlocking
face centered cubic lattices, one of potassium ions and other of chloride ions.

2. An ionic compound does not exist as a definite entity as molecules.

3. The ionic compounds does not conducts electricity in solid state but can conduct
electricity in fused state or in solution in a suitable solvent.

4. In an ionic compound the ions tend to adhere by poerfful attaractive forces in crystals ,
therefore ionic compounds exist only in solid state and their melting and boiling points
are high.

5. An ionic bond is non rigid and non directional hence ionic compounds does not show
isomerism.

6. A polar liquid such as water alcohol or liquid ammonia diminishes the forces of
attaraction between the ions of the ionic compoundshence ionic compounds dissolves
in polar solvents but not in non polar solvents.

COVALANCY
This type of valancy involves..the sharing of electrons between the concerned atoms to attain the octat
configuration with the sharing pair being contributed by both species equally.The sharing of one pair of

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electrons is called a single covalant bond while sharing of more than one pair is called multiple bonds.

General properties of covalant compounds

1. A covalant cmpound is consists of dicrete molecules generally. Due to this

discreteness the covalant compounds are found generally in gaseous of liquid state
with low melting and boiling points.

2. A purely covalant compound is a non polar substance and does not conducts electricity

3. A covalant bond is rigid and directional hence covalant compounds shows isomerism.

4. Due to non polar nature covalant compounds are soluble in non polar solvents like
benzene , carbontetrachloride , toluene etc.

Valence bond theory (VBT)

A covalent bond is formed by overlapping of valence shell atomic orbitals of the two atoms having
unpaired electron. As a result of overlapping, there is maximum electron density between the
bonding atoms and large part of bonding forces arises due to electrostatic force of attraction
between accumulated electron cloud and two nuclei. Greater the overlapping of atomic orbitals
higher is the strength of chemical bond.The paired electron of valence shell of an atom can take part
in covalent bonding subject to availbility of vacant orbitals of slightly higher energy of the same
main energy shell and availability of energy for unpairing of paired electron and their shifting to
vacant orbitals. The point explains the trivalency of boron, travalency of carbon, pentvalency of
phosphorous hexavalency of S and hepta valency of Cl, Br, l.

Depending on type of overlapping atomic orbitals bond can be classiied int two types.

1. Sigma ( ) . 2. Pi ( ) bond.

Bond: When covalent bond is formed by overlapping of atomic orbitals along the same axis it
is called bond . Such type of bond is symmetrical about the line joining the two nuclie e.g.
Overlapping Shape predicted by V.B.T. By M.O.T.
a) s - s
overlapping Overlapping
Molecular axis
a) s - pb) s-p
overlappingoverlapping +
P
c) p - p
overlapping +
p p

2. Bond: This type of bond is formed by the sidewise or lateral overlapping of two half
filled atomic orbitals.

P
P

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The strength of a bond depends upon the extent of overlapping of half- filled atomic orbitals.The
extent of overlapping is between two atoms is always greater when there is end to end overalapping
of orbitals than, when there is sidewise overlapping of orbitals. Hence  -bond is always stronger
then  bond.
The average distance between the nuclei of the two bonded atoms in a molecule is called bond
length and the energy required to break one mole of bonds of particular type in gaseous state is
called Bond energy or Bond strength. The same amount of energy is released in formation of one
mole of particular Bond.

Limitation :VBT cannot explain the paramagnetic properties of B2, O2 etc.

VBT does not explains the formation of H2+ and other ions.

Hybridization

The mixing of merging of dissimilar orbitals of nearly similar energies to form new orbitals is
known as hybridization and the new orbitals formed are known as hybrid orbitals.

The following points are to be remembered about hybridization.

* Orbitals belonging to the same atom or ion having similar energies get hybridized.

* No. of hybrid orbitals is equal to the no. of orbitals taking part in hybridization.

* The reason hybridization takes place is to produce equivalent orbitals which give
maximum symmetry.

* It is not known whether actually hybridization takes place or not. It is a concept which
explains the known behaviour of molecules.

1. sp3 Hybridization : In this 1 ‘s’ and 3 ‘p’ orbitals of the same principle quantum number
mix to form 4 sp3 hybridized orbitals. These orbitals orient theselves towards the corners
of a regular tetrahedron . The angle between the orbitals is 109o28’.
For example CH4
H

C
H
H H
2. sp2 hybridization : In this 1 ‘s’ and 2 ‘p’ orbitals of the same principle quantum number
mix to form three sp2 hybridized orbitals. These orbitals orient themselves towards the
corners of an equilateral triangle E.g. BF3

F F
B

F
In cases like ethene (C2H4), the two carbon atoms have one p orbital each with an unpaired
electron. The p-orbitals overlap in sideways fashion to give rise to a double bond.
H  H

C  C
H H

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When a bond is formed with head - to- head overlap, It is called a sigma () bond. When a bond is
formed with sideways overlap, it is called a pi ( ) bond.

3. sp hybridization : In this one ‘s’ and one ‘p’ orbital of the same principle quantum number
mix to form 2sp hybridized orbitals . eg. BeCl2
In cases like ethyne C2H2, two p orbitals with two unpaired electrons are present in each
carbon atom. These overlap in sideways fashion and produce a triple bond.

H C  C H


4. sp3 d hybridization : In this one ‘s’ three ‘p’ and one ‘d’ orbital of the same principle quantum
number mix to give 5 sp3 d hybridized orbitals.
These orbitals orient themselves towards the corners of a trigonal bipyrmaidal structure.
e. g . PCl5
Cl

Cl Cl
P

Cl

Cl

5. sp3d2 hybridization : In this one ‘s’ three ‘p’ and two ‘d’ orbitals mix to form 6 sp3d2
hybridized orbitals .These orient themselves towards the corners of a regular octahedron.
e. g . SF6
F
F

s F
F

F
F

VSEPR (Valence Shell Electron Pair Repulsion ) Theory

The geometric arrangement of atoms in molecules and ions may be predicted by means of the
valence - shell electron - pair repulsion (VSEPR) theory. This type includes molecules which may
or may not obey the octet rule but have only single bonds.

VSEPR theory may be summarized as follows :

1. The shape of the molecue is determined by repulsions between all of the electron
pairs present in the valence shell.

2. A lone pair of electrons takes up more space around 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 angle between the atoms

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 must be decreased.
Lone pair Lone pair repulsion > Lone pair Bond pair repulsion > Bond pair Bond pair repulsion

3. The magnitude of repulsions between bonding pairs of electrons depends on the

electronegativity difference between the central atom and the other atoms.

4. Double bonds cause more repulsion than single bonds and triple bond cause more
repulsion than double bonds.

To find the shape of a molecule follow the steps given below :

i) Identify the central atom and decide the oxidation state.

ii) Write the outermost ground state electronic configuration in box form.

iii) Write the outermost exited state electronic configuration in box form having the no. of
unpaired electrons equal to the oxidation state.

iv) Determine the no. of hybrid orbitals (N) by following formula

F
no. of electrons I
1 G
G
N  in outermost shell  no. of other  no. of negative  no. of positive J
J
2
H
ofcenral atom monovalent atoms ch arg es ch arg es K
v) Draw the basic structure of molecule as indicated by the hybridization , The hybrid
orbitals will form sigma bonds.

vi) The orbitals which do not participate in hybridisation will form pi bonds.

A brief summary of molecular shapes resulting from different configurations of electrons pairs is
presented below. With very few exceptions , the predictions have been shown to be correct.

a) CO 2 S P
Central atom is C
O.S of C = 4
Electronic configuration of C

El. conf. after excitation

No. of Hybrid orbitals

sp hbridisation

N
1
2
b
4  0  0  0 2 g
Therefore hybridisation of C atom is sp and the structure is linear

O C O

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 b) SO 2

Central atom is S
O.S of S = 4
Outermost El. Configuration of s p d
S

El. Conf. after excitation

No. of Hybrid orbitals

sp 2

N 
1
2
b6  0  0  0 g 3 ..

Therefore hybridisation of S atom is sp2 and S

the structure is angular with one ppone pd O O
bonds.

c) SO 3
Central atom is S
O. S of S. = 6
Electronic configuration of S s p d

El. conf. after

excitation

sp 2
No. of Hybrid orbitals
O
1
b
N  6  0  0  0 3
2
g S
O O

 Shape of the moleculae is Trigonal planar

d) ClO3-

Central atom is Cl
O.S of Cl. = 5
Outermost conf. of Cl s p d

El. Conf. after excitation & No. of

unpaired electrons = 5 = O.S . of Cl.

No. of Hybrid orbitals sp 3

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 N
1
2
b
7  0  1  0 4 g ..

Cl
Therefore hybridisation of Cl atom is sp3 and
the structure is angular Trigonal pyramidal O
O O
two pdbonds.

e) SO 42-
Central atom is S
O.S of S = 6 s p d
Electronic configuration of S

El. of Conf. after Excitation

sp3 hybridisation
N
1
2
b
6  0  2  0 4 g O

S
Therefore hybridisation of S atom is sp3 and
the structure is tetraheadral with two pdbonds. O O
O

f) CO 2- 3
O.S of C. = 4 s p
Electronic configuration of C

El.conf. after excitation

N
1
2
b
4  0  2  0 3 g
sp2 hybridisation
O
Therefore hybridisation of C atom is sp2 and
the structure is trigonal planar with one ppbond
C

O O
g) ClO-
O.S of Cl. = 1 s p d
Electric configuration of Cl

El. conf. after excitation

N
1
2
b
7  0 1  0  4 g
sp3

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 Therefore hybridisation of Cl atom is sp3 and ..
the structure is linear with three of the hybrid
orbitals are occupied by lone pairs.
Cl
.. O
..

h) ClO2-
s p d
O . S.of Cl. = 3
Electronic configuration of Cl

El . conf. after excitation

N
1
2
b g
7  0 1  0  4 sp3

..

Therefore hybridisation of Cl atom is sp3 and Cl

the structure is angular with two of the hybrid
.. O
orbitals are occupied by lone pairs and one pd bond.
O
i) ClO4-
O . S.of Cl. = 7 s p d
Electronic configuration of Cl

El . conf. after excitation

N
1
2
b g
7  0 1  0  4
sp3
O

Therefore hybridisation of Cl atom is sp3 and

the structure is tetraheadral with one pd bond. Cl

O O
O
j) SO 32-

O . S.of S. = 4 s p d
Electronic configuration of S

El . conf. after excitation

b g
1 sp3
N  6  0 2  0 4 O
2

Therefore hybridisation of S atom is sp3 and S

the structure is pyramidal with one pd bond.
..
O O

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 k) PO 43-
O.S of P. =5 s p d
Electronic configuration of P

El. conf. after excitation

N
1
2
b
5  0 3  0 4 g sp3

Therefore hybridisation of P atom is sp3 and

the structure is tetraheadral with one pd bond. P

O O O
l) XeOF2
s p d
O.S of Xe = 4
Electronic configuration of Xe

El. conf. after excitation

N
1
2
b
8  2 0  0 5 g sp3d

..
Therefore hybridisation of Xe atom is sp3d and Xe O
the structure is T shape with one pd bond.
..
F

m) XeOF4
s p d
O.S of Xe = 6
Electronic configuration of Xe

El. conf. after excitation

N
1
2
b
8  4 0  0 6 g sp3d2

O
F F
Therefore hybridisation of Xe atom is sp d and
3 2
Xe
the structure is square pyramidal
with one pd bond. F F
..

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 n) XeOF6
O.S of Xe. = 8 s p d
Electronic configuration of Xe

El. conf. after excitation

N
1
2
b
8  6 0  0 7 g sp3d3

O
F F
Therefore hybridisation of Xe atom is sp d and
3 3
Xe F
the structure is pentagonal bipyramidal or
with one pd bond. F F
F

o) NO3- s p
O.S of N.= 5
Electronic configuration of N

El. conf. after excitation(d orbitals absent)

N
1
2
b
5  0 1  0  3 g sp2

Therefore hybridisation of N atom is sp2 and O

the structure is trigonal planar with one pd bond
one of the hybrid orbital will forn coordinate bond
with oxygen by donating its lone pair electron. N

O O
Bent’s rule : This rule appears natural consequence of the expected tendency of s rich orbitals for
dreater covalance. According to it the more electronegative substituent prefers hybrid orbital with less
s character. An electronegative substituent will displace the bonding pairs away from the central atom
thereby reducing the bp. bp. repulsions , this is most favoured by the orbitals with more p character
since the p orbitals have a larger spatial distribution than more compect s orbitals.If we consider sp 3d
hybridization the 5 hydrir orbitals resulting are not equivalent . The three orbitals directed trigonally
known as equitorial orbitals are different then two orbitals directed linearly perpendicilar to the plane of
equitorial orbitals these orbitals are called axial orbitals. The equitorials orbitals may be looked upon as
sp2 hybrids while the axial ones as dp hybrid orbitals. This leads us to the following conclusions.
i) The bonds formed by one set of orbitals (equitorial orbitals) are different from the bonds
formed by other set , (axial orbitals) even when the bonded atoms are all identical.as in
PCl5 the equitorial bonds are stronger than axial bonds which are longer by 0.015 nm .
ii) In PCl3F2 the fluorine atoms occupy the axial positionsas the more electronegative
substituent prefer hybrid orbital with more s character.
Exercise-1

1. Predict the hybridisation and shape of the following

(A) BeF2 (B) BBr3 (C) PBr3Cl2 (D) H2O (E) PCl5
(F) ClF3 (G) SF4 (H) l3- (I) SF6

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The covalent nature of ionic bond

Fajan’s Rule : Although atomic bond in a compound like M+ X- is considered to be 100 % ionic,
actually it also has some covalent character . An explanation for the partial covalent character of
an ionic bond has been given by Fajan.According to Fajan,if two oppositely charged ions are
brought together , the nature of the bond between them depends upon the effect of one ion on
the other.
When two oppositely charged ions (say A+ and B-) approach each other the positive
ion attracts electrons on the outermost shell of the anion and repels its positively charged
nucleus . This result in the distrotion, deformation or polarization of the anion. If the polarization is quite
small, an ionic bond is formed , while if the degree of polarization is large , a covalent bond results.

Thus the power of an ion (cation ) to distort the other ion is known as its polarizaiton
power and the tendency of the ion(anion) to get polarized by the other ion is known as its polarisabbility.
Greater the polarization power or polarisability of an ion, greater will be its tendency to form a
covalent bond.

The polarising power, or polarisabiltiy and hence formation of covalent bond is favoured by the
following factors :

i) Small Positive Ion (Cation ) : Due to greater concentration of positive charge on

a small area, the smaller cation has high polarising power.This explains why
LiCl is more covalent than KCl.

ii) Large Negative Ion (Anion ) : The larger the anion, the greater is its polarisability,
i. e susceptibility to get polarised . It is due to the fact that the outer electrons of
a large anion are lossely held and hence can be more easily pulled out by the
cation. This explains why iodides, among halides, are most covalent.

iii) Large Charge on Either of the Two Ions : As the charge on the ion increases,
the electrostatic attraction ofthe cation for the outer electrons of the anion also
increases, with the result its ability for forming the covalent bond increases.
Thus covalency increases in the order : Na+ Cl-, Mg2+ (Cl2)2- , Al3+ (Cl3)3-

iv) Electronic Configuration of the Cation : For the two ions of the same size and
charge ,one with a pseudo noble gas configuration (i. e., 18 electrons in outer -
most shell ) than a cation with noble gas configuration (i.e. 8 electrons in outer
most shell ) will be more polarising .Thus copper (I) chloride is more covalent
than sodium chloride although Cu+ ion (0.96Å) and Na+ ion (0.95Å) have same
size and charge.
The orbital overlapping involved in covalency reduced , the charge on each ion and
so weakens the electrovalent forces throughout the solid, as is evident from the melt
ing point of lithium halides.

LiF = 870oC LiCl = 613oC

LiBr =547oC Lil = 44oC

From the above discussion, we find that greater the possibility of polarisation lower is
the melting point and heat of sublimation and greater is the solubility in non-polar
solvents.

Illustration 4: The melting point of KCl is higher than that of AgCl though the crystal radii of
Ag+ and K+ ions are almost the same.

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Solution : K+ = [Ar+]’ Ag+ = [Kr] 4d10. This is a comparison between a noble gas core and preudo
noble gas core. So according to fajan’s rule the AgCl will have more covalent character
and hence its molecules will have discreteness resulting in weaker attaractive forces

Exercise-2

1. SnCl2 is solid but SnCl4 is liquid -Explain.

The ionic nature of covalent bond

We had seen in the previous section how an ionic bond could change to a covalent one.The reverse
of this is also true. A covalent bond could change bond to partially ionic . This happens when the
electronegativity values of the two atoms forming the bond are similar but not same.Such bonds are
referred to as polar covalent bonds. For example, bond formed between hydrogen atom and halo-
gen atom, bonds in water, ammonia etc.

    
H  Cl ; H  O H

Dipole Moment : Molecule like H- X having two polar ends are known as dipole or polar molecules
.The degree of polarity in a polar compound is given by its dipole moment () Which is defined as the
product of the net positive or negative charge and distance between the two charged ends, i. e ,
the bonds length.

Dipole moment ( ) = electronic charge (e) x Distance (d).

Dipole moment is measured in debye unit (D) :
1D = 3.33 x 10-30 Cm .

Dipole moment is usually indicated by an arrow, having + on the tail ( +  ),above the m o l e c u l e
and pointing towards the negative end, e. g.


H Cl

1. In a bond H-X, hydrogen, atom is the positive end of dipole where X is any atom other
than C or H .

2. In a bond C- X , the carbon atom is the positive end of the dipole where X is any atom
other than carbon. However, in the C- H bonds of hydrocarbons the value and direction of the
dipole are not constant and depends upon the state of hybridisation of the carbon. For
example , the direction and value of dipole moments in C- H bonds of methane and ethylene
are as below .

+ +
C H C H
methane ethylene

3. Dipole moment is a vector quantity . So to get the net dipole moment of a molecule
the individual dipole moments must be added vectorally.

4. Zero dipole moment of a molecule indicates that the molecule is symmetic.

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Illustration 5 : CO2 has got dippole moment of zero why ?

Solutions : The structure of CO2 is O = C = O . This is a highly symmetrical structure

with a plane of symmetry passing through the carbon. The bond dipole of C- O
is directed towards oxgyen as it is the negative end.Here two equal dipoles
acting in opposite direction cancel each other and therefore the dipole moment
is zero.

Percentage lonic Character :

Every ionic compound having some percentage of covalent character according to Fajan’s rule.
The percentage of ionic character in a compound having some covalent character can be calcu-
lated by the following equation.

Observed dipole moment

The % ionic character  x100
Calculated dipole moment assuming 100 % ionic bond

Illustration 6 :Calcualate the% of ionic character of a bond having length = 0.92 Å and 1.91
D as it’s observed dipole moment.

Solution : Calculated considering 100 % ionic bond

= 4. 8 x 10-10 x 0.92 x 10-8 esu cm
= 4.8 x 0.92 x 10-18 esu cm
= 4.416 D
1.91
 % ionic character = x 100  43.25
4.416
The example given above is of a very familar compound called HF. The % ionic
character is nearly 43.25 % , so the % covalent character is (100- 43.25) = 56.75 % .
But from the octet rule HF should have been a purely covalent compound but actually
it has some amount of ionic character in it which is due to the electronegativity
difference of H and F. Similarly knowing the bond length and observed dipole moment
of HCl , the % ionic character can be known. It was found that HCl has 17 % ionic
character. Thus it can be clearly seen that although we call HCl and HF as covalent
compounds but it has got appreciable amount of ionic character. So from now
onwards we should call a compound having more of ionic less of covalent and vice
versa rather than fully ionic or covalent.

Exercise -3

1. Dipole moment of CCl4 is zero while that of CHCl3 is non zero.

2 Calculate the percentage of covalent character of Hl having bond length = 1.62

Å and observed dipole moment = 0.39 D

Hydrogen Bonding
It is an electrostatic attractive force between covalently bonded hydrogen atom of one mol-
ecule or a part of a molecule and an electro negative atom (such as F,O, N ) of another molecule
or another part of the same molecule . It is very weak (strength about 2 - 10 k cal mol -1 or 8.4 -

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42 kJ mol-1 ) as compared to a covalent bond strength 50 - 100 kcal mol-1 or 209-418. 4 KJ mol-1)

Conditions for Hydrogen Bonding

1. The molecule must possess a highly electronegative atom linked to hydrogen atom.
2. The size of the electronegative atom should be small.

Types of Hydrogen Bonding

1. Inter- Molecular Hydrogen Bonding : In this, two molecules of the same compound join to
form aggregates . For example, Intermolecular hydrogen Bonding increases the boiling point
of the compound and also its solubility in water.

2. Intramolecular Hydrogen bonding : In this Hydrogen bonding occurs between the atoms of the
same molecules present on the different sites. This type of Hydrogen bonding is generally
known as Chelation. Some examples are.

O H
H
O O
Cl
N
O

Consequence of hydrogen bonding

Intermolecular hydrogen bonding increases boiling point of the compound and also the water
solubility on the other hand intramolecular hydrogen bonding decreases the boiling point of the
compound and also its water solubility. High boiling points and melting points of NH3,H2O, HF in
comarison to hydrides of othe elements of group V, VI and Vll to which N, O and F belong
respectively are due to hydrogen bonding , H2O exists in liquid state whereas H2S in gaseous state
because hydrogen bonding exist in water and no H-bonding exists in H 2S. Strength of certain
acids and bases can be explained on the basis of hydrogen bonding. The organic compounds like
alkane, alkenes , alkynes are insoluble in water due to absence of H- bonding whereas alcohols,
organic acids, amines are soluble in water due to H-bonding . Density of ice is less than water
and water contracts when heated between 0oC and 4oC because ice has open cage structure due
to hydrogen bonding.

Illustration-7: Ethyl alcohol (C2H5OH) has got a higher boiling point that dimethyl ether
(CH3- O- CH3) although the molecular weight of both are same.

SOLUTON : Though ethyl alcohol and dimethyl ether have the same molecular weight
but in ethyl alcohol the hydrogen of the O- H groups forms intermolecu
lar 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.

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 Exercise -4

1. O- hydroxy benzaldehyde is more insoluble in water than p-hydroxy benzaldehyde.

Weak Interactions

Van der Waals forces : Although the covalent , ionic , as well as the metallic bond can be used to
explain the structural characteristics and the physical states of many substances , a large number
of system do not fit into these categories e. g., inert gases, non polar molecules like H2, N2 Cl2,
CH4 etc. . Obviously weak attractive forces operate between these molecule (else they would not
exist in the liquid state ).The existence of these forces was first recognised by van der waals as
early as 1813, hence these forces are called vander Waals forces.Three obvious sources of van der
waals forces are

* Weak dipole -dipole electrostatic attractive forces which would exist in any
molecule with permanent dipole eg. HCl, H2O etc.

* Weaker dipole - included dipole interactions resulting from the polarisation of one
molecule by the dipole of a neighbouring molecule.

* London dispersion forces. For symetrical molecules ( like Ne, Cl2, H2 CH4 etc.) only London
forces operate .Very weak dipoles form even in non- polar molecules due to temporary
fluctations in the electron density distribution . These transient dipoles can now induce
dipoles in neighbouring molecules producing a flux of weak temporary interactions.

Molecular Orbital Theory

The molecular orbital theory was developed by F. Hund and R.S. Mulliken in 1932. The salient features
of this theory are:
(i) Just as electrons of atoms are present in various atomic orbitals, electrons of a
molecule are present in various molecular orbitals.

(ii) Molecular orbitals are formed by the combination of atomic orbitals of comparable
energies and proper symmetry.

(iii) While an electron in an atomic orbital is influenced by one nucleus, in a molecular

orbital it is influenced by two or more nuclei depending upon the number of atoms in the
molecule. Thus an atomic orbital is monocentric while a molecular orbital is
polycentric.

(iv) The number of molecular orbitals formed is equal to the number of combining atomic
orbitals. When two atomic orbitals combine, two molecular orbitals called bonding
molecular orbital and antibonding molecular orbital are formed.

(v) The bonding molecular orbital has lower energy and hence greater stability than the
corresponding antibonding molecular orbital.

(vi) Just as the electron probability distribution around a nucleus in an atom is given by an
atomic orbital, the electron probability distribution around a group of nuclei in a
molecule is given by a molecular orbital.

(vii) The molecular orbitals like atomic orbitals are filled in accordance with the Aufbau
principle obeying the Pauli principle and the Hund’s rule.

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Linear Combination of Atomic Orbitals (LCAO)

In principle, Schrödinger equation can be written for any molecule. However, since it cannot be solved
exactly for any system containing more than one electron, molecular orbitals which are one electron
wave functions for molecules are difficult to obtain directly from the solution of the Schrödinger equa-
tion. This difficulty is overcome by resorting to an approximation method called the linear combina-
tion of atomic orbitals (LCAO) method to form molecular orbitals.
Let us consider the application of the LCAO method to the homonuclear diatomic
hydrogen molecule. The two hydrogen atoms in the H2 molecule, for the sake of convenience may be
labelled as A and B. Each hydrogen atom in ground state has one electron in the 1s orbital. These
atomic orbitals may be represented by the wave functions A and B. Mathematically the formation of
molecular orbitals is described by the linear combination (addition or subtraction of the wave functions
of the individual atomic orbitals) of A and B as shown below.

MO = A ± B
Therefore, two molecular orbitals and are
formed as
= A + B
. = A – B
The molecular orbital ó formed by the addition of atomic orbitals is called the bonding molecular
orbital and the molecular orbital ó* formed by the subtraction of atomic orbitals is called antibonding
molecular orbital

ANTIBONDING ORBITAL
HAVING ENERGY HIGHER
IncreasingEnergy

THAN ATOMIC ORBITALS .

1S

1S 1S
BONDING ORBITAL HAVING
1S ENERGY HIGHER THAN
ATOMIC ORBITALS .
A.O. M.O. A.O.

Types of Molecular Orbitals

Molecular orbitals of diatomic molecules are designated as

 (sigma),
 (pi),
 (delta), etc.
In this nomenclature, the sigma (ó) molecular orbitals are symmetrical around the bond-axis
while pi (ð) molecular orbitals are not symmetrical.For example, the linear combination of 1s
orbitals centered on two nuclei produces two molecular orbitals which are symmetrical around the
bond-axis. Such molecular orbital’s are of the type and are designated as 1s and *1s .
If internuclear axis is taken to be in the zdirection, it can be seen that a
linear combination of 2pz- orbitals of two atoms also produces two sigma molecular orbitals
designated as 2pz and *2pz. Molecular orbitals obtained from 2px and 2py orbitals are not sym-
metrical around the bond axis because of the presence of positive lobes above and negative lobes
below the molecular plane. Such molecular orbitals, are labelled as  and * . A  bonding MO has
larger electron density above and below the internuclear axis. The * antibonding MO has a node
between the nuclei.

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 Nodel Plane

IncreasingEnergy
+ + - +
1S 1S
1S 1S
Anti Bonding sigma
1S 1S molecular orbital

1S
+ + +

A.O. A.O. 1S 1S 1S

M.O. Bonding sigma
molecular orbital
IncreasingEnergy

- + - + - - +- +
2pz 2pz 2pz
2pz
2pz 2pz
2p z
- + + + - - + -
A.O. M.O. A.O. 2pz 2pz 2p z
IncreasingEnergy

- + -
2px - +

2px 2px 2px 2px 2px

2 p x
+
A.O. A.O. +
M.O. -

2px 2px 2 p x

In simple homonuclear diatomic molecules the order of MO’s bases on increasing energy is
 2p y  * 2py
1s,  *1s, 2s,  * 2s , 2 p z , ,  * 2p z    
 2p x  * 2px

For molecules including O2 and above, the order is

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  2py  * 2py
1s,  * 1s, 2 s,  * 2s  2 p z , ,  * 2 p z,    
 2px  * 2px

Bond order
Bond order is a number which indicates the no. of bonds a molecule possesses and the stability of
the molecule in comparision toanother . An integral value implies that so many bonds exist in the
molecule. Anything fractional indicates that the bond is intemediate.

Bond-order =1/2( no. of bonding electronss - No. of anitbonding electrons).

Application of MOT to Homonuclear Diatomic Molecules .

1. H2+ molecule ion .Total no. of electrons=1

Arrangement : 1s1
An unpaired electrons always indicates that the molecule is paramagnetic.

2. H2 molecule , Total no. of electrons = 2

Arrangement : 1s2
Paired electrons, so diamagnetic .
BO = 1/2 ( 2 - 0) = 1
Therefore No.of bonds = 1

3. He2+ molecule ion, Total no. of electrons = 3

Arrangement : 1s2, 1s1
Unpaired electron, so paramagnetic
BO = 1/2 ( 2 -1 ) = 1/ 2
Bond existing by virtue of a single electron.

4. He2 molecule .Total No. of electrons = 4,

Arrangement : 1s2, 1s2
Diamagnetic BO = 0
Molecule does not exist .

Illustration 8 : Which diatomic molecule of second period besides O 2 should be para-

magnetic.

B2- 1s , 1s , 2s , 2s , 2p  2p , 2p

2 *2 2 *2 1 1 o
Solution :
As , paramagnetism arises due to unparied electron .ThereforeB2 is
paramagnetic molecule.

Exercise-5:

1. Why He2 molecule cannot exist ?

2. Calculate the bond order of the following chemical species.
CO , NO , NO+ , NO- , CN- , HF , O2 , O2+ O2-

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Answers to Exercise

Exercise 1 : A) Linear B) Trigonal Planar C) Shape- Trigonal bipyramidal

D) angular E) trigonal bipyramidal F)T-Shaped

G) Irregular tetrahedral H) linear I) Octahedral

Exercise 2 : Apply Fajan’s rule. SnCl2 is ionic but SnCl4 is covalent

Exercise 3
1: Both CCl4 & CHCl3 have tetrahedral structure but CCl4 is symmetrical while
CHCl3 is non- symmetrical
Cl H

C C

Cl Cl Cl
Cl
Cl Cl
Symmetrical Non-Symmetrical
Due to the symmetrical structure of CCl4 the resultant of bond dipoles comes out to
be zero. But in case of CHCl3 it is not possible as the presence of hydrogen introduces
some asymmetry.

2: Calcualate  considering 100 % ionic bond.

= 4. 8 x 10-14 cm x 1.62 x 10-8 cm
= 7.776 D
0.39
 % ionic character = x100  5%
7.776
 % covalency = (100 - 5 ) = 95 %

Exercise 4: A substance is said to be soluble in water if it is capable of forming H- bonding

with water molecule. In o- hydroxy benzaldehyde due to intramolecular chela-
tion 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-
hydroxy benzaldehyde to form H-bond with water and hence it is more soluble
compared to the o - isomer.

O
H H O------ H O H

O
C

H
H C O p - isomer
o - Isomer

Exercise 5: 1. Bond order He2 is zero. A molecule with bond order zero can not exist.
2. 2 , 2.5 , 3 , 2 , 2.5 , 1 , 2 , 2.5 , 1.5

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Solved Problems

Subjective
Problem1 : The bond angle of H2O is 104o while that that of F2O is 102o

Solution: Both H2O and F2O have a lone pair of electrons .But fluroine being highly electrone
-gative , the bond pair electrons are drawn more toward F in F2O, whereas in H2O it
is drawn towards H. So in F2O the bond pairs being displayed away from the central
atom has very little tendency to open up the angle . But in H2O this opening up is
more as the bond pair of electrons are closer to each other . So bondangle of F2O
is less than H2O.

repulsion more F
H
Repulsion less F
H
Problem 2 : Compare the dipole moment of NH3 and NF3
Solution : Let’s draw the structure of both two compounds and they analyse it.

.. ..
N N
H H F F
H F

In both NH3 and NF3 the struture is quite the same.In NH3 as N is more electronegative
than hydrogen so the resultant bond dipole is towards N, which means both the lone
pair and bond pair dipole are acting in the same direction and dipole moment of NH3
is high . In case of NF3 the bond dippole is acting towards fluorine , so in NF3 the lone
pair and bond pair dipole are acting in oppositin resulting in a low dipole.

Problem 3 : Compare the dipole moment of Cis 1,2 dichloroethylene and trans, 1, 2
dichloretheylene.
Cl Cl
Cl Cl
Solutions :
C C C C
H H H 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 in Cis Compound the dipole do not cancel
each other resulting in a higher value.
Generally all Trans compounds have a lower dipole moment corresponding to
cis. Isomer, when both the substituents attached to carbon atom are either
electron releasing or electron withdrawing.

Problem 4 : Compare the bond energies of N2, N2+,& N2-

Solutons : The configuration of N2 is

 12s  1*2s  22 s  1*2s

R
S
 U R
V 
 S V
2py U 2
*
2py

T W T W
2px
pz *
2px

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 Now N2+ means removal of an electron from a bonding M.OThis will decrease
the B. O
 B. O of N+2 = 1/2 ( 5 - 0 ) = 2.5
Now again for N2- bond order is 1/2 (6-1 ) = 2. 5
So from the bond order it may seem that both N+2 & N2- may have the same bond
energy. But removal of an electron from a diatomic species tend to decrease the
inter electron repulsion and thereby shortens the bond length . So the bond
energy becomes more than compared to N2-

 N2 > N2+ > N2-

Problem 5 : The dipole moment of HF bond is 1.98 D, H - F inter nuclear distance is 0.92
Å . Calculate the % ionic character.

Solution : When HF bond is 100 % ionic

  0.92 x10 8 x4.802 x10 10 esu cm

0.92 x4.802 x10 18

  4.42D
1x10 18
1.98
 % ionic character of HF = x100  44.8  45%
4.42

Problem-6 : Which of the following molecuels are polar : H2O ,NH3, SO2, CH3Cl, BF3
Solution :
Cl
O F
S
O N
C
H H H O = C= O B
H H H
(Polar ) Non -polar (Polar ) F
H H F
1.84 D (Polar ) 0 D 1.60 D
(Polar ) (Non-Polar )
1.8 D
1.86 D 0

Problem 7 : Explain giving reason :

ClF2- is linear, but the ion ClF2+ is bent

Solution : In ClF2- central chorine atom involves sp3d hybridisation , to have minimum
electronic repulsion three lone pairs should be in equitorial positions as follows
: giving linear shape to the ion. Whereas, in case of ClF 2+ ion central atom Cl
involves sp3 hybridisation having two lone pairs, resulting in bent shape for the
ion, ( bond angle less than 109o28’ due to repulsion of bond pair by lone pair.)
F’
......
......

Cl
120o
....

......
..

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

)
.

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

Bent shape

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Problem 8 : Arrange in order of increasing dipole moment BF3 ,H2S, H2O

Solution : BF3 has zero dipole moment because of symmetry, H2S has a lower dipole
moment than H2O because of much lower bond polarity of H-S bond comapred to
H- O bond. Henc e the order is
BF3 < H2S < H2O

Problem 9 : Explain with reason: Two different bond lengths are observed in PF 5 but
only one bond length observed in SF6
Solution : PF5 has triogonal bipyramidal structrue (sp3d hybridisation of central atom ) in which
bond angles are 90o and 120 o respectively and there are two types of bond axial and
equatorial . In case of SF6 the structure is octahedral ( sp3d2 hybridization of the
central atom - S ) resulting only one type of bond, bond angle (90o) and one type of
bond length .
F
F F

F F
F P
F F F Bond angle -90o

(SF6)
(P F5)
F F

Problem-10 : Explain the following

0- hydroxy benzaldehyde is liquid at room temperature while p- hydroxy
benzaldehyde is high melting solid.

Solution ; There is intramolecular H bonding in O - hydroxy benzaldehyde while intermo-

lecular hydrogen bonding in p- hydroxy benzaldehyde

CH=O - H CH = O- H - O
O

O- hydroxy benzaldehyde
CHO
O-H----OCH

P- HydroxybenzaldehydeOH

Problem 11: By the use of molecular orbital considerations,account for the fact that
oxygen is paramagnetic .What is the bond order of oxygen ?

Solution : ‘O’ atom in ground state has the electronic configuration - 1s22s2 2p4 . Aside from the
K electrons of the two ‘O’ atoms in O2 which are so deeply embedded in their respective

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 atoms as not to overlap with other electrons the reamaining 12 electrons ( 6 from
each of the atoms) will fill the lowest of the available molecular orbitals.

Molecular electronic configuration Of O2 :  22s  *22s  22pz  22px   22py ,  *21px   *21py
The last two electrons go into the anti-bonding degenerate  orbitals one into
and x and other in y so as to maximize electron spin in accordance with Hund’s
rule.These two electrons confer paramagnestism upon the molecule.
Bond order =
No.of electrons in bonding M.O.- No. of electrons in anti bonding M.O
2
84
= 2
2

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Objective :
Problem 1: Which molecule is T- Shaped ?
(A) BeF2 (B) BCl3
(C) NH3 (D) ClF3

Solution : ClF3 has sp3d hybridisation with two lone pairs of electron on central Cl- atom.
 (D)

Problem 2 : The species which does not show paramagnetism is

(A) O2 (B) O2+
(C) O2 2-
(D) H2+

Solution : O2-2 has no unpaired electron

 (C)

Problem 3 : CO2 has the same geometry as

(A) HgCl2 (B) NO2
(C) SnCl2 (D) C2H2

Solution : both HgCl2 and C2H2 are linear like CO2 because of sp2 hybridisation
 (A) & ( D)

Problem 4 : Which ion has the highest polarising power

(A) Mg2+ (B) Al3+
(C) Ca2+ (D) Na+

Solution 4 : Small cation has more polarising power

 (B)

Problem 5 : The correct order of decreasing polarisability of ion is

(A) Cl- >Br- > I- > F- (B) F- > I- > Br- >Cl
(C) I- > Br- > Cl- > F- (D) F- >Cl- > Br- > I-

Solution: Larger the ion, more is its polarisability

 (C)

Problem 6 : Which of the following compounds is (are ) non- polar

(A) HCl (B) CH2Cl2
(C) CHCl3 (D) CCl4

Solution : CCl4 has symmetrical structure hence non- polar

 (D)

Problem 7 : Which of the following cannot exist on the basis of MO theory ?

(A) H2+ (B) He2+
(C) He2 (D) O2

Solution :  Bond order of He2 is zero, hence can not exist.

 (C)

Problem 8 : Highest covlent character is found in

(A) CaF2 (B) CaCl2
(C) CaBr2 (D) Cal2

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Solution : Higher the polarisability, greater is the covalent character, Since polarisability
of I- is maximum.
 (D)

Problem 9 : o- Nitrophenol is more volatile than p- nitro phenol because of

(A) Resonance
(B) Presence of intramolecular hydrogen bonding in the o- isomer
(C) Absence of intramolecular hydrogen bonding in the o-isomer
(D) none of these

Solution : Ortho nitro phenol is more volatile than para due to presence of intra molecular
hydrogen bonding.
 (B)

Problem 10 : Amongst LiCl,RbCl, BeCl2 and MgCl2 the compounds with greatest and
least ionic character respectively are
(A) LiCl and RbCl (B) RbCl and BeCl2
(C) RbCl and MgCl2 (D) MgCl2 and BeCl2

Solution : See Fajan’s rule  (A)

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Assigments
Subjective

Level - I

1. o- nitrophenol is more volatile than p - nitrophenol .Explain

2. Predict the order of basicity

RCN, RNH2,

N
3. Predict the hybridisation state of underline carbon in the following
(A) HCOOH (B) (H2N) 2 CO (C) ( CH3 ) 3 COH (D) CH3 CHO

4. BF3 has zero dipole moment - Explain

5. What is the number of molecular orbitals obtained by mixing two atomic orbitals ?

6. Explain -H2O is liquid but H2S is a gas.

7. Which one of each of the following pairs is expected to have the large bond angle
(A) H2O and NH3 (c) NH3 and NF3

8. Predict the shape of the following

(A) SOF2 (B) SO2F2

9. Write the Lewis structure of the following compounds

(A) BaO (B) MgCl2 c) K2S

10. Carbondioxide molecule is linear whereas sulphurdioxide is non- linear .Explain .

11. Arrange the following compounds in order of increasing dipole moments

CH3 Cl Cl Cl

Cl Cl

Cl

I II III IV Cl

12. For molecule MX3, having zero dipole moment, what will bethe nature of the sigma bonding
orbitals used by M(Atomic Number is less than 21 ) .

13. Arrange the following in decreasing covalent character

BaCl2 ,CaCl2 , MgCl2 , BeCl2

14. If the observed dipole moment of LiF is 3.3D .Calculate percentage ionic cahracter given
(Li- F bond length is 0.11 6 nm )

15. Explain how the dipole moment could be used to distinguish between the Cis and trans
Isomer of 1, 2 dibromethene.

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 LEVEL - II

1. How many sigma bonds and how many pi- bonds are present in a benzene molecule?

2. Write down the resonance structure of nitrous oxide.

3. a) Amongst BBr3 and BF3 which is a stronger acid and Why ?

b) Amongst o - hydroxy benzaldehyde and p- hydroxy benzaldehdye which is more

soluble in water and why ?
c) Amongst LiF and Lil. Which has more covalent character and why ?

4. The largest dipole moment among CH4,CF4 ,CO2, CH3F is of CH3F why?

5. Valency of oxygen is generally two whereas sulphur shows valencies of two, four and six.
why ?

6. Explain the following :

a) PCl5 is a cavalently bonded liquid. When added to water the solution conducts
electricity.
b) PCl5 exists in the solid state in the form of [PCl4 ]+ [PCl6]- yet it is a non-conductor of
electricity .
c) The H3PO4 acid is tribasic but H3PO4 acid is dibasic in aqueous solution .

7. Why is ice lighter than water ?

8. Suggest a reason for the large difference between the boiling points of butanol and butanal,
although they have almost the same solubility in water.

9. Give reason for the following :

a) Covalent bonda are called directional while ionic bonds are called non directional

b) Water molecules have bent structure where as carbon dioxide moelcules are linear.

c) Ethylene molecules are planar.

10. Water is generally, a good solvent for ionic compounds. Why ?

11. Salt like KHF2 is stable but KHCl2 is not known - Explain

12. N2 has a greater dissociation energy than N2+ whereas O2 has a lower dissociation
energy than O2+ .Explain .

13. A diatomic molecule has a dipole moment of 1.2 D it’s bond distanc e is 1.0Å what
fraction of an electronic charge exists on each atom.

14. Maleate acid ion is more stable than fumarate acid ion - explain.

15. PF5 and BrF5 appear similar formulae but structures are different -explain.

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 LEVEL- III
Explain Why ? ( Question No. 1 to 8 )

1. Li+ ion has got the smallest radius among the alkali metals, yet its mobility is less
than other alkali metal ions is aqueous solution.

2. NF3 does not undergo hydrolysis while NCl3 undergoes hydrolysis.

3. CO2 is a monomer where SiO2 is a polymer . Explain why ?

4. Which of the following has highest dipole moment ?

CCl4 , CH3Cl, CH2Cl2, CHCl3

5. LiF is the least soluble of alkali metal halides while Agl is the least soluble of the silver
halides.

6. Bond angle of H2O is 104o while that of H2S in 92o

7. PH5 is not possible while PCl5 is

8. HF forms stronger H-Bonds than H2O , Still Hrvap of HF is lower than that of pure
water.

9. 2Li  12 O2 
 Li2O
2Na  O2 
 Na 2O2
Why the number of oxygen atoms combining with each metal increases

10. In water the H - O - H bond angle is 105o , Determine the magnitude of the charge on
the oxygen atom in the water molecule.
Given dipole moment of water = 1.85 D
Covalent radii of Hydrogen = 0. 28 Å
Oxygen = 0.66 Å

11. Using VSERR theory identify the type of hybridization and draw the structure of OF2 what
are the oxidation state of O and F ?

12. Draw the structure of P4O10 and

(A) Identify the no. of single and double P- O bond
(B) Explain the difference in the nature of bonding in LiF and Lil

13. a) Arrange the following ions in order of their increasing radii Li+ ,Mg2+, K+ , Al3+
b) Arrange the following sulphates of alkaline earth metals in order of decreasing
thermal stability: BeSO4 , MgSO4 , CaSO4 and SrSO4.

14. Interpret the non- linear shape of H2S molecule and non planar shape of PCl3 using
VSEPR theory.

15. Draw the moelcular structure of XeF2 , XeF4 and XeO2F2, indicating the location of
lone pairs of electrons

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Objective
LEVEL-I

1. The molecule which has T - shaped structure is

(A) BCl3 (B) NH3
(C) XeOF2 (D) PCl3

2. Which of the following will be planar trigonal ?

(A) PCl3 (B) NH3
(C) ClF3 (D) BCl3

3. The structure of lF5 can be best described as

F
F F
(A) 72O (B)
F 90
)
(
) F
I
120 ( F

F F F
F
F F
90O
(C) (D) None of these
(

) F
90o I

F F

4. Which of the following molecule has highest dipole moment ?

(A) BF3 (B) NH3
(C) NF3 (D) B2H6

5. The pair having similar geometry is

(A) BF3, NH3 (B) H2O , C2H2
(C) CO2, SO2 (D) NH3, PH3

6. Of the three molecules XeF4 , SF4 , SiF4 which have tetrahedral structures
(A) all the three (B) Only SiF4
(C) both SF4 and XeF4 (D) Only SiF4 and XeF4

7. Which of the following statements is correct for carbon monoxide ?

(A) A double bond between carbon and oxygen
(A) 1, 1 and 1 coordinate bond between carbon and oxygen
(C) One lone pair of electrons one each atom
(D) 1 and 2 bonds between carbon and oxygen

8. If Na+ ion is larger than Mg2+ ion and S2- is larger than Cl- ion, which of the following will
be more covalent.
(A) NaCl (B) Na2S
(C) MgCl2 (D) MgS

9. Compound in which cental atom assuemes sp3d hybridisation is

(A) SO3 (B) PCl5

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 (C) SO2 (D) PCl3

10. The Compond in which C uses its sp3 hybrid orbitals in bonding is
(A) HCOOH (B) (H2N) 2 CO
(C) ( CH3 ) 3 COH (D) CH3 CHO

11. The effect of hydrogen bonding is greatest in

(A) HF (B) NH3
(C) CH3NH2 (D) H2 O

12. Which of the following species have intra molecular Hydrogen bonds ?
(A) Phenol (B) o-Nitrophenol
(C) p-Nitrophenol (D) Nitroethane

13. Among HF, CH3OH,N2O4 and CH4 which would have inter molecular hydrogen
bonding.
(A) CH3OH,CH4 (B) HF,CH4,CH3OH
(C) N2O4, HF (D) HF,CH3OH

14. Which of the following has a bond order of one - half ?

(A) H2 (B) O2-
(C) N2 (D) He2

15. Paramagnetism is not shown by

(A) O2- (B) H2+
(C) O2 (D) O22-

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 LEVEL - II
1. The types of bonds present in CuSO4 .5H2O are only.
(A) electrovalent and covalent
(B) electrovalent and coordinate covalent
(C) electrovalent, covalent and coordiante covalent
(D) covalent and coordiante covalent

2. The bonds present in N2O5 are

(A) only ionic (B) covalent and coordinate
(C) only covalent (D) covalent and ionic

3. The number of unpaired electrons in Ni2+ is

(A) 0 (B) 2
(C) 4 (D) 8

4. The shape of lF5 is

(A) square planar (B) Square pyramidal
(C) Trigonal bipyramidal (D) None of these

5. The shape of XeF4 is

(A) Tetrahedral (B)Square planar
(C) Pyramidal (D) Trigonal planar

6. Which one has minimum dipole moment ?

(A) Butene- 1 (B) cis-Butene- 2
(C) Trans-Butene-2 (D) 2- Methylpropene

7. The molecule which has zero dipole moment is

(A) CH2Cl2 (B) BF3
(C) NF3 (D) ClO2

8. Which of the following model best describes the bonding within a layer of the graphite
structure.
(A) ionic (B) metallic
(C) non- metallic covalent (D) Van der Waals

9. Which has got the smallest bond angle ?

(A) NH3 (B) AsH3
(C) PH3 (D) SbH3

10. Which of the following has the highest boiling point ?

(A) CH4 (B) SiH4
(C) GeH4 (D) SnH4

11. Which of the following doesn’t undego hydrolysis ?

(A) NCl3 (B) NF3
(C) PCl3 (D) PCl5

12. The type of hybrid orbitals used by chlorine atom in ClO-2 is

(A) sp3 (B) sp2
(C) sp (D) dsp2

13. Which one among the following does not have the hydrogen bond ?

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 (A) Phenol (B) Liquid NH3
(C) Water (D) Liquid HCl

14. The maximum number of hydrogen bonds a water molecule can form is
(A) 2 (B) 4
(C) 3 (D) 1

15. Which of the following is paramagnetic ?

(A) O-2 (B) CN-
(C) CO (D) NO+

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Answers
Subjective

Level 1
1. The o- nitrophenol has intramolecular H bonding however p- nitrophenol has intermolecular H
bonding.

2. RNH2 > > RCN

N

3. a) sp2 b) sp2 c) sp3 d) sp2

4. The central aton boron has sp2 hybrid orbitals which lie in trigonal planer geometry.

5 Two

6 H2O has intermolecular H bonding hence it is assosiated liquid , while H2S does not.

7. a) NH3 > H2O

b) NH3 > NF3

8 SOF2 = Pyramidal
SO2F2 = Tetraheadral

9 Ba2+ O2-
Mg2+ O2-
2K+ O2-

10 Carbondioxide is linear because it has sp hybridisation while sulphurdioxide is non linear due to
sp2 hybridisation.

11. II > III > I > IV

12. sp 2

13. BeCl2 > MgCl2 > CaCl2 > BaCl2

14 59.62 %

15 Cis > trans

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 Level 2
1. 12 sigma and 3 pi

2. N=N=O
N N O
3. a) BBr3 is stronger acid than BF3 because BF3 has back bonding due to fluorine atom.

b) p- hydroxybenzaldehyde is more soluble in water because it is capable of H bonding with

water while o- hydroxybenzaldehyde is not because it already has intramolecular H bonding.
c) LiI has more covalent character due to high polarizibility of I.

4. CH4 , CF4 and CO2 will have zero dipole moment due to symmetrical structure.

5 Due to presence of vacant d orbitals sulphur can expand its octat.

6 a) In gaseous state PCl5 is a covalent compound but in aqueous state it exists in the form of
[PCl4]+ and [PCl6]- ions hence it conducts electricity.

b) In solid state the ions are not free to move.

c) In H3PO3 one of the Hydrogen is directly attached to P atom and hence it is not acidic.

7. The ice has diamond like structure held by hydrogen bonding . These H bonds are rigid due to
which the volume of ice is high and hence density of ice is lesser then water.

8 Butanol is assosiated liquid due to intermolecular H bonding while Butanal does not has
intermolecular H bonding , so boiling point of butanol is higher than butanal . With water both
can form hydrogen bond so they have almost same solubility in water.

9 a) The sterngth of a covalent bond depends on the direction of overlaping of orbitals however
the strength of ionic bond does not depends upon the direction of approach of ions.

b) In water the central atom O has sp3 hybridization and two lone pairs while in CO2 the central
` atom C has sp hybridization
c) due to sp2 hybridization of the two C atoms

10 water has high dielectric constant due to high dipole moment , so it can break the lattice of
ionic compounds.

11. HF2- ion can exist due to H bonding between F- and HF but it is not the case with HCl2-

12. N2 has greater bond order (3) than N2+ (2.5) whereas O2 has lower bond order (2) than O2+
(2.5)

13. 0.25

14 Maleate acid ion has chelation due to intramoleular H bonding.

15 In PF5 the hybridization of central atom P is sp3d while in Br5 the hybridization of central atom
Br is sp3d2

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 Level 3
1. In aqueous solution the Li ion is heavly hydreted due to its high charge density.
+

2. In NF3 neither N atom nor F atom has vacant d orbitals. In NCl3 Cl atom has vacant d orbitals
which can accept lone pair of electron from water.

3. CO2 can form discrete molecules because carbon can form multiple bonds with oxygen but
silicon cannot form stable multiple bonds with oxygen hence it forms a gaint lattice.

4. CH3Cl has highest dipole moment becaise of small bond angles among the four molecules.

5 Both have high covalent character.

6 Due to low electronegativity of S atom the bond pairs are shifted towards H atom hence the
lone pair lone pair repulsion is moer perdominating.

7. Due to high electronegativity the Cl atoms can force the d orbitals of Phosphorous to undergo
sp3d hybridization but it is not the case with H atom which can form PH3 with sp3 hybridization
of P

8 The nunber of H bond per molecule is more for water than for HF

9 The smaller cation (Li+) can form stronger lattice with smaller anion (O2-) while the larger
cation (Na+) can form stronger lattice with larger anion (O22-).

10 3.23 x 10-10 esu.

:O :
11. sp3 , angular The oxidation state of O is +2 and that of F is -1
F F
O
12. a) 12 single and 4 double bonds
P
O O

b) In LiF the bonding is more ionic than LiI O O

O P P O

O P O
13. Li < Al < Mg < K
+ 3+ 2+ +

BeSO4 < MgSO4 < CaSO4 < SrSO4 O

14 Both S atom and P atom will have sp3 hybridization and lone pair of electrons.

15
..
F
.. F ----------- F
F
O
..--- Xe
-----------
-----------

..---- Xe Xe
-- --
- --- -
----
----
..
--- ---
F -----------F O
F .. F
sp d hybridization
3
sp d hybridization
3 2
sp3d hybridization
shape linear shape square planer shape see saw

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Answer

Objective
LEVEL- I

1. C 2. D 3. C 4. B 5. D

6. B 7. B 8. D 9. B 10. c

11. A 12. B 13. D 14. B 15. D

LEVEL- II

1. C 2. B 3. B 4. B 5. B

6. C 7. B 8. C 9. D 10. D

11. B 12. A 13. D 14. B 15. A

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