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Chemistry Notes Created By

Waqar Ahmed Mirani

Chapter 03
Theories of Covalent Bond and Shapes
Of the molecule

( Chemical Bond )

The attractive force or linkage which holds two atoms together in

a molecule is called chemical bond .
=>The atoms form bond to become stable like inert gases .
=>Inert gas configuration is obtained by two ways :
1)By loosing and gaining the electron ( ionic bond ) .
2)By sharing the electron ( covalent bond ) .

( Ionic Bonds )

This bond was given by Scientist W . Kossel in 1916 which

state that : “The bond which is formed by complete transfer of electron from
one atom to another” .
Or
Electrostatic attractive force between two opposite ions is called ionic or
covalen bond .
Ex:- NaCk , MgO2 ( all salts contain ionic bond )
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( Covalent Bond )

This bond was given by The American Scientist G.N Lewis in

1916 which state that : “The bond which is formed by mutual sharing of
electrons between two similar or dissimilar atoms is called covalent bond .
=>This bond is formed between non – metals , mostly they are liquids and
gases .
=>There are three types of covalent bond : 1) Single Covalent bond ,
2) Double covalent bond 3) Triple Covalent bond .

( Modern Theories of Chemical Bonding )

The Lewis concept of chemical bond is failed to explain the

varying strength of multiple bonds , shape or geometry of the molecules and
paramagnetic character of O2 atom .
=>The two modern theories were developed to explain these factors .
1) Valence bond theory , london and Heitler gives this theory in 1927 .
2) Molecular Orbital theory , Mullikan , Hund and Huckel in 1927 .

1)Valence Bond Theory :- This theory was introduced by London and

Heitler in 1927 . This theory tells how the bonding in covalent moleule takes
place by the overlapping of atomic orbitals . It not only provides basic
information for analyzing the structure and the bonding in the molecule but
also the strength of covalent bond as well as molecular shape on the basis of
atomic orbital interaction .
Postulates :
1)A covelent bond is formed due to the overlap of half filled orbital of
combining atoms ( The term of overlap represents sharing of some common
region in space ) .
2)As a result of overlapping there is a maximum electron cloud somewhere
between the two overlapped orbitals .
3) The electron present in both overlapped orbitals should be in opposite spin .
4)The strength of bond is determined by extent of overlap . The greater the
overlap , the stronger is bond .
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5)Each atoms involves in overlapping keep its own atomic orbital but electron
pair is shared up by both atoms which take part in overlapping .
Valence bond theory describes two ways of overlapping of atomic
orbital which results in the formation of following two types of covalent bonds .
1)Sigma ( σ ) bond 2) Pi ( π ) bond .

1)Sigma ( σ ) Bond :- The bond which is formed by linear or head to head /

end to end overlapping of partially filled atomic orbital , is called Sigma ( σ )
bond .
=>This overlapping is effective and ocurs on the bond axis . So maximum
overlapping is occurring , hence it is very strong bond .
=>It is formed by overlapping of S to S , S to P and P to P orbitals .

a)S – S overlap :- This occurs when two S orbitals overlap head – on .

Ex :- H2 molecule .

b)P – P Orbital :- When two P orbitals overlap head – on along their axis it
results in sigma bond .
c)S – P orbital :- This occurs when an S orbital overlap with a P orbital along
their axis , it results in sigma bond .

2)Pi ( π ) Bond :- The bond which is formed by parallel or side to side

overlapping of partially filled atomic orbital is called Pi bond .
=>This overlapping is not effective because it doesn’t lies on bond axis and due
to side to side overlapping , so minimum overlapping is occuring hence it is
very weak bond . It is so weak that it can’t holds two two atoms together in a
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molecule . It is formed only when two atoms are already bounded by sigma
bond . It is formed by the overlapping of p – p orbitals .

2)Molecular Orbital Theory :-

Mullikan , Hund and Huckel (1927) developed
an alternate theory known as molecular orbital theory to overcome the short
comings of VBT .
Postulates :
1)Atomic orbital of similar energies linearly combine together to produce
molecular orbital .
2)Combination of two atomic orbital gives two molecular orbital one of them
has lower energy and other has higher energy than any of the atomic orbital
from which they formed .
3)The molecular orbital with lower energy is called as bonding molecular
orbital and the orbital with higher energy is called as anti boding molecular
orbital .
4)The movement of electrons in molecular orbital is influenced by both nuclei
of combining atoms .
5)The filling of electrons into the molecular orbital is followed by fundamental
rules of electronic configuration i.e. Aufbau principle , Hund’s rule and Pauli
rule .

(Shape of The Molecules)

Simple polyatomic molecules and ions generally
acquire linear , tetrahedral , pyramidal and angular shapes etc . These shapes
can be determined experimentally , however also predicted on theoretical
basis . Beside VBT there are two more significant theories which describe the
shape of molecules .
1)Valence Shell Electron Pair Repulsion Theory (VSEPR) :-
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This
approach to the structure of a covalent molecule is due to sidgwick and powell
(1940) . They pointed out that the shapes of molecules can be determined by
the repulsion b/w electron pairs present in valence shell of central atom .
Postulates :
1)There may be two types of electron pairs surrounding the central atom .
a)Bond pairs :- These are the result of the sharing of unpaired electrons of
central atom with unpaired electrons of surrounding atoms . These are also
called active set of electrons .
b)Lone Pairs :- These are the paired electrons of central atom which don’t
take part in sharing . They are also called non – bonding pairs .
2)Being similarly charged (i.e. –ve) the bond pairs as well as the lone pairs
repel each other .
3)Due to repulsion , the electron pairs of central atom try to be as far apart as
possible ; hence they orient themselves in space in such a manner that force of
repulsion b/w them is minimized .
4)The force of repulsion b/w lone pairs and bgond pairs is not the same . The
order of repulsion is as follows : Lone pair – Lone pair repulsion > lone pair –
bond pair repulsion > bond pair – bond pair repulsion .
5)In case of molecules with double and triple bonds , the π electron pairs are
not considered to be an active set of electrons , hence not included in the
count of total electron pairs .
6)The shape of molecules depends upon total number of electron pairs
(bonding and lone pairs) .

Prediction of five basic shapes by VSEPR :

1)Linear shape :- (AX2 type)
(Lewis structure – X – A – X)
The central atom A possess two electron pairs , both are bonded pairs . They
will repel eachother due to similar charges and will live at maximum
separation , which is possible in linear shape at an angle of 180 0 .
Ex:- BeCl2 , C2H2 etc .

2)Trigonal (Planar Shape) :- (AX3 type)

Lewis structure
X
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A
X X

The central atom A possess three electron pairs , all are bonded pairs . They
will repel eachother due to similar charges amd will live at maximum which is
possible in Trigonal Planar shape at an angle of 1200 .
Ex :- BF3 , C2H4 etc .

3)Tetrahedral Shape :- (AX4 type)

Lewis structure
X
X A X

The central atom A possess four electron pairs . All are bonded pairs . They will
repel eachother due to similar charges and will live at maximum separation
which is possible in tetrahedral shape at an angle of 109.5 0 .
Ex:- CH4 , C2H6 etc .

4)Trigonal Pyramidal shape :- (AX3E type)

Lewis structure
(..)
A

X X X

The central atom A possess 4 electron pairs , three are bonded pairs and one in
lone pairs . The repulsion of lone pair is greater the bond angle will be reduced
from 109.50 to 1070 . The shape become trigonal pyramidal .
Ex:- NH3 , PH3 PCL3 etc .

5)Angular shape :- (AX2E2 type)

Lewis structure
(..) (..)
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A
X X

The central atom A possess 4 electron pairs , two are bond pairs and two are
lone pairs . The repulsion of lone pair is greater the bond angle will be reduced
from 1070 to 1040 . The shape become angular .
Ex:- H2O , H2S etc .

(Hyberdization)
The concept of hyberdization was introduced by the
Scientist Lineaus Pauling (1885) which state that : “The process of
interionizing orbitals of different energy and different shape to form same
number of orbitals , having same shape and same energy is called
hyberdization .
=>The orbitals before mixing are called hyberdized orbitals , the orbitals after
mixing are called hyberdized orbitals .
=>The energy of hyberdized orbitals is lower than unhyberdized orbitals
(during mixing energy reduced) .
There are three types of hyberdization i.e. Sp3 , Sp2 and Sp hyberdization .

1)Sp3 hyberdization :-
The `process in which one s and 3 p orbitals mix
together to form Sp3 hyberdized orbitals are called Sp3 hyberdization .
=>The central atom will give this hyberdization when it has to link with four
other atoms .
Ex : CH4 (methane) .

2)Sp2 Hyberdization :-
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The process in which one S and 2 p orbitals mix
together to form Sp2 hyberdized orbitals is called Sp2 hyberdization .
=>The central atom will show this hyberdization when it has to link with other
atoms .

3)Sp Hyberdization :-
The process in which one S and one P orbitals mix
together to form Sp hyberdized orbital is called Sp hyberdization .
=>Two orbitals will remain unhyberdized .
=>Central atom will show this hyberdization when it has to link with two other
atoms .

(Characteristics of Covalent Bond)

Bond Energy :-
The amount of energy required per mole to break a bond is
called bond energy .
Or
The amount of energy released per mole to form a bond is called bond energy .
=>Bond breaking is a endothermic process (energy absorbed) symbolized by
( Δ H +ve) and formation is a exothermic process symbolized by ( Δ H –ve) .
=>Most accurate measure is obtained in the case of bond breaking , so bond
energy is considered mostly for breaking of bond .
=>In S.I system it is measured in KJ/mole .
=>Bond energy is measure the strength of the bond , greater the bond energy
stronger is the bond .
=>Strength of bond depends upon three factors .
1)Polar and non – polar characters :- Polar bonds are stronger than non –
polar covalent bonds .
Ex:- HCL --- H + CL ( Δ H = 431 Kj / mole ) .
Cl2 -- Cl + Cl ( Δ H = 242 Kj / mole )
2)Size of an atom :- Bonds of the smaller atomic size molecule are stronger
than larger atomic size molecule .
Ex:- H2 -- H + H ( Δ H = 436 kj / mole )
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Cl2 --- 2Cl ( Δ H = 242 Kj / mole) .
3)Multiple Bonds :- Higher the bond order , higher will be bond energy ,
shorter bonds are stronger than larger bonds .
Ex :- C C ( 348 Kj / mole ) .
C C ( 614 Kj / mole ) .
C C ( 839 Kj / mole ) .
Bond Length :-
The distanmce between the nucleus of two bonded atoms in a
molecule is called bond length .
=>Due to the vibration of the atoms , accurate bond distance can’t be
measured hence we take the average of bond length .
=>Bond length is experimentally determined by X – ray diffraction method .
=>It is very small distance and is measured in angstrome unit of length .
1 Angstrome = 10—8 cm .
=>From bond length we can determined the strength of the bond that depends
upon following factors .

1)Bond Order ( , , ) :- Greater the number of bonds , shorter

is bond distance , stronger is the bond .
=> triple bond ( bond distance 1.20 ) are stronger than double bond (1.32) is
stronger than single bond (1.53) .

2)Bond Polarity :- Polar bonds are stronger than non – polar bonds due to
smaller bond distance of polar .
Ex :- HCL ( b.L = 1.27 ) stronger .
Cl2 ( b.L = 1.79 ) weaker .

(Ionic Characters of Covalent bond )

1)Non – polar covalent bond :-

When covalent bond is formed b/w similar
atoms or dissimilar atoms in which (E.N) difference is from 0 to .4 , the shared
pair in these molecule will remains b/w two atoms , poles are not produced ,
such bonds are called non – polar covalent bonds and molecules are called non
– polar molecules .
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Ex :- Cl2 , H2 , O2 etc .

2)Polar Covalent bonds :-

When covalent bond is formed b/w two dissimilar
atoms , having (E.N) difference is greater than 0.4 . The shared pair doesn’t
remain b/w two atoms , it will be shifted towards more electronegative atoms ,
creating partial positive on towards (E.N) atom and partial negative on high
(E.N) atom , poles are produced . Such bonds are called polar covelent bonds
and molecules are called polar molecules .
Ex:- HCL , HF , H2O etc .
=>The bond is covalent but slight ionic character is produced which is called
ionic character of covalent bond .

(Dipole Moment)
The measure of the polarity or ionic character of a polar
molecule product due to (E.N) difference ( > 0.4 ) is called dipole moment .

Mathematically
It is the product of magnitude of the charges on the poles and the distance
between the poles , is called dipole moment symbolized by mue ( μ ) .
μ=e × d
e = charge on pole , d = distance b/w poles .
charge of electron = 10—10 esu ( partial charge )

μ=e × d

= 10--10 x 10—8
−18
μ=10 esu . cm→ unit∈CGS .

=>In diatomic molecule (D) only depends on (E.N) difference .

=>In polyatomic , it depends on (E.N) and shape .
=>in diatomic molecule , it only depends upon (E.N) difference , greater the
(E.N) difference , greater is the dipole moment .
Ex:- HF molecule possess greater dipole moment than HCL molecule .
=>In polyatomic molecule , it doesn’t only depends upon geometry or shape of
the molecule .