CHEMICAL BONDING

SESSION – 1
AIM
• To define Chemical Bond
• To understand the reason for chemical bond formation
• To introduce Ionic bond
CHEMICAL BOND is an attractive force which holds various constituents
(atoms, molecules or ions) together in different species.
Chemical bonds devided into two types:
a) Bonds which constitute molecules or formula units. These are ionic
bonds, covalent bonds and co-ordinate or dative bonds.
b) Bonds which hold various particles in solid or liquid state of the
substances. These are also called INTERMOLECULER FORCES.
These are: metallic bonds, dipole-dipole forces, van der Waal forces,
hydrogen bonds.
Cause of Chemical Combination:Chemical bonding takes place due
• To acquire a state of minimum energy and maximum stability
• To convert atoms into molecule to acquire stable noble gas
configuration.
LEWIS THEORY
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.
OCTATE RULE- ‘Atoms combine with each other either by sharing or by
the transfere of electrons to attain stable noble gas configuration I n
outer most shell.’
H × O × H
Obeys octet rule

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

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

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.
.. .. .. ..
For example, F2 is : F.. : ..F :or : F.. ..F : and a molecule of hydrogen fluoride
.. ..
is shown as H : ..F : or H F.. :

Arrangement of valence electrons and symbol of elements in a molecules

are called Lewis structures.
..
..
(i) In water (H2O), one .
H and two .O :
. complete their :O H
duet
H
and octet respectively
.. ..
(ii) In ammonia (NH3), three and one fit together and .
H .N .
. H N H

satisfy their duet and octet respectively as H

.. .
(iii) In carbon tetrachloride (CCl4), four : Cl
..
. and one .C .
. complete their
octet as ..
:Cl:
.. ..
:Cl
.. C Cl
.. :

:Cl
.. :
Limitations of Octate rule
• It is failed to explain the stability of incomplete octate.
For example, BH3, BF3, BCl3, AlCl3, GaCl3 etc.
i.e., contraction of octet < 8e-
BeF2 BF3 AlCl3 BCl3

(4e) (6e) (6e) (6e)

Cl ×Be× Cl
×
Cl In BCl 3 
 
Boron has only 6 electrons 

• It is failed to explain the stability of extended octate.It is possible in

those molecules having vacant d−orbitals.
Cl Cl
For example, PCl5, SF6 etc. × ×
P ×
Cl × Cl
i.e., Expansion of octet > 8e- ×

PCl5 SF6 ClF3 ICl5 IF7

Cl
Electron dot formula of PCl5
(10e) (12e) (10e) (12e) (14e)

• It is failed to explain the stability of odd electron species.

For example, NO, NO2 and ClO2.
NO NO 2 ClO 2 ××
×N × O
(11e ) (17e ) (19e ) ×

7e– 8e–
• It is failed to explain the stability of duplet structure of Hydrogen
atom.
• It is failed to explain the stability of Cations of transition metals,
which contains 18 electrons in outermost orbit
Examples : Ga+3, Cu+, Ag+, Zn+2, Cd+2, Sn+4, Pb+4 etc.
Electronic configuration of Ga - 1s2, 2s2 2p6, 3s2 3p6 3d10,4s2 4p1
Electronic configuration of Ga+3 - 1s2, 2s2 2p6,
• Octate rule based on the chemical inertness of noble gases but some
noble gases able to form compounds like XeF2 , KrF2 etc
• Failed to explain the geometry of molecules.
• It is failed to explain the relative stability of molecules.
METHOD OF DRAWING LEWIS STRCUTURES of polyatomic species
(i) First calculate n1.
n1 = Total valence electron of all the atoms of the species  net
charge on the species.
For anion, electrons are added and for cations electrons are
subtracted.
(ii) Then calculate n2.
n2 =(8  no, of atoms other than H) + (2  no, of H atoms)
(iii) Subtract n1 from n2, which gives n3.
n3 = n2− n1 = number of electrons shared between atoms = number
of bonding electrons.
n 3 n 2 − n1
2
=
2
= number of shared electron or bps = number of bonds.
(iv) Subtracting n3 from n1 gives n4.
n4 = n1−n3 =number of unshared electrons or non−bonding electrons.
n4
2
= n1 − n 3
2
= no, of unshared electron pairs = number of lone pairs.

(v) Identify the least electronegative atom in a molecule as central

atom,when the other atoms do not contain hydrogen.
When other atoms are hydrogen only, then the central atom
would be the more electronegative atom.
(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) Calculate the formal charge on each atom.
(ix) Lewis structure should obey like resonance (delocalization), bond
length, p−d back bonding etc.
Exp- Determine Lewis structure of NO − ion. 3

(i)n1 = 5 + (6  3) + 1 = 24

(ii)n2 = ( 4  8) = 32

(iii)n3 = n2 − n1 = 32 − 24 = 8

 Number of bonds = 8
2
=4

(iv)n4 = n1− n3 = 24 − 8 = 16  Number of lone pairs = 16

2
=8

(v)Nitrogen is central atom (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
0.. +1 .. .. +1 .. .. +1 ..0
:O : O.. ..O: :O O:
..O:
N N ..
N

: O..: −1 : O: 0 : O..: −1

Final structure of NO 3− is therefore shown as

.. ..
:O N ..O:
: O..:

which even accounts for resonance in NO 3− ion.

Classification of bonds : -

CHEMICAL BONDS

STRONG BOND WEAK BOND

(Inter atomic) (Inter Molecular)
(Energy ~– 200 KJ/mole) (Energy ~– 2 - 40 KJ/mole)

(A) (B) (C) (D) (E) (F)

Ionic Covalent Co-ordinate Metallic Hydrogen Vander waal's
bond bond bond bond bond bond
(10 - 40 KJ) (2 - 10 KJ)

• IONIC or ELECTROVALENT BOND

Ionic bond is formed by transference of electrons from electropositive
atom to electronegative atom.
Atom losing electrons becomes cation while the atom gaining
electrons becomes anion.
Electro +ve atom loses electron (group IA to IIIA)
Electro –ve atom gains electron (group VA to VIIA)
‘The electrostatic force of attraction holding the oppositely charged
ions’ is called electrovalent bond or ionic bond.
Exp- *IA and VIIA group elements form maximum ionic compound.
+
Na + Cl Na + Cl–
2, 8, 1 2, 8, 7 2, 8 2, 8, 8
1e– (Ne configuration) (Ar configuration)

• More the distance between two elements in periodic table more will
be ionic character of bond.
• Total number of electron lose or gained by an atom during the
formation of ionic bond is called electrovalency.
(a) In MgCl2 formation, electovalelency of Mg and Cl are 2 and 1
respectively.
Mg O
(b) 2, 8, 2 2, 6 electrovalency of Mg = 2
2e– electrovalency of O = 2

Ca Cl
2, 8, 8, 2 2, 8, 7 electrovalency of Ca = 2
(c) One e– electrovalency of Cl = 1
Cl
2, 8, 7
One e–

Ca + O CaO
Ca O
(d) 2, 8, 8, 2 2, 6 electrovalency of Ca = 2
electrovalency of O = 2
2 e–
Factors favouring formation of ionic bond:
• Atomic Size: Larger atoms can easily form cations.
i.e., form ionic compounds easily, due to decrease in force of
attraction of the nucleus on the valence electrons.
Order of formation of alkali metal cations is:Li+ < Na+ < K + < Rb+ < Cs+
Smaller atoms can easily form anions.
Ex: The ease of formation of halide ions is: F + > Cl− > Br− < I−
• Ionisation Potential: Atoms with low I.P can easily form cations.
Lesser i e Greater tendency to form cation.
Ex:The I.P of Na is 117.3 Kcal / mole, while that of K is 100
Kcal/mole. Therefore 𝐊+ ion is formed more easily than Na+ ion.
e.g Na +  Mg +2  Al +3 

 Cation formationtendency
+ + +
Cs  Rb  K  Na  Li + +



• Charge of the ion: Cations with low charge are formed more easily
than the cations with high charge.
Ex: Ease of formation:Na+ > Mg 2+ > Mg 3+
• Electronic Configuration:Cations with inert gas configuration are
formed more easily than the cations with pseudo inert gas
configuration. (18 valence electrons).
Ex:Ca2+ ion (2, 8, 8) is formed more easily than Zn2+ ion (2, 8, 8).
• Electron Affinity/Electronegativity: Atoms with high electron
affinity are able to form anion more easily.
Ex: halogens possess high electron affinity.So the formation of their
ions is very common.
 Higher electron affinity Greater tendency to form anion
e.g. Cl– > F– > Br– > I– F– > O–2 > N–3
• Charge of the ion: Anions with low charge are formed more easily
than the anions with high charge.Vice versa for cation.
Ex: Ease of formation:F − > O2− > N3−
• Lattice energy –‘Amount of energy released when one mole of
crystal product is formed from gaseous reactants’. Or
‘Amount of energy absorbed when one mole of ionic crystal is
dissociated into its gaseous reactants’.
Factors affecting lattice energy :
(i) Magnitude of charge U  z+ z– (Ionic charge)
High lattice energy Greater stability of ionic compound.
• Lattice energy  Magnitude of charge
NaCl MgCl2 AlCl3
Na+ Mg+2 Al+

– Lattice energy increases

– Size of cation decreases.
• Size of Cation : – Lattice energy
LiCl NaCl KCl RbCl CsCl

– Size of cation increasing

– Size of anion is constant – Lattice energy decreases
 SESSION – 2
AIM
1]To understand the properties of ionic compounds
2]To introduce lattice energy
PROPERTIES OF IONIC COMPOUNDS
• Physical state- They are hard, crystalline and brittle solids due to
strong electrostatic force of attraction.

Attraction Repulsion
(Same charged ions comes nearer. So they repell each other)

• Isomorphism Ionic compounds are isomorphous i.e.,they have same no. of

electrons.(similar configuration of their cation and anion)with same
crystal structure.
Example – Na+ F– Mg+2 O–2
Valency + 1, –1 + 2, –2
electronic configuration 2, 8, 2, 8 2, 8 2, 8

• Boiling point and melting point is high due to strong electrostatics

force of attraction among oppositely charged ions.
• Conductivity depends on ionic mobility.
In solid state - No free ions - Bad conductor of electricity.
In fused state or aqueous solution Due to free ions - Good conductor
of eletricity.
conductivity order : Solid state > Fused state < Aqueous solution
* Reactivity: Ionic compounds undergo ionic reactions which have very high
reaction rates. i.e., quite fast
* They do not exhibit isomerism due to non-directional nature of the
polar bonds present in these compounds.
* Solubility Highly soluble in water (Polar solvents) with high value of
dielectric constant but insoluble in non-polar solvents due to low
dielectric constant. The solubility of ionic compounds decreases with
increase in covalent character of ionic compounds.
Example : NaCl in water
(I) The Na+ ions get associates with –vely charged ‘O’ of water
(II) And Cl– ions associates with +vely charged ‘H’ of water.

H2O–
H2O–

+
+

Na+ Cl–
+
H2O– +
H2O–

+
Oxygen atom of H2O give its electron to Na H atom of H2O gain electron from Cl–

Solubility of Ionic compound is governed by

a)Lattice energy: Larger the lattice energy, the lesser is the solubility.
e.g., sulphates and phosphates of Ba & Sr are insoluble in water due to
high lattice energy.
b)Heat of hydration: Larger the heat of hydration, the more is the
solubility of ionic compound.
e.g., AlCl3, though covalent in nature is soluble in water due to high
Born - Haber Cycle
(Energy changes involved in the formation of an ionic bond):
The energy changes which take place in the formation of an ionic
compound from its component elements can be studied with the help of a
thermochemical cycle known as Born-Haber cycle.
For example, in the formation of one mole of sodium chloride from sodium
and chlorine the following steps are involved.
• Conversion of metallic sodium (solid) into gaseous sodium atoms:
Na + H
(s) → Na (sub) Here H sub = H atomisation
(g)
1mole 1mole

where H is the enthalpy of sublimation of sodium. It is the

sub

amount of energy required for converting one mole of solid sodium into
gaseous sodium atoms.
• Dissociation of chlorine molecules into chlorine atoms:
Cl 2(g) + D → 2Cl(g)
Chlorine Chlorineatom
molecule(1mole) (2moles)

where D is the dissociation energy (bond energy) of Cl2. It is clear that

the energy needed for the formation of one mole of chlorine atoms is
D/2.
• Conversion of gaseous sodium atoms into gaseous sodium ions:
Na (g ) + Ionization energy → Na + (g )
(I.E)
+ e-
1mole 1mole

• Conversion of gaseous chlorine atoms into gaseous chloride ions:

Cl(g ) + e − → Cl − (g ) + E.A.
(Electron affinity)
1mole 1mole

• Combination of gaseous sodium ions and gaseous chloride ions to give

solid crystal.
Na + (g) + Cl− (g) → Na + Cl− (s) + U
lattice energy
1mole 1mole 1mole
 The overall formation of ionic solid may be represented as below:
Na (s) + 1
2 Cl2(g ) → Na + Cl(s)
−
; Hf

Where H f is the heat of formation of 1 mole of Na+Cl–(s) .

Steps may be represented in the form of Born-Haber cycle.
Na(s) + 1
Cl2 (g) ⎯⎯→ NaCl(s) ;Energy change = ( Hf )
2
1
S D
2

S= Sublimation of sodium
D= Dissociation energy of Cl2
Na(g) Cl(g)
U IE = IE of sodium(IE)
EA EA = EA of chlorine(EA)
−e − IE
U= Lattice energy of NaCl

Na+ (g) Cl− (g)

According to Hess law of constant heat summation, the heat of formation

of one mole of Na+Cl–(s) should be the same whether its formation takes
place directly in a single step or through a number of steps.
Hence, Hf = Hsub + IE + 12 D + (−EA) + (− U)

On substituting values in the above expression,

we get: Hf = (+108.5) + 495.2 + 12 (243.0) + (−348.3) + (−758.7) = −381.8kJ mole−1

The negative sign in the values shows the energy released, while the
positive signs indicate that the energy is absorbed.
Formation of NaCl molecule,involves net fall in the energy of the
system,hence Na+Cl–(s) is quite stable.
Higher the negative values of heat of formation, greater will be the
stability of the resulting ionic compound.
 SESSION – 3
AIM
1]To introduce covalent bond
2]To explain covalent bond formation and types of covalent bond
3]To explain Lewis -dot structures.
COVALENT BOND-The bond is formed by mutual sharing of electrons
between the atoms. The atoms participating in bonding contribute
equal number of electrons for mutual sharing.
It is of 3 types
a)Single covalent bond:Here covalent bond formed by sharing of two
electrons(i.e.,1 electron pair).
It is represented by a single line between two atoms.
Example :
• formation of H2 molecule
H + H H H H–H
or Single bond
→

Shared pair
electrons

• formation of Cl2 molecule:

Cl + Cl Cl Cl or Cl Cl

• formation of HCl :
H + Cl H Cl or Cl Cl
b) Double bond or double covalent bond formed by sharing of two electron
pairs, between two atoms, it is represented by a double line ( = )
between two atoms.
Example . Formation of O2 molecule :
O + O O O or O O

Shared es−

c) Triple covalent bond formed by sharing of three electron pairs. It is

represented by a triple line (  ) between two atoms.
Example. Formation of N2 molecule
N + N N N or N  N

Thus, the number of covalent bonds formed by an atom depend on

i) the number of unpaired electrons in their valency shell.
ii) the number of electrons required to attain inert gas configuration.
Generally p block elements are involved in the covalent bond
formation.
Some more examples of formation of covalent Bonds:
• BeCl2:
Cl + Be + Cl Cl Be Cl or Cl – Be - Cl

Short of 4 electron pair

• BF3 or BCl3:
F
B + 3 F F F
B
(Cl)
Short of 2-electrons

O + C+ O O C O or O = C = O
e
• CO2:
 • NH3 (Pyramidal):
H N H
N + 3H or N

H H H
 H
HNH = 1070 (Pyramidal)

• H2O (Angular) :
H + O + H H O H or H – O – H
or

H H
1040,
300
(V-Shaped)

Based on nature of atoms b/w electrons, covelent bonds devided into

1. Non-Polar Covalent Bonds:Here bond is formed between similar atoms,
shared pair of electrons lies almost in the centre and electron cloud is
uniformly distributed around the two atoms.

2. Polar Covalent Bonds bond is formed between dissimilar atoms having

different electro negativities, the bond pair is displaced towards
more electronegative atoms creating partial positive charge on the
less electronegative atom and partial negative charge on more
electronegative atom. Such a bond develops some ionic character.

Ex: HCl or 𝐻 𝛿+ − 𝐶𝑙 𝛿−
 SESSION – 4
AIM1]To introduce properties of covalent compounds
2] To introduce dative bond
3]To introduce Fajan’s rules
Characters of Covalent compounds
* Constituents:They made with discrete molecules and strong bonding
forces exist between the atoms of a covalent compound.
* Physical State: They occur as liquids or gases or soft solids (e.g.,
sulphur, phosphorus and iodine).
The various molecules are held together by weak van der Waal’s forces.
* Solubility:They dissolve in non-polar solvents (organic solvents) like
ethanol, ether, benzene, chloroform etc. and insoluble in polar solvents.
Some of the covalent compounds like alcohols, amines dissolve in water due
to hydrogen bonding.
* Electrical Conductivity: Covalent compounds contain neither ions nor
mobile electrons, so they are unable to conduct electricity in either the
solid, liquid or gaseous state.
* Melting and Boiling Points : is low bcz in covalent compounds, molecules
are held together by weak van der Waal’s forces.
Some giant molecules (eg. diamond,SiC & Silica have high MP and BP.
* Nature of Reaction:is molecular reactions which are slow and complex.
* Covalent compounds show structural and space isomerism because covalent
bonds is rigid and directional.
Covalency : It is defined as the number of electrons contributed by an
atom of the element for shairing with other atoms to achieve noble
gas configuration.
If the outermost orbit has empty orbitals then covalent bonds are formed
in exicted state.
Variable valency in covalent bonds :
(I) Variable valencies are shown by those elements which have empty
orbitals in outermost shell.
(II) Lone pair electrons gets excited in the subshell of the same to
form the maximum number of unpaired electrons. Maximum covalency
is shown in excited state.
(III) The energy required for excitation of electrons is called promotion
energy.
(IV) Promotion rule – Excitation of electrons in the same orbit.
(a) Phosphorus → Ground state
Covalency 3 (PCl3)
3s 3p

Phosphorus → Excited state

Covalency – 5 (PCl5)
3s 3p 3d
 (b) Sulphur → Ground state.
Covalency–2 (SF2)
3s 3p 3d

Sulphur → Excited state 1stexcitedstate

Covalency – 4 (SF4)
3s 3p 3d

2st excited state Covalency–6 (SF6)

3s 3p 3d

So variable covalency of S is 2, 4 & 6.

CO-ORDINATE BOND OR DATIVE BOND “ a covalent bond in which
both electrons of the shared pair are contributed by one of the two
atoms”. It is represented by an arrow (→) pointing its head towards
the acceptor atoms.
The atom which supplies the electron pair (a lone pair) is called
donor(Lewis base) and the other atom accepting the share in this
lone pair is called the acceptor(Lewis acid).
Ex: Formation of ammonium ion: Even though ammonia molecule has a
stable electronic configuration, it can react with a hydrogen ion H+
by donating a share in the lone pair of electrons, forming the
ammonium ion, NH4+.
Ex:NH3 reacts with BF3 by its lp, to form a complex [NH3 BF3].

O
SO 3
O S O
 Cl
Cl
Cl P Cl
PCl 6
Cl
Cl

F
F
F Sb F
SbF6
F
F

Comparison of ionic, covalent & coordinate compounds

Property Ionic Covalent Coordinate
binding force Between ions Between molecules in between
strong smaller (Vander
(coulombic) Waal’s)
mp/bp High less than ionic in between
condition conductor of bad conductor Greater than
electricity in covalent
fused state
&
in aqueous
solution
solubility in polar High Less in between
solvent (H2O)
Solubility in non Low High in between
polar solvent
(ether)
6. Physical generally solid liquid & gaseous solid, liquid gas
state
POLARISATION OF IONS
(Fajan’s Rule) (Covalent nature in ionic bond)
In ionic compound,cation approaches an anion closely,positive charge on the
cation attract the electron cloud of the anion towards itself due to
electrostatic force of attraction.
At the same time the cation also tends to repel the positively
charged nucleus of the anion.As a result electron cloud of the anion no
longer remains symmetrical and elongated towards the cation is called
deformation or Polarization of the anion by the cation and the anion is
said to be polarised.
The ability of a cation to polarise a nearby anion is called its
polarization power.

Polarizability is the ability of anion to get polarised by the cation.

• Polarisation of anion causes some sharing of electron between the
ions so ionic bond acquires certain covalent character.
i.e., Polarisation  Covalent character
Factors affecting the polarisation of an ion: (Fajan’s Rule)
• Charge on the ions: Charge on the cation increases, its tendency to
polarize the anion increases and covalent nature increases in ionic
compound.
 Whereas with the increasing charge of anion, its ability to
get polarized, by the cation, also increases.
i.e., Polarisation  charge on cation anion
Charge on cation  Polarisation (covalent character)
eg. NaCl MgCl2 AlCl3 SiCl4
Na+ Mg++ Al+++ Si++++

- Charge on cation increases

- Covalent character increases
- Ionic character decreases (M.P. decreases)
Charge on anion  polarisation  covalent nature  1
M .P.
- Among PbCl2 and PbCl4 having charges +2 and +4 respectively.
PbCl4 shows covalent nature.
- Among NaCl, Na2S, Na3P, the charge of the anions are increasing,so
order of covalent character is NaCl < Na2S < Na3P
• Size of the cation: Smaller the size of cation more will be the
polarizing power and higher is its covalent nature.
Polarisation  1
size of cation

- In a group –
BeCl2
MgCl2 - Size of cation increases
CaCl2 - Covalent character decreases
SrCl2 - Ionic character increases
BaCl2

Greatest polarising power of Be2+, shows its maximum covalent character.

- In a period – Na+, Mg+2, Al+3, Si+4
 - Size of cation decreases
- Covalent charater increases
• Size of anion::Larger the size of the anion,polarized by the cation
and covalent character increases.
Polarisation  size of anion
For example, in the case of halides of calcium, the covalent character
increases from F– anion to I– anion i.e.
CaF2
CaCl2 - Size of anion increases
CaBr2 - Covalent character increases
Cal2 - Ionic character decreases

Similarly,

• Nature or Electronic configuration of cation : -

Polarisation capacity of cation having pseudo inert gas
configuration is high. If the size of cations is same than that of
cation having inert gas configuration.
CuCl (M.P. 442°C) Cu+ 2, 8, 18(Covalent)
NaCl (M.P. 800°C) Na+ 2, 8(Ionic)
Cu+ and Na+ both the cation (Pseudo & inert) have same charge
and size but polarising power of Cu+ is more than Na+ .
So CuCl has more covalent character than NaCl.
 SESSION – 5
AIM - To introduce VBT
Valency Bond Theory:VBT was proposed by Heitler and London. It was
modified by Pauling and Slater. (According to this theory, a covalent
bond is formed by overlapping of atomic orbitals].
• A covalent bond is formed by overlapping of unpaired atomic
orbitals of two atoms.
After overlapping both orbitals got common region of electron density.
• Overlapping of orbitals causes delocalisation of electrons which in
turn, lowers the energy and increases the stability.
Resulting bond acquires a pair of electrons with
opposite spins to get stability.
• The strength of the bond depends on the extent of overlapping.
Overlapping of orbitals is higher, the bond formed is stronger.
Order of overlapping s-s overlappinf > s-p overlapping > p-p
overlapping
• The direction of the bond formed is the direction in which the
bonding orbitals are oriented.
• As the value of n increases, bond strength decreases.
1-1>1-2>2-2>2-3>3-3
If n is same 2p - 2p > 2s - 2p > 2s - 2s
1s - 2p > 2s - 2 p > 3s - 3p
 • Orbitals can overlap in 2 ways,
Axial overlapping results in sigma ( ) bond here atomic orbitals
overlap along the inter-nuclear axis and involve end to end or head
on overlap.Here electron cloud is cylindrically symmetrical about
inter-nuclear axis. The electrons constituting sigma bond are called
sigma electrons.
Three types of axial overlapping
- s-s overlapping - Overlapping of two half-filled s-orbitals of the atoms
approaching to form a bond s-s 𝝈bond.
Formation of H2 molecule:
Hydrogen atom has one electron in 1s orbital. H → (1) 1s1. This
orbital having unpaired electron overlaps axially with 1s orbital of
another H atom to form a sigma bond. H-H molecule is thus formed.
+

1s 1s  bond 1s 1s
(Formation of H2 molecule)

- s-p overlapping. involves overlapping of half-filled s-orbital of the one

atom with half-filled p-orbital of the other, bond formed is called s-p
bond. Formation of HCl molecule:
Electronic configuration of H is 1s1 with 1s orbital.
Electronic configuration of chlorine is 1s2 2s2 2p6 3s2 3p5 with unpaired
electron in 3pz orbital.
 - Hydrogen’s 1s orbital and chlorine’s 3Pz orbital overlap with each
other axially to form a sigma bond.

1s of Hydrogen 3p of Chlorine H–Cl

- p-p overlapping.involves overlapping of half-filled p-orbitals of the two

atoms. The bond so formed is called p-p bond.
Formation of Cl2 molecule:
The electronic configuration of chlorine atom is 1s2 2s2 2p6 3s2 3p5
with an unpaired electron in 3Pz orbital.3Pz orbital of two chlorine
atoms overlap with each other axially to form a sigma bond.
p p
– + + + – + –
p-p overlapping

• Side ways overlapping of orbital is called 𝝅 (Pi) bond. Here electrons

are oriented above and below the inter nuclear axis.
- Formation of O2molecule:Electronic configuration of oxygen 1s2 2s2
2p4 . It has 2 unpaired electrons in 2Py and 2Pz orbitals.
2px orbitals of each oxygen atoms overlap each other axially to form a
sigma bond, 2Py orbitals of the oxygen atoms are perpendicular to
the axis.So they overlap laterally to form π bond. Thus O = O is
formed.
Py Py

Pz + Pz 

O2 molecule


• 𝜎 bond stronger than π bond due to higher overlapping of orbitals.

 • In a 𝜎 bond, the electrons are oriented along the inter nuclear axis
but in a  bond,.
• Free rotation of molecule about𝜎 bond is possible but free rotation
of molecule about π bond is not possible.
Differences between Sigma and Pi bond:
Sigma Bond Pi Bond
It is a stronger bond. It is a weaker bond.
It can exist independently. It exists along with bond
It allows the free rotation of It restricts the free rotation of
bonded atoms. bonded atoms.
The electron cloud of sigma bond The electron cloud of the bond
is along theinter nuclear axis liesaboveand below this axis.
of the bonded atoms.
All orbitals s, p, d...... can form Except ‘s’ orbital, all other
sigma bond. orbitals can form bond
Both pure and hybrid orbitals Hybrid orbitals cannot form
can form bond. bond
This bond is formed by the axial This is formed by the lateral
overlappingof orbitals. overlappingof orbitals.
 SESSION – 6
AIM - To introduce VSEPR Theory
VALENCE SHELL ELECTRON PAIR REPULSION THEORY:
VSEPR theory was proposed by Gillespie and Nyholm. This theory helps us
to predict the shape of covalent molecules based on the repulsive
interactions of valence electrons.
• The shape of the molecule depends upon the number and nature of
electron pairs present in the valency shell of the central atom.
• Electron pairs around the central atom of a molecule repell one
another bcz negative charge on the electron cloud.
• In order to minimise the repulsion and to maximise the stability,
valence electron pairs arranged away from each other around the
central atom in a space.
• Central atom in a molecule surrounded with 2 types of electrons.
- Bonding or shared electrons(bond pair)
- Non-bonding electrons(lone pair)
• Bond pair of electrons are under the influence of two nuclei but the
lone pairs are under the influence of only one nucleus. Hence lone
pairs are spread around the central atom and occupy more space
• If central atom surrounded with only bond pair electrons,molecules
shows definite geometry.
If central atom surrounded by atleast one lone pair electrons,
molecules shows altered or distorted or indefinite geometrty.
ie. the original bond angle will disturbed due to repulsion between lone
pair of electrons. Bond angle  1
No. of lone pair of electron

• The various repulsive forces experienced by these electron pairs is of

the order l.p -l.p > l.p - b.p > b.p - b.p repulsions
Shape of molecule having only bond pairs
No. of bp es- Shape Molecule
2 Linear BeF2, BeCl2, CO2
3 Triangular BF3,BCl3,SO3, CO32-
4 Tetrahedral CH4, CCl4 etc
5 Trigonal bipyramidal PF5, PCl5 etc
6 Octahedral SF6, SiF6-2
7 Pentagonal IF7
bipyramidal
Shape of molecule having bond pairs as well as lone pair electrons.
bond lone Total Shape of Molecule
Example
pairs pairs No. basic shape actual shape
SnCl2,
2 1 3 Triangular Angular
SO2
NH3,
3 1 4 Tetrahedral Pyramidal
H3O+
2 2 4 Tetrahedral Angular H2O
Folded
4 1 5 square
See Saw SF4
Trigonal
3 2 5 bipyramid T-shaped ClF3
al
Trigonal
2 3 5 bipyramid
Linear XeF2
 al
IF5,
5 1 6 Octahedral Squarepyramidal
BrF5
4 2 6 Octahedral Square planar XeF4
Pentagonal
Distored
6 1 7 bipyramid
octahedral XeF6
al

GEOMETRY OF MOLECULES
• Two Charge Clouds: When there are two charge clouds, as in carbon
atoms(two double bonds) and HCN (one single bond and one triple
bond), the clouds are far apart or in opposite directions. Thus, CO2
and HCN are linear molecules with bond angles of 180°.

• Three Charge Clouds: When 3 charge clouds, as in 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 lp), the
clouds are farthest aptwhen they lie in the same plane and point to
the corners of an
equilateral triangle
with bond angle
120°
ratherthan180°.
• Four Charge Clouds: is 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 with
bond angle 109.5°.

• Five Charge Clouds:found in central atoms in PCl5, SF4 and ClF3

are oriented toward the corners of trigonalbipyramidal. 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: shows regular octahedron,
 SESSION - 7 AND 8
AIM - To introduce hybridization
HYBRIDIZATION
The intermixing up of pure atomic orbitals of an atom having nearing
energies to give a set of equal number of identical hybrid orbitals of
same energy is called Hybridization.
This is a hypothetical concept and was proposed by Pauling and Slater
Rules for Hybridization:
• Atomic orbitals of an atom can intermix
• Atomic orbitals having nearing energy can intermix
• Vacant, half-filled or completely filled atomic orbitals can intermix
to form hybrid orbitals
• No. of hybrid orbitals formed is equal to number of atomic orbitals
intermixing
• Hybrid orbitals are identical in shape and have same energies but
differ in orientation in space.
• The electrons are redistributed in these hybrid orbitals following
Hund’s rule and Pauli’s exclusion principle
• Atomic orbitals only participating in Hybridization but not
electrons.
• Hybrid orbitals form  bonds, unhybridized orbitals form  bonds.
Molecule has a regular geometry, when hybrid orbitals contain shared
pair of electrons if one or more lone pairs of electrons in the valence
shell,molecule shows distorted geometry.
• Each hybrid orbital having two lobes, one is larger and other is
smaller. Bond will be formed from large lobe.
• The hybrid orbitals are oriented in space as far apart as possible.
Thus, they help in determining the shape or geometry of a molecule.
 Difference between hybridisation & overlapping
Overlapping Hybridisation
• It occurs between orbitals of • It occurs among orbitals
two atoms of the same atom
• Only half filled orbitals takes • Any type of orbital can
part inoverlapping participates
• It occurs during bond • Process, just before
formation bond formed after overlapping.
hybridisation
• Orbital of different energies •It may takes place in
may participatesin excited ground or in excited
states. state
Inground state– NH3, NCl3,
PH3, PCl3,
• Molecular orbitals are formed • Hybridised orbitals are
formed

TYPES OF HYBRIDISATION:
• sp Hybridization:
One s & one p orbital intermix to form two sp hybrid orbitals. This
process is called sp hybridization.sp-hybridised orbitals of equivalent
shapes and energies and arrange in straight line(linear shape) with
angle of 180°. Each sp hybrid orbital having 50% s -character
and 50% p –character
Example: BeH2 - central atom is Be.
2s 2p
Be (ground state)
2s 2p
Be (excited state)
Be-atom accepts 2 electrons from H in BeH2,
2s 2p

sp sp
sp hybridisation sp hybridisation

These two sp hybrid orbitals of Be overlap axially with the 1S1 orbitals
of 2 H atoms to form 2 sigma bonds with linear in shape and bond
angle 180°

CO2 Molecule (O = C = O ) :Here C has two sp hybrid orbitals & two

unhybridised p orbitals.It shows linear in shape with 180° bond angle .
 bond

 bond
Bond length between
Molecular orbital picture of CO2

C–O bond is reduced due to the presence of  bond.

CHCH [H–CA  CB–H] Here each C atom contains two sp hybrid
orbitals & two unhybridised p orbitals
2s 2p
C(ground state)
C(excited state)
C atom accepts four electrons from H & C
sp hybridisation
• sp hybrid orbital of each C overlaps to give sigma bond C – C.
• The remaining one sp hybrid orbital of each C atom overlaps with s
orbital of H, forming sigma bonds between C – H.
• The two unhybridised p orbitals of each C atom (py and px) overlap
laterally or sideways to form two pi()bonds.
Therefore in H–CA  CB–H
sigma bond between CA – CB is formed sp – sp overlapping
sigma bond between CA – H is formed sp – s overlapping
sigma bond between CB – H is formed sp – s overlapping
pi bond between CA – CB is formed : py–py,px–px overlapping
• Each C atom forms two sigma bonds but in C2H2 3 sigma bonds
• Each C atom forms two  bonds. Total  bonds in C2H2 are two
• Total number of bonds in acetylene are : 3 + 2 bond = 5
bonds

• sp2 Hybridisation: is intermixing of one s and two p orbitals to give

3 sp2 hybrid orbitals is called sp2 hybridisation.
3 sp2-hybrid orbitals lie in the same plane, directed towards corners of
equilateral triangle with is 120° bond angle between them. sp2 hybrid
orbitals shows 33.3% of s –character , 66.7 % of p –character.
Example: - BF3
In BF3 molecule the central atom is B electronic configuration is in
B (ground state)
2s 2p

B (excited state)
B atom accepts 3 electrons
From 3 F atom  in BF3
2
sp hybrid orbitals

One S orbital and two P orbitals of B atom intermix to form 3

sp2hybrids orbital. These 3 hybrid orbitals orient in space in a
planar triangular manner with bond angle 120°

These three hybrid orbitals overlap axially with 2pz orbitals of 3F

atoms to form 3 sigma bonds
Ethylene (C2H4). Here each C atom contains three sp2 hybrid orbitals
& one unhybridised p orbitals arranged in trigonal manner with bomd
2s 2p
angle 120 0
C(ground state)
C(excited state)
C atom accepts four electrons from H & C
Sp2 hybridisation

• sp2 hybrid orbital of each C overlaps to give sigma bond C – C.

• The remaining two sp2 hybrid orbital of each C atom overlaps with
s-orbital of two H atoms, forming 2 sigma bonds between C – H.
• The one unhybridised p orbital of each C atom (px) overlap
laterally or sideways to form one pi()bonds.
• Each C atom forms 3 sigma bonds but in C2H4 5 sigma bonds
• Each C atom forms one  bond. Total  bonds in C2H2 are two
• Total number of bonds in ethene are : 5 + 1 bond = 6 bonds

• sp3 Hybridisation:is intermixing of one s and 3 p orbitals to form 4 sp3

hybrid orbitals is called sp3 hybridisation. Formed hybrid orbitals
Oriented in tetrahedral manner with angle between them is 1090 28’.sp3
hybrid orbital shows 50% of s and 50% of p characters.
 Example: CH4 (methane)
In CH4 , the central atom is C. Electronic configuration of
6C = 1s , 2s 2px 2py 2pz
2 2 1 1 0

C (ground state)

C (excited state)
C atom share four electrons
with 4 hydrogen atoms
sp3 hybridisation

- One ‘s’ orbital and three p orbitals of C intermix to form 4 sp3

hybrid orbitals. The hybrid orbitals orient in pace tetrahedrally with
bond angle 1090 28’
- These 4 sp3 hybrid orbitals overlap with 1s orbitals of four H atom
to form 4 sigma bonds

Note:
- In organic compounds, wherever C forms 4 sigma and zero pi bonds, it
is sp3 hybridised.
- When C forms 1 π bond, it is sp2hybridized.
- When C forms 2π bonds, it is sp hyrbridised.
Find the hybridization of all c atoms in the following
• CH2 = CH ___CH2___ CH3
SP2 SP2 SP3 SP3
• CCl4 – All carbon atoms shows SP3
• CH2 = C = CH2
SP2 SP SP2
• CH2 = CH __CH = CH2
SP2 SP2 SP2 SP2
Ammonia (NH3 )molecule In NH3 the central atom is N.
It’s G.E.C = 2s2 2p3 ↑ ↑↓ ↑ ↑ ↑ ↑ ↑ ↑
↑
- One fully filled s and three half filled p orbitals intermix to form 4
sp3 hybrid orbitals
- After hybridization Nitrogen with 5 valence electrons has 3 unpaired
e- in 3sp3 hybrid orbitals and a lone pair in the fourth one.
- The three H s - orbitals each are having an unpaired electron overlap
with the 3 sp3 hybrid orbitals of N-atom. Thus 3 N __ H electron
pair bonds are formed
- Due to the presence of lone pair, the bond angle decreases to 107°
due to 1p - bp and bp - bp interactions and shows pyramidal shape.
 • H2O molecule: In H2O the central atom is O.
Its G.E.C is 2s2 2𝑝𝑥2 2𝑝𝑦1 2𝑝𝑧1
- One s and three p orbitals intermix to form 4 sp3hybrid orbitals
Oxygen with 6 valence electrons has 2 unpaired e- in two sp3
hybrid orbital and two lone pair in remaining two.
- The two 1s orbitals of H each are having an unpaired e- overlap with
sp3 hybrid orbitals of Oxygen atom. Thus two O–H sigma bonds are
formed.
- Due to the presence of two lps ,the shape is distorted to angular or
bent-V shape and bond angle is decreased from 109° 281 to 104° 30’

• sp3d Hybridisation :
- Here one s orb three p and one d orbital are mixed to give five new
hybrid orbitals which are equivalent in shape and energy called as
sp3d hybrid orbitals.
- Out of these five orbitals, three hybrid orbitals are at 120° angle
present on the plane and two hybrid orbitals are perpendicular to the
plane, shape of molecule becomes is trigonal bipyrmaidal.
(a) Five sigma and zero lp electron : trigonal bipyramidal
PF5, PCl5, PBr5, Pl5, AsF5, AsCl5, SbCl5, SbF5 etc.
 Cl Cl

P
Cl
Cl
Cl

(b) Four sigma bonds and one lone pair of electron :

SF4, SeF4, TeF4, PoF4, PF4–, SbF4–, SCl4, SeCl4, TeCl4 etc.
The shape of all above examples will be irregular tetrahedron.
F
F

F
F
Structure of SF4

(c) Three sigma bonds & two lone pair of electrons - CIF3, BrF3,
IF3, BrCl3, ICI3 etc.The shape of all above compounds is ‘T’ shape
(d) Two sigma bonds & three lone pair of electrons :ICl2–, IBr2–, ClF2–,
IF2–, BrF2–, XeF2–, I3–, Br3– shows linear shape.
• sp3d2 Hybridisation :
- one s-orbitals, three p-orbitals & two d-orbitals are mixed to give six
new hybrid orbitals known as sp3d2 hybrid orbitals.
- The shape of molecule obtained from above six hybrid orbitals will be
symmetrical octahedral.
- The angle between all hybrid orbitals will be 90°.
Example : SF6, AlF6–2, PF6–, ICl5, XeF4, XeOF4, ICl4–,
F

F F

F F
F
Shape of molecules or ions involving hybridization with bond pair electrons

Hybridization Bond Shape of molecules Example

angle
sp 180° Linear BeF2, BeCl2, CO2 CS2,
HgCl2 MgCl2, C2H2
sp2 120° Trigonal Coplanar BF3, BCl3, BH3, AlCl3,SO2
SO3, C2H4, NO3–, CO32–
sp3 109°28 Tetrahedral SiCl4,CH4,SnCl4,SO42–, ClO4-
sp3d 120°,90° Trigonal bipyramid PCl5, PF5, SbCl5
sp3d2 90° Octahedral SF6,SnCl62–, PF6–, SeF6
sp3d3 90°,72° Pentagonal bipyramid IF7
dsp2 90° Square planar [Ni(CN)4]2–,[PtCl4]2–,

Geometry of molecules or ions involving hybridization with lone pair of electrons

Hybridization No. of lone Bond Shape of Examples
pair of angle molecule
electron
s
sp2 1 < 120° Angular or V SnCl2, SO2, NO2–
shape
sp3 1 <109°28 Pyramidal NH3, PH3, PCl3,
AsH3, ClO3–
sp3 2 <109°28 V Shaped H2,H2S,I3+
sp3d 3 180° Linear XeF2, I3–
sp3d 2 180°, 90° T shape ICl3, ClF3
sp3d 1 186°, See saw SF4, TeCl4
116°
sp3d2 2 90° Square planar XeF4
sp3d2 1 90°, 180° Squarepyramidal IF5, XeOF4
sp3d3 1 72° & Pentagonal XeF6
90° pyramid
 Method of predicting the Hybrid state of the central atom
Simple Molecule Polyatomic Anion Poyatomic Cation
1 1 1
X = [V + G ] X = [V + G + a ] X = [V + G − c]
2 2 2

Hybridisation or X = 1
2
[Total number of valence e– in the central atom + total number
of monovalent atoms – charge on cation + charge on anion]
In the above formulae,
V = No, of monovalent atoms or groups attached to the central atom
G = No, of outer shell electrons in ground state of the central atom
a = Magnitude of charge on anion
c = Magnitude of charge on cation
X 2 3 4 5 6 7
Hybrid state sp sp2 Sp3 sp3d sp3d2 sp3d3

Calculate the value of X and decide the hybrid state of central atom as follows
For Example:
PF5 COCl2 NH4+ ClO4 -

X =12 [5 + 5] X =12 [2 + 4] X =12 [4 + 5 − 1] X =12 [0 + 7 + 1]

=5 =3 =4 =4
Hybrid state of P is Hybrid state of C is Hybrid state of N is Hybrid state of Cl is
sp3d sp2 sp3 sp3
NO3 – IF5 CO2 XeF4
X =12 [0 + 5 + 1] X =12 [5 + 7] X =12 [0 + 4] X =12 [4 + 8]
=3 =6 =2 =6
2 3 2
sp sp d sp sp3d2
PCl6– PH3 SF3+ SF4
X =12 [6 + 5 + 1] X =12 [3 + 5] X =12 [3 + 6 − 1] X =12 [4 + 6]
=6 =4 =4 =5
Hybrid state Hybrid state Hybrid state Hybrid state
3 2 3 3
sp d sp sp sp3 d
 SESSION – 9
AIM
• To introduce dipole moment.
• To introduce resonance
DIPOLE MOMENT ()
A polar covalent molecule behaves like a dipole.degree of polarity of
a bond or molecule is expressed in dipole moment.
The product of magnitude of negative or positive charge (e) on either
atom and the distance between them is called dipole moment
Mathematically,
 = electric charge X bond length = q x d.
Special Unit of dipole moment is Debye (D).
1D = 1 x 10-18 e.s.u x cm
or 1D = 3.335 x 10-30 coulimb metere (SI unit)
- Dipole moment is a vector quantit and is indicated by an arrow having
a symbol ( ) pointing towards the negative end.
O S
O=C=O S=C=S Cl − Hg − Cl
H H O O
1.84D 1.63D 0D 0D 0D

- Greater the dipole moment, greater is the polarity of the bond.

- In case of polar diatomic molecules there is one polar bond so, dipole
moment of molecule = dipole moment of the polar bond.
𝜇𝑏𝑜𝑛𝑑 = 𝜇𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒
- In case of polyatomic molecules, there are more than one polar bonds,
so,  = Resultant dipole moment of all individual polar bonds.
Resultant dipole moment may be calculated by the vectorial addition
of the bond moments, as  =  +  + 2  cos 
R
2
1
2
2 1 2
 e.g.(i)Dipole moment of water is 1.84D, which is equal to the resultant
dipolemoment of two O – H bonds.
 -3
-2 N
O H +
+ + + H
H H +
H

 = 1.84 D  = 1.49 D
Dipole moment of unsymmetrical molecules.
e.g. (ii)Dipole moment of Ammonia is 1.49D, which is equal to the
resultant of dipole moments of there N – H bonds.
- The molecule having zero resultant dipole moment are said to be non
polar molecules like CO2, BeCl2, BeF2, CS2, BF3, BCl3, CH4, CCl4
having zero dipole moment but contain polar bond.
The molecules having certain dipoloments are said to be
polar molecules like H2O ( = 1.84D), NH3 ( = 1.40D), NF3
(0.24D) CH3Cl (1.86D), CHCl3, PCl3, SO2 etc.
Molecule has zero dipole moment under the following conditions:
(a)If it has sp hybridisation (linear geometry) because 1 = 2 and  = 180o
e.g., CO2, BeCl2, HgF2 etc
(b)If it has sp2 hybridization(trigonal planar geometry) and the atomic
number of the central atom is less than 21:
e.g., BF3, BCl3, SO3 etc.

(c) Molecules which have symmetrical tetrahedral structure:

e.g, CCl4, CH4, SiCl4 etc
(d) If it is a Trans isomer:
e.g., Trans 1, 2, dichloro butene -2

If there are 3 different groups around the double bond, then both
cis and trans isomers show dipole moment but.𝜇𝑡𝑟𝑎𝑛𝑠 < 𝜇𝑐𝑖𝑠
e.g., 3, 4 dichloro heptene – 3

(e) A para isomer has no dipole moment.

e.g., p-dichloro benzene.
Dipole moment follows the order o > m > p.

Applications of Dipole moment

Dipole moment used to predict
(a)Geometry of the molecule
If  = 0 compound is non polar and symmetrical
eg. CO2, BF3, CCl4, CH4. BeF2 etc.
If   0 compound will be polar and unsymmetrical.
H2O, SO2, NH3, Cl2O, CH3Cl, CHCl3 etc.
(b) cis or trans form of a geometrical isomer.
- Dipole moment of cis isomers is normally higher than trans isomers
Cl—C—H Cl—C—H
Cl—C—H Cl—C—Cl
µ0 µ0
cis-form Trans-form
Polar (µ  0) Non Polar (µ  0)

- If two groups have opposite inductive effect than trans-isomer will have
greater dipole moment
 H Cl H Cl

C C
C C

CH3 H H CH3

(c) Orientation in benzene derivatives or to locate position of substituents

in aromatic compounds.   Bond1angle
- If same substituents are preset in the symmetrical position of
benzene ring compounds will be zero
Cl
Cl Cl
Cl

Cl
Cl
µ=0 µ0
Angle 180º Angle 120º Angle 60º
p-dichloro benzene m-dichloro benzene o-dichloro benzene

- As angle between subtituents decrease value of  increase

(d)% ionic character of a bond.
Observed dipole moment
Percent ionic character = × 100
Calculated dipole moment assuming 100% ionic bond

Experimental value of 
% Ionic character =  100
Theoritical value of 
e.g. Experimental dipole moment for HCl = 1.03
Suppose charge on H+ or Cl-, q = 4.8 x 10-10 esu
d = 1.27A0
 theoretical value of  = q x d = 4.8 x 10-10 x 1.27  10−8
= 6.09 D
Thus, % ionic character in H – Cl bond or HCl molecule
1.03
= x100  16.9
6.09

(e)Extent of polarity
Molecules having zero dipole moment (R) are nonpolar molecules and
those having R  0 are polar in nature.
e.g., H2, N2, O2 etc are nonpolar (=0) and HF, HCl, HBr, HI, etc are
polar molecules (R0).
Thus, dipolemoment can also be used to distinguish between polar and
nonpolar molecules.

RESONANCE
In certain molecules, a simple Lewis structure cannot explain all the
properties of the molecule. The molecule is then supposed to have
many structures.
The actual structure is in between of all the contributing structures
and is called resonance hybrid. The different individual structures
are called resonating structures or canonical forms. This phenomenon is
called resonance. In representing resonance, a double headed arrow
(↔) is put between different contributing structures.
For example we can write two electronic structures of O3
(+) (+)
(−) (−) O
O O
O O
O a O O b O (C)

Structures (A) and (B) are called resonating or canonical structures

and C is the resonance hybrid. This phenomenon is called resonance
Some other examples
(i) CO32– ion
O O O
O

− O O
O O O O O O

(ii) Carbon−oxygen bond lengths in carboxylate ion are equal due to

resonance.
-
O O O
R R R
-
O O O
(iii) Benzene

(iv) Vinyl Chloride

H2C H2 C
+
Cl Cl
.. ..
S S

:..O .. O: ..O:
- Sulphur dioxide SO2 .. ..O:

- Nitrous oxide (dinitrogen oxide), H2O N N O N N O

. .. .. .
:N O: :N O:
- Nitric oxide, NO

- Nitrate ion, NO 3− (planar, triangular)

O O O

O N O N O N

O O O

O O O

O N O C O C

O O O

No. ofbondsbetweenthesametwoatomsinallthestructures
BondOrder =
totalno. ofresonatingstructures
Examples of Resonance:
(i) Ozone (O3)

3
Bond Order = = 1.5
2

(ii) Carbon dioxide (CO2)

 6
Bond Order = = 2
3
(iii) Carbon monoxide (CO)

6
Bond Order = =2
3

(iv)Carbonate ion (CO2−

3 )
Resonance explain why all bonds are equivalent in length, energy.
Resonance energy:Difference in the energies of the canonical forms and
resonance hybrid is called resonance stabilization energy.
The resonance hybrid is more stable than any of the resonating
structure.Greater the resonance energy more will be the stability to
species.
Rules for writing Resonating Structures:
(i) The various resonating structures differ in the position of electrons
and not in the relative positions of atoms.
(ii) All the contributing structures should have the same number of
unpaired electrons.
(iii)The various canonical structures shows same energy.
(iv)Resonance structures in which the negative charge resides on
electronegative atom and positive charge resides on electropositive
atom in resonance hybrid
(v) Resonance structures should be so written that unlike charges reside
on adjacent atoms.
(vi)Resonance structure with greater number of covalent bonds
contributes more towards the resonance hybrid.

SESSION - 10
AIM
1] To introduce bond parameters
2] To introduce formal charge
BOND PARAMETERS
◼ Bond Length: The average distance between the nucleus of two

bonded atoms is known as bond lenght, normally it is represented in

Å or pm (10-10 cm) or A0 (10-8 cm).
- For the same atoms, bond length decreases with the multiplicity of
bonds. Bond length  Number of bond1 or bond order
C___C > C = C > C  C
Ex: C2 H6 (1.54Å) > C2 H4 (1.34Å) > C2 H2 (1.20Å)
- Bond length decreases with increase in s-characters of the hybrid
orbital used in bonding.
sp3-s𝜎> sp2-s𝜎> sp– s𝜎
- Polar bonds are shorter than theoretical non-polar bonds.
Actual H–Cl distance < theoretical H–Cl distance.
- When the size of the atom increases, the bond length increases
Ex: F - F < Cl -Cl < Br - Br < I – I
 ◼ Bond Energy or bond strength:It is amount of energy required to
break one mole of the bonds to separate the bonded atoms in
gaseous state.

Factors affecting bond energy:

- Size of the atoms: Larger the size of the bonded atoms, larger is the
bond length and lesser is the bond energy.
Bond energy  1
Atomic size

Ex: HF > HCl > HBr > HI

- Multiplicity of bonds: For the bond between the same two atoms, bond
energy increases with the multiplicity of the bond.
Bond energy  Bond order
Ex: C  C> C = C > C - C
- The energy required for homolytic cleavage is more than that required
for heterolytic.
- 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
- Bond Polarity :- Bond energy  polarity
eg. H-F > H-Cl > H-Br > H-I
- Hybridisation :- Bond energy  s-character in hybrid orbitals.
eg. Sp-sp > sp2-sp2 > sp3-sp3
s –character- 50% 33.3% 25%
 ◼ Bond Angle :- The angle between any two adjacent bond is known
as bond angle.
It is represented in degree (°), min (‘) and second (‘’)
Factors affecting the bond angle
Following factors can affect bond angle:

- Hybridisation of central atom:% of s character increases bond angle

also increases
sp 180°
sp2 120°
sp3 109.5°
- Presence of lone pair: Then bond angle  No.of lone
1
pair

bcz lp─bp repulsion is more than bp─bp

- 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─bp repulsion increases.
- bond angle  electrongativity of central atom

- Multiple bonds:Electron density for double bond is more than in

single bond,so repulsion in double bond is more than single bond.
Bond angle  Number of bonds (Bond order)
109° 120° 180°

C C C C C C
 FORMAL CHARGE
In a molecule,no charge on the molecule as a whole or in a polyatomic
ion (e.g.,𝐶𝑂32− or 𝑁𝐻4+ ion etc.)but charge present on the ion is the
charge on the ion as a whole and not on the individual atoms,
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. or
Individual charge possessed by an atom in a molecule.
Formal charge = Valence electrons of the atom − (Shared electrons
of that atom + Unshared electrons of that atom).
Formal charge = Valence electrons of the atom − total number of
lp electrons − ½ total number of bondind or shared electrons of
that atom.
Ex. 1] Calculate formal charge on each O – atom of O3 molecule.
Sol: Lewis structure of O3 is:

The atoms have been numbered as 1, 2 and 3.

Formal charge on end O – atom numbered 1 = 6 – 4 - 12(4) = 0
Formal charge on end O – atom numbered 2 = 6 – 2 - 12(6) = +1
Formal charge on end O – atom numbered 3 = 6 – 6 - 12(2) = -1

Hence, we represent O3 along with formal charges as:

Ex. 2] Write the formal charges on atoms in (i) carbonate ion (ii)
nitrite ion.

Sol:(i) Lewis structure of CO2−

3 ion is
1
Formal charge on C atom = 4 – 0 – (8) = 0, Formal charge on
2
double bonded O atom
= 6 – 4 − 12 (4) = 0
Formal charge on single bonded O atoms = 6 – 6 − 12(2) = –1
ii) Lewis structure of NO−2 ion is

Formal charge on N atom = 5 – 2 − 12 (6) = 0,

Formal charge on double bonded O atom = 6 – 4 − 12(4) = 0
Formal charge on single bonded O atom = 6 – 6 − 12(2) = –1
 SESSION – 11
AIM To introduce hydrogen bonding
HYDROGEN BONDING is electrostatic force of attraction existing
between covalently bonded H atom of one molecule and the
electronegative atom of the other molecule.
This bond comes into existence when H atom is directly bonded to highly
electronegative atom such as N, O or F.
Properties and conditions of HYDROGEN BOND
- H should be covalently bonded with high electro–ve element like F,O,N.
- Atomic size of electro–ve element should be small.
Decreasing order of atomic size is N > O > F
Decreasing order of atomic size is F > O > N
1
- Strength of H–bond  Electronegativity of Z (element)  atomic size of Z
- Hydrogen bonding occurs in HCN,due to (–CN)triple bond (sp
hybridisation), electronegativities of carbon and nitrogen increases.
H—CN………H—CN………H—CN
- A hydrogen bond is a bond of hydrogen between two electronegative
atoms only. It never involves more than two atoms.
- Hydrogen bond is very weak compared to a covalent bond. The bond
energy is in the range of 3-10 kcal/mole.
- Formation of H-bond does not involve sharing of electrons.
 Types of hydrogen bonding
Total of Hydrogen Bonding

Inter Molecular Intra Molecular

Homoo Inter Molecular Hetero Inter Molecular

(a) Inter-molecular H-bonding present between two or more molecules
(similar or different)
Example: (i) In H2O, NH3 and HF molecules:
H H H H H H
O—H----- O — H ------ O — H ------ | | |
     N− H      N− H     N− H    
| | |
H H H

F F
0 H
H 120 0 H 120 0
H 120 H 1200
F F F

No. of H-bonds in a molecule = No. of H-atoms attached to electro-

negative element + No. of lp electrons on electronegative element.
e.g.,NH3, No. of H-bonds = 3 + 1 = 4
in H2O, No. of H-bonds = 2 + 2 = 4
Effect of Intermolecular H-bonding:
- It increases the boiling point of the compound.
E.g. BP of ethanol is higher than that of diethyl ether.
- With increase in intermolecular hydrogen bonding the physical state
changes from gaseous to liquid and to solid.
Ex: HF, H2O and NH3 are associated liquids.
- Intermolecular hydrogen bonding increases the solubility of the
substance in water.
Ex: organic compounds like alcohols,amines are soluble in water
 - Ice has less density than water In ice H-bonding absent so density
decreases thats y ice floats on water
- It increases the acidity of an acid
b)Intermolecular Hydrogen Bonding here H - bonding takes place when
hydrogen and the electronegative atom are present in the same
H
H O O
O
H C O C
O O
O H
N H H
O F O
O
molecule. O-nitrophenolSalicyladehyde O-fluorophenol 2-6 dihydroxgyl benzoate

Conditions for formation of intramolecular hydrogen bonding:

- The ring formed should be planar
- Position of the interacting atoms should be such that there is minimum
strain in ring formation.
e.g., Intramolecular H-bonding is not possible in m- & p- isomers of
nitrophenol.
Effect of intramolecular H-bonding
- It decreases the boiling point of the compound.
- It increases the steam volatile nature of the compound.
e.g., o-nitrophenol is steam volatile but p-nitrophenol is not.
- It increases the acid strength.
e.g., salicyclic acid is stronger than p- Hydroxybenzoic acid.
 SESSION – 12
AIM To introduce MOT
MOLECULAR ORBITAL THEORY (MOT)put forward by Hund &
Mulliken, to overcome the limitations of VBT (Valence bond theory) was
unable to explain
eg. Paramagniic nature Of O2 molecule, as per VBT (:O: :O:) it should
be diamagnetic.
According to this theory,all the atomic orbitals of the atoms
participating in molecule formation.They all get mixed up to an
equivalent number of new orbitals that belong to the molecule now.
These are called Molecular Orbitals.
This theory is based on principal of
Linear combination of atomic orbitals (LCAO).
◼ Electron waves nothing but atomic orbitals have positive and
negative phase. When waves are combined, they may interact either
constructively or destrcuctively.
- If two identical waves are added, they combine constructively to
produce the wave with double the amplitude and same wavelength and
form two new orbitals called ‘bonding molecular orbital’ (BMO)
- Conversely, if they are subtracted, they combine destructively to
produce the wave with less or zero amplitude gives antibonding
molecular orbital’ (ABMO).
Suppose 𝝍𝑨 and𝝍𝑩 represents the amplitude of electron waves of the 2
atomic orbitals of the atoms A and B respectively, then the situation
may be represented as follows:
Case I: When the two waves are in phase (constructive interface), so
that they add up and the amplitude of the new wave is:
ϕ = ψ A + ψB
The probability pf electron density is given by the square of the
amplitude, therefore, we have
ϕ2 = (ψA + ψB )2 = ψ2A + ψ2B + 2ψA ψB
i.e., ϕ2 > ψ2A + ψ2B
The molecular orbital formed by the additive effect or constructive
interference of the atomic orbitals are called BMO.
Case I: When the two waves are out of phase (destructive interface), the
waves are subtracted from each other so that the amplitude of the new
wave is: ϕ = ψA − ψB
The probability pf electron density is given by the square of the
amplitude, therefore, we have
ϕ2 = (ψA − ψB )2 = ψ2A + ψ2B − 2ψA ψB
i.e. ϕ12 < ψ2A + ψ2B
The molecular orbital formed by the subtractive effect of the atomic
orbitals is called ABMO.

Combination of 1s atomic orbital of both atoms

Energy of BMO is always less than the energy of the atomic orbitals.
But energy of the ABMO is higher than the energy of atomic orbitals.
 Bcz in the BMO,electron density in the intern clear region is high so
the nuclei are shielded from each other and the between the nuclei
are very small.
In ABMO, the electron density in the internuclear region is very low. As
a result, the nuclei are directly exposed to each other i.e., there is
very less shielding. Hence the repulsions between the nuclei are very
large.
- Electrons present in BMO contribute towards the stability of molecule
where electrons present in ABMO destabilize the molecule
- Atomic orbitals participating in combination must have comparable
energies.
Ex: For homogeneous diatomic molecule, 1s atomic orbital of one atom
can combine with 1s atomic orbital of another atom or 2s can combine
with 2s and 2p with 2p and so on.
- Combining atomic orbitals must have proper orientation.
I.e. same symmetry about the molecular axis.
Ex: Taking 2-axis as the molecular axis, 2Pz orbital of one atom
can combine with 2pz of another atom but not with 2px or 2py
orbitals because of their different symmetry.
- BMO’s are represented as 𝛔 , 𝛑, 𝛅 𝐞𝐭𝐜. While ABMO’s are represented
as 𝛔 , 𝛑 , 𝛅 𝐞𝐭𝐜.
∗ ∗ ∗
Thus 1s atomic orbitals of ∗ two atoms combine to form two MO’s
labeled as 𝜎1s(BMO) and 𝛔 1s(ABMO).
Similarly ,2s atomic orbitals combine to form 𝜎2s and 𝛔∗ 2s of the 2p-
orbitals.
If z-axis is taken as molecular axis ,
Combination of two 2px or two 2py atomic orbitals to form 𝛑(2px) and
𝛑*(2px) or 𝛑(2py) and 𝛑*(2py) molecular orbitals
- Filling of electrons in Molecular Orbitals occurs according to Aufbau
principle, Pauli’s exclusion principle and Hund’s rule.
- The shape of the molecular orbitals depends upon the shapes of

combining orbitals.
 - The presence of one or more unpaired electrons in a molecule shows
paramagnetic nature. Electronic configuration having all the
electrons paired suggests its diamagnetic nature.
Comparision of Bonding molecular orbital & Antibonding molecular orbital
Bonding molecular orbital (BMO) Antibonding Molecular orbital
- Bonding MO is the result of the - ABMO is resulting of linear
linear combination of AO when combination of AO when their wave
their wave function are added function are substracted
ϕ = ψA + ψB ϕ = ψA − ψB

- It does not have node - It always have a node between two

nuclei of bonded atom
- Charge density increase between - Charge density decrease in between
two nuclei resulting between two two nuclei,leads to repulsion between
atoms two atoms.
- Energy of BMO is less, hence - Energy of ABMO is high, hence
stable unstable
Energy Level Diagram of molecular orbital :
◼ For diatomic homonuclear molecules such as Li2, Be2, B2, C2, N2 is
(where the energy difference between 2 s and 2 p-orbitals is
large and hence they cannot interact)
σ1s < σ∗ 1s < σ2s < σ∗ 2s < π2px= π2py<σ2pz <π∗ 2px= π∗ 2py
<σ∗ 2pz
For N2 type molecule

2pz

 
2px 2py
2p 2p
Increasing energy in N2 molecule

2pz

2px 2py

2s

2s 2s

 2s

1s

1s 1s

 1s
 ◼ For homogeneous diatomic molecules such as O2, F2, Ne2, (where the
difference in energies between 2s and 2p-orbitals is small and
hence they can interact)the energy diagram is
σ1s < σ∗ 1s < σ2s < σ∗ 2s < σ2pz < π2px= π2py<π∗ 2px= π∗ 2py
<σ∗ 2pz
For O2 type molecule-

2pz

1
Bond order (8 – 4) = 2
  2
2px 2py
Bond order O2 = 1/2 [8 – 4] = 2
2p 2p
O+2 = 1/2 [8 – 4] = 2.5
Having two unpaired 2px 2py O2– = 1/2 [8 – 5] = 1.5
electrons so paramagnetic
O 22 – = 1/2 [8 – 5] = 1.5
2pz
O +2 2 = 3
Increasing energy

Stability order -
2s O +2 2 > O+2 > O2 > O2– > O 22 –
Bond length –
O 22 – > O2– > O2 > O+2 > O +2 2
2s 2s

 2s

1s

1s 1s

 1s

INFORMATION FROM MO CONFIGURATIONS

𝟏
(a) Bond order (B.O.) = (Nb - Na) or it is defined as half of the
𝟐
difference between the number of electrons present in the bonding
and the antibonding orbitals.
Where Nb = no. of electrons in the bonding MO’s
Na= no. of electrons in the antibonding MO’s.
If bond order is more than zero, the molecule/ion exists, otherwise not.
 ◼ Bond dissociation energy - Higher the bond order, higher is the bond
dissociation energy.
◼ Stability - Higher the bond order, greater is the bond stability.

If Nb> Na the molecule is stable .bcz greater number of bonding

orbitals are occupied than antibonding orbitals, resulting in a net
force of attraction.
If Nb< Na, the molecule is unstable. Bcz the antibonding
influence is greater than the bonding influence, resulting in a net
force of repulsion.
If Nb = Na, the molecule is again unstable.Bcz the numbers of
electrons are equal, the antibonding influence of the electrons in the
antibonding molecular orbitals is greater than the bonding influence of
the electrons in the bonding molecular orbitals.
◼ Bond length- Higher the bond order, shorter is the bond length.

(b)Magnetic properties: Molecule/molecular ion are paramagnetic

(atleast one electrons is unpaired) or diamagnetic(if all the electrons
are paired).
Bonding in molecules :-
(I) H2 molecule- Having two H atoms with one electron(1s’)
M.O. configuration of H2 = (  1s)2 (  *1s)0
Bond order = ½ [Nb – Na] = ½ [2 – 0] = 1 i.e. single bond
Having paired electron so diamagnetic.
2s

1s 1s
(Atomic orbital) H2 (Atomic orbital)
 1s
Molecular orbital
 1s
(II)H2+ ion – 1s 1s

M O Configuration of H2+ = (  1s)1 (  1s)0

+
H2
 1s

One electron in bonding molecular orbital - paramagnetic

Bond order = ½ [1– 0] = ½
Less stable
(III) H2– anion -
M.O. configuration - (  1s)1 (  1s)1 1s

Paramagnetic 1s 1s
H2–
Bond order = ½ [2 – 1] = ½  1s

Stability is less than [H2+] because H2– Contain ABMO electron

(IV) Helium molecule (He2) :
M.O. configuration ( 1s)2 ( 1s)2
1s

Diamagnetic 1s 1s

Bond order = ½ [2 – 2] = 0 (zero) He2  1s

Bond order is zero shows no bond between He atoms.So He2

molecule does not exist
Stability (He2) Highly unstable molecule
(V) (He )
2
+

EC of He = 1s2, He+ = 1s1.

MOC = (1s)2 < (*1s)1
Bond order = 21 ,
Nature – paramagnetic (stable).
(V)Lithium molecule (Li ) : ECof Li − 1s ,2s
2
2 1

MOC = (1s)2 < (*1s)2 < (2s)2, Bond order = 1

Nature = diamagnetic.
(Vl)Beryllium molecule (Be2) : Be – 1s2, 2s2
MOC = ( 1s)  (  *1s)  ( 2s)  (  *1s)
2 2 2 2

Bond order = 0, nature – diamagnetic (does not exist)

(Vll)Boron molecule (B2) : B − 1s2 2s2 2p1

MOC = ( 1s )  (  * 1s )  ( 2s )  (  * 2s )  ( 2px ) = 2p y ( )

2 2 2 2 1 1

BO = 1, Nature = paramagnetic
x) Carbon molecule (C2) : C − 1s 2s 2p 6
2 2 2

MOC = ( 1s )  (  * 1s )  ( 2s )  (  * 2s )  ( 2p ) = ( 2p ) < (2pz) ,

2 2 2 2 0 2 2
x y

Bond order = 2, Nature = diamagnetic

xi) Nitrogen molecule (N2):
MOC = ( 1s )  (  * 1s )  ( 2s )  (  * 2s )  ( 2p ) = ( 2p ) < (2pz)
2 2 2 2 2 2 2
x y

Nature – diamagnetic.
BO = 3,
Order of bond order of N2, N2+, N2−, N22− is N  N 2 2
+
= N2 −  N22−

xi) Oxygen molecule (O2) : O – 1s2 2s2 2p4

Molecular orbital energy level diagram for O2
MOC = KK  ( 2s )  (  * 2s )  ( 2pz )  ( 2p x ) = 2p y ( )  (  * 2p ) = (  * 2p )
2 2 2 2 2 1 1
x y

BO = 2, Nature – paramagnetic
Order of bond order of O2, O2+, O2+, O2−, O22− is O22+  O2+  O2  O2−  O2−−
xii) Fluorine molecule (F2) : F – 1S2 2S2 2P5
MOC = ( 1s )  (  * 1s )  ( 2s )  (  * 2s )  ( 2p )  ( 2p ) = ( 2p )  (  * 2p ) = (  * 2p )
2 2 2 2 2 2 2 2 2
z x y x y

BO = 1, Nature diamagnetic (Stable, BDE = 151 kJ mol-1)

xii) Neon molecular does not exists because Bond order is zero.
 MO CONFIGURATIONS OF HETERONUCLEAR DIATOMIC SPECIES:
Molecule Molecular Bondor upaired Magentic
or ion orbitalConfiguration der Electrons character
7−2
CN(13e–) KK(2s) 2 * (2s) 2 (2p x ) 2
2
2.5 1 Paramagnetic
(2p y )2 (2p z )1

8−2
CN–(14e– KK(2s) 2 * (2s) 2 (2p x ) 2
2
= 3.0 Nil Diamagnetic
) (2p y )2 (2p z ) 2

8−3
NO (15e– KK(2s)2 * (2s)2 (2px )2
2
= 2.5 1 Paramagnetic
) (2p y )2 (2pz )2 * (2p x )1

8−2
NO+ (14e– KK(2s)2 * (2s)2 (2px )2
2
= 3.0 Nil Diamagnetic
) (2p y )2 (2pz )2 * (2p x )0

7−2
NO2+(13e KK(2s)2 * (1s)2 (2pz )2
2
= 2.5 1 Paramagnetic
–) (2p x )2 )(2p y )1 * (2p x )0

8−2
CO (14e– KK(2s)2 * (2s)2 (2px )2
2
= 3.0 Nil Diamagnetic
) (2p y )2 (2p z ) 2