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Chemical Bonding and

Molecular Structure
 NaCl CaCO3

Iodine crystals Aluminium

The substances are formed as a result of combination of

atoms or molecules or ions.
 So Many Why?

Why do some atoms combine while

certain others do not?

What is the nature of the force that

exists between combining atoms?
Why does definite number of various atoms
constitute a particular molecule?
Why is it easy for some elements to lose
electrons while it is harder for others?
 Chemical Bond

A chemical bond forms in

The attractive force which order to reduce the energy
holds various constituents of the chemical species
(atoms, ions, etc.) together, in involved in bonding,
different chemical species. thereby increasing their
stability.
 Potential Energy Curve

Potential energy (kJ/mol)

Internuclear distance, r (pm)

r0
0
r = 300

r = 150 H H

H H
- 435.8
r = 74 At 74 pm, two H atoms have
together minimum potential energy
H H (hence maximum stability in the
form of a H2 molecule).
Observed bond distance in H2
 Chemical Bonds

Ionic Bond Covalent Bond Metallic Bond

Electropositive & Two Two

Electronegative electronegative electropositive
atoms atoms atoms
How Ionic Bonds are Formed?
 Ionic Bond

To attain stable electronic configuration

Electrostatic force of
attraction between
oppositely charged ions.

Elements lose or gain electron(s) in order to

have a stable electronic configuration in
their valence shell
 Formation of Ionic Bond

Elements involved in the ionic bond should possess

The element losing electron Large difference in

should have LOW ionisation electronegativity of two
(1) enthalpy.
(3) elements

The element accepting electron

should have HIGH electron gain High Lattice enthalpy
(2) enthalpy.
(4)
 Covalent Bond and Coordinate Bond

A Covalent bond is A bond in which the shared pair

formed by sharing of electrons originate
electrons. from one atom and none from
the other is called coordinate
bond.

Shared pair of electrons

H + H
O
H H Covalent Bond

Coordinate Bond H
 Metallic Bonds

Electrostatic force of
attraction between a metal
kernel and valence
electrons.
 Lattice Energy

Energy required to
completely separate one
mole of solid ionic
compound into gaseous
constituent ions.

NaCl (s) Na+ (g) + Cl─ (g)

AB(s) A+(g) + B─(g); Lattice Energy = Positive

A+(g) + B─(g) AB(s); Lattice Energy = Negative

 Factors Affecting Lattice Energy

1
Lattice Energy (L.E.) ∝ r

─
r＋ + r─ = r Lattice Energy (L.E.) ∝ Z+×Z

r Interionic distance
Z+ Charge on the cation

r＋ Radius of the cation

Z─ Charge on the anion

rー Radius of the anion

 Lattice Energy

Charge is the deciding

factor

Ionic
compound
r (Å) Z+ × Z
─
L.E. (kJ mol─1)

LiF 2.01 1 1004 kJ mol─1

MgO 2.10 4 3933 kJ mol─1

 Order of Lattice Energy

KI < KBr < KCl < KF

BaO < SrO < CaO < MgO < BeO

NaF < MgF2 < AlF3

 Properties of Ionic Compounds

Exhibit isomorphism &

01 Soluble in polar solvent
polymorphism 04

High Melting point and Forms crystal in Solid

Boiling point
02 05 state

Conduct Electricity in
03 aqueous & molten state
Highly Polar 06
 Isomorphism

FeSO4.7H2O
Different ionic compounds Green vitriol
having similar crystal structure
are called isomorphs and this MgSO4.7H2O
Epsom salt
phenomenon is called
isomorphism.
ZnSO4.7H2O
Isomorphous compounds have White vitriol
the same type of formula .
 Polymorphism

Occurence of a
For example, ZnS exist as
particular substance
in more than one
crystalline form is
called polymorphism
Sphalerite
(1)

Wurtzite
(2)
 Hydration Energy

Energy released when

one mole of a gaseous
ion is hydrated in large
amount of water to form As the dielectric
an aqueous ion. constant of solvent
increases, more
energy is released
on solvation.
Size of ion Hydration energy

Charge of ion Hydration energy

 Solvation

The interaction of the solute and the solvent

molecules which stabilizes the solute in the solution

If the solvent is water, then it is known as Hydration

Dissolution of solute in water depends on

Lattice energy and Hydration energy
 Types of Covalent Bond

01 Single Bond

Formed by the mutual

sharing of electrons Number
of shared pair 0
between two atoms. Double Bond
2
of electrons

0 Triple Bond
3
 Types of Covalent Bond

One pair of
(1) electrons is shared Three pairs of
(3) electrons are shared

Two pairs of
(2) electrons are shared

Single Covalent bond Triple Covalent bond

Double Covalent bond

 Theories of Covalent
Bonding

Kössel-Lewis
MOT
Electronic theory

VBT VSEPR
Kossel Lewis Electronic Theory

Atoms can combine by the

transfer of valence electrons
from one atom to another or
by sharing of electrons.
 Lewis Dot Structures

Combining
atoms Attains noble
contribute ≥ 1 Covalent Bond gas
electron(s) to configuration
the shared pair

Shared pair of Shared pair

electrons (e─) of electrons

O2
8e─ 8e─ Octet complete
 It’s a theoretical charge
01 over an individual atom of
a molecule or an ion.

In polyatomic ions, the net

Formal 02 charge is possessed by the
Charge whole ion.

Feasible to assign a formal

03
charge on each atom.
 Formal Charge

2 2

1 1
3 3
Used to give the relative
stability of possible Lewis
structures
F.C. on O (1) = -1

F.C. on O (2) = +1 Lowest energy structure:

Smallest formal charge on the
atoms
F.C. on O (3) = 0
 Limitations of Octet Rule

Molecules with incomplete

1 octet of the central atom

Hypovalent Electrons around

compound central atom < 8
4 valence
electrons

6 valence
electrons
 Limitations of Octet Rule

2 Molecules with odd Molecules with expanded

electrons 3 octet

Electrons
NO, NO2, ClO2, ClO3 Hypervalent around central
compound atom > 8

10 valence
electrons
 Limitations of Octet Rule

4 Formation of Xe & Kr compounds Doesn’t account for the

5 shape of the molecules

Xe and Kr form compounds with F and O

even though their octet is already Doesn’t explain about the
complete.
6 relative stability of
the molecules
 Valence Bond Theory

A covalent bond is formed

by the overlap of half filled
atomic orbitals that yield a
pair of electrons shared
between the two bonded
atoms.
 Linus Pauling  J.C. Slater
 Orbital Overlap

All orbital overlappings do

Types of Overlap
not result in bond formation

Positive Negative Zero

Bond will be formed Bond will not be

formed
 Directional Properties of Bonds

Covalent Ionic
Bond: Bond:
Directional Non-Directional
Coordinate or Dative Bond

Bond formed
by sharing of electrons
between two atoms. Shared
pair of electrons is contributed
by only one of the two atoms.
Co ordinate bond once
formed cannot be
distinguished from covalent
bond. Covalent and
coordinate bond are same
with respect to bond
properties.
 How to Identify Coordinate Bond?

Different covalency Presence of

than usual coordinate bond

Example: N2O Example: [H3O+]

Fourth bond formed by N is always Third bond formed by O is always

coordinate coordinate

H + H
+ - O
N N O

H
 Lewis Acid and Lewis Base

Lone pair donors are Lone pair acceptors

called Lewis bases are called Lewis
acids

H3N + H+ [NH4]+

Donor Acceptor
 Co-ordinate Bond or Dative Bond

H +
H O H + H+ H O H

or H3O+
 Sigma and pi-bonds

Covalent Bond

Sigma (σ)
Pi (𝛑) bond
bond

Sigma bond is formed Pi (𝛑) bond is formed when

when overlapping takes axes of combining orbitals
place along the are perpendicular to the
internuclear axis of internuclear axis i.e., lateral
orbitals or when an axial or sidewise overlapping
overlap takes place. takes place.
 Axial or Head-on Overlapping

Cylindrically
Can undergo rotation about
symmetrical about the
the internuclear axis
internuclear axis

Generally, 𝛑 bond between two atoms is

formed in addition to a σ bond
 Types of
π bond

p𝛑-p𝛑 overlap p𝛑-d𝛑 overlap d𝛑-d𝛑 overlap

 Bond Strength

In general, order of strength of

bond

𝛑 < 𝞂

● Greater the extent of overlapping, more will be the bond

strength.

● For same value of n,

s-s sigma overlap < s-p sigma overlap < p-p sigma overlap

● Strength of 𝜋 bonds: 3p-3p 𝜋 overlap < 2p-2p 𝜋 overlap

 Bonding in H2 Molecule

H 1
1s1
H ↿⇂ H
H 1
1s1 1s 1s

𝜎
i.e. H H
 Bonding in O2 Molecule

O ⥮ ⥮ ⥮ ↿ ↿ ↿ ↿

1s2 2s2 2p4

O ↿⇂ O

O ⥮ ⥮ ⥮ ↿ ↿
2p 2p
1s2 2s2 2p4

𝜎
i.e. O O
𝜋
 Bonding in N2 Molecule

N ⥮ ⥮ ↿ ↿ ↿ ↿ ↿
↿ ↿
1s2 2s2 2p3
N ↿⇂ N
N ⥮ ⥮ ↿ ↿ ↿
1s2 2s2 2p3

𝜎
i.e. N N
2𝜋
 Limitations of VBT

Paramagnetic nature
of O2 could not be explained.

Fails to account for the geometry

and shapes
of various molecules.
 Steps to Draw Structures

Largest size
01 Select the central atom

Least
electronegative
SO3 - Sulphur Central
atom
Less in number

Can form
maximum bonds
 Steps to Draw Structures

Draw a symmetrical Calculate the total number

02 skeleton of atoms. 03 of valence electrons

O
Valence electrons in SO3 = 6 +(3×6)
= 24
S
24
Electron pairs = = 12
2
O O
 Steps to Draw Structures

Make a single bond using the

electron pairs. Then complete the
04 octet of the side atoms. If any
electron pair is left, assign it to the
central atom.

..
: O:

: O:
: O:

..
..
 Steps to Draw Structures

If the octet of central atom is not

complete, use the lone pairs of side
05 atoms to make the bonds and
complete the octet.

Assign formal charge on

06 each atom
 VSEPR Theory

Used to provide shape and

electronic geometry of
covalent compounds.

1. Shape of a 2. Valence shell 3. Electron pairs

molecule depends is taken as a in the valence
upon the number sphere with the shell repel one
of valence shell electron pairs another since,
electron pairs localising on they are all
around the central the spherical negatively
atom surface charged
 VSEPR Theory

5. Lone pair occupies

4. Electron pairs occupy more space on the
positions in space that sphere. So, the order of
tend to minimise repulsion is:
repulsion. lp-lp > lp-bp > bp-bp
(lp: Lone pair,
bp: Bonding pair)
 VSEPR Theory

6. A multiple bond is There is no effect of

treated as a single pi bond on
bonding pair. geometry and shape

Compound Shape 𝛑 bond(s)

Cl - Be - Cl Linear 0
+
O=C-H Linear 1

O=C=O Linear 2

H-C≡N Linear 2
Point to Remember!!

Both bond pairs and

For electronic geometry
lone pairs are considered

Only bond pairs

For shape
are considered
 VSEPR Theory

General Formula: AB2 (A: Central atom, B: Side atom)

Electron Bonding Lone Electronic

Shape
pairs pairs pairs Geometry

2 2 0 Linear Linear

Bond Angle = 180o

Example: CO2, BeCl2

 VSEPR Theory

General Formula: AB3 (A: Central atom, B: Side atom)

Electron Bonding Lone Electronic

Shape
pairs pairs pairs Geometry

Trigonal Trigonal
3 3 0
Planar Planar

Bond Angle = 120o

Example: BF3, SO3

 VSEPR Theory

General Formula: AB2L (A: Central atom, B: Side atom, L: Lone pair)

Electron Bonding Lone Electronic

Shape
Pairs Pairs Pairs Geometry

Trigonal Bent/
3 2 1
Planar V-Shape

Bond Angle < 120o

Example: SO2, SnCl2

 VSEPR Theory

Steric Number: 4 (sp3)

(AB4)

109.50

Bond Angle = 109.5o

Example: CH4, [NH4]+ , XeO4

 VSEPR Theory

General Formula: AB3L (A: Central atom, B: Side atom, L: Lone pair)

Electron Bonding Lone Electronic

Shape
Pairs Pairs Pairs Geometry

4 3 1 Tetrahedral Pyramidal

Bond Angle < 109.5o

Example: NH3, XeO3, PCl3

 VSEPR Theory

General Formula: AB2L2 (A: Central atom, B: Side atom, L: Lone pair)

Electron Bonding Lone Electronic

Shape
Pairs Pairs Pairs Geometry

Bent or
4 2 2 Tetrahedral
V-Shape

Bond Angle < 109.5o

Example: H2O, OF2

 VSEPR Theory

General Formula: AB5 (A: Central atom, B: Side atom)

Electron Bonding Lone Electronic

Shape
Pairs Pairs Pairs Geometry

Trigonal
Trigonal
5 5 0 Bipyramidal
Bipyramidal (T.B.P.)
(T.B.P.)

Bond Angle = 90o, 120o, 180o

Example: PCl5, SOF4

Valence Shell Electron Pair Repulsion
Theory (VSEPR)

Steric Number: 5 (sp3d)

(AB4L)

Bond Angle < 90o , 120o

Example: SF4, XeO2F2

 VSEPR Theory

(A: Central atom, B: Side atom, L: Lone pairs)

General Formula:
AB3L2 Electron Bonding Lone Electronic
Shape
Pairs Pairs Pairs Geometry

Trigonal
5 3 2 T-Shape
Bipyramidal (T.B.P.)

Bond
Angle < 90o, 180o

Example: ClF3
 VSEPR Theory

General Formula: AB2L3 (A: Central atom, B: Side atom, L: Lone pairs)

Electron Bonding Lone Electronic

Shape
Pairs Pairs Pairs Geometry

Trigonal
5 2 3 Bipyramidal Linear
(T.B.P.)
 AB2L3

Bond Angle = 180o

Example: XeF2, I3─

 VSEPR Theory

Steric Number: 6 (sp3d2)

(AB6)

900

Bond Angle = 90o

Example: SF6
 VSEPR Theory

General Electron Bonding Lone Electronic

Shape
Formula Pairs Pairs Pairs Geometry

Square
AB5L 6 5 1 Octahedral
Pyramidal

Square
AB4L2 6 4 2 Octahedral
Planar

(A: Central atom, B: Side atom, L: Lone pairs)

 AB5L

Bond Angle < 90o, 180o

Example: BrF5, XeOF4

 AB4L2

Bond Angle = 90o, 180o

Example: XeF4
 VSEPR Theory

Steric Number: 7 (sp3d3)

(AB7)

900

720

Bond Angle = 72o, 90o

Example: IF7
 Need for
Hybridisation
 Shape of CH4 Molecule

Electronic configuration of carbon is:

CGround State : [He] 2s2 2p2 ⥮ ⥮ ↿ ↿

1s2 2s2 2p2

On excitation, Release of energy due

to overlap between the
CGround State : [He] 2s2 2p2 ⥮ ⥮ ↿ ↿ orbitals of C and H

1s2 2s2 2p2

CExcited state : [He] 2s1 2p3 ⥮ ↿ ↿ ↿ ↿

1s2 2s1 2p3

 Shape of CH4 Molecule

C-H bonds formed H

H
by
H
H s (H)-p (C)
overlapping
H

H
Angle between
H
them will be
90o
4th C-H Bond will be formed
by s (C)-s (H) overlap
Shape of CH4 Molecule

s-orbital overlap can

be in any direction

Direction of fourth C–H

bond cannot be
determined
 Shape of CH4 Molecule

Expected Experimental
observations observations

All H-C-H bond angles

All H-C-H bond angles are identical
are not certain with a value of 109.5°

3 C-H bonds formed by s-p

All C-H bond lengths and bond
overlap are stronger than 1
C-H bond formed by strengths are identical
s-s overlap
 Limitations of VBT

Formation of diatomic molecules are satisfactorily

explained (except the paramagnetic nature of O2)

VBT fails to explain the bond

properties in polyatomic molecules

Hybridization + VBT

More complete
theory to explain
polyatomic molecules
 Hybridisation

Intermixing of atomic orbitals of

equal or slightly different energies,
(1) results in the formation of new set
of orbitals of equivalent energies
and shape.

Pauling J.C. Slater

The orbitals present in the valence
shell (and sometimes penultimate
(2) shell also) of the atom can
hybridise.
Hybridisation and Shape of Hybrid
Orbitals

Number of Number of
hybrid orbitals = atomic orbitals
(H.O.) intermixing

Larger lobe of H.O. takes part

in bond formation (σ-bond)
Did you Know?

Hybrid Orbital

Shape used for

Actual Shape
representation
 Naming of Hybrid Orbitals

On the basis of atomic orbitals participating in

hybridization:

s-orbital + ‘n’ p-orbital + ‘m’ d-orbital

spndm hybrid orbital

 Types of Hybridisation

sp

sp2

sp3

sp3d

sp3d2

sp3d3
 Important Conditions for Hybridisation

Orbitals can

Have a pair of
Have an unpaired e– Be vacant
electrons

All three types can undergo

hybridisation
 Salient Features of Hybridisation

Promotion of electron is not an essential

condition prior to hybridisation.
Orbitals undergo hybridisation and not the
electrons.

Hybrid orbitals generally form 𝛔 bond.

Number of
Participating
hybridised Hybridisation
atomic orbitals
orbitals

One s + One p
2 sp
+
 % s Character

%s Number of s orbitals
character = Number of (s+p) orbitals
✕ 100

sp > sp2 > sp3

Decreasing order of s character

 Percentage Character of Orbitals

sp sp2 % p or % d
% s character
character
increases
increases

50% s 50% p 33.33% s 66.66% p Orbital becomes Orbital becomes

bulkier and thinner and
shorter longer

sp3 Energy of hybrid

orbital decreases Energy of hybrid
orbital increases

Electronegativity Electronegativity
25% s 75% p increases decreases
 Features of Hybridisation

% s character Stability of
Bond Strength
in hybrid orbital hybrid orbital

sp - p > sp2 - p > sp3 - p > p- p

Decreasing order of bond strength

Hybrid orbitals are directed in space

in order to obtain a
in a way to have minimum repulsion
stable arrangement
between the electron pairs
 Steric Number

Type of hybridisation is estimated by steric number

Steric Number of σ bonds Number of lone pairs

Number
= of central atom + on central atom

Steric V+M-q
Number =
2

Type of hybridization indicates

the geometry of the molecule
 Steric Number, Hybridization and Geometry

Steric
Hybridization Geometry Involving Orbitals
number
2 sp Linear s, px/ pz/ py

s, px, pz/ py, pz/px, py

3 sp2 Trigonal Planar

s, px, pz, py
4 sp3 Tetrahedral

3 s, px, pz, py, dz2

5 sp d Trigonal bipyramidal

3 2 s, px, pz, py, dz2, dx2-y2

6 sp d Octahedral

3 3 s, px, pz, py, dz2, dx2-y2 , dxy

7 sp d Pentagonal bipyramidal
 Methods for Finding Hybridisation

Determination of type
of hybridisation

Orbital Box Finding Steric Formula for

Diagrams Number Steric Number
 sp Hybridisation

Participating Number of
Hybridisation
atomic orbitals hybridised orbitals

One s + One p
2 sp
+

180°

Linear

+─ ─ +
 sp2 Hybridisation

Atomic orbitals participating in Number of

Hybridisation
hybridisation hybridised orbitals

One s + two p
3 sp2

3 new sp2 Trigonal planar

hybridised +
orbitals
120°
─ ─
─
+ + sp2 Hybridisation
 sp3 Hybridisation

Number of
Atomic orbitals participating
hybridised Hybridisation
in hybridisation
orbitals

One s + three p

4 sp3
 sp3 Hybridisation

4 new sp3
hybridised + Tetrahedral
109.5°
orbitals

+ +
+
 Bonding of CH4 Molecule

Here, electronic configuration

of carbon is

Needs
energy
2s2 2p2

CGround State : [He] 2s2 2p2 ⥮ ↿ ↿

CExcited state : [He] 2s1 2px1 2py1 2pz1 ↿ ↿ ↿ ↿

 Bent’s Rule

In T.B.P. geometry,

Occupied by
Equatorial High % s
lone pair,
position character
multiple bond

Occupied by
Axial Low % s more
position character electronegative
element
 Berry Pseudorotation

Fluxional behaviour
Energy difference
of PF5 due to fast Thermal energy
b/w T.B.P. and
exchange between axial
square pyramidal < at room
and equatorial F atoms temperature
geometry

All P-F bonds are

observed to be equivalent
Examples of sp3d Hybridisation
 sp3d2 Hybridisation

SF6
On excitation:

SGround state : [Ne] 3s2 3p4

⥮ ⥮ ↿ ↿
3s 3p 3d

Hybridized orbitals

SExcited state : [Ne] 3s1 3p3 3d2 ↿ ↿ ↿ ↿ ↿ ↿

3s 3p 3d
 sp3d2 Hybridisation

All Bond lengths are

No equatorial & no axial bonds
observed to be identical

SF6 XeOF4 XeF4

Hybridisation in Odd Electron Species

C
F H
H C
F H
F

Hybridisation: Hybridisation:
sp3 sp2
Did you Know?

PCl5(s) [PCl4]+ [PCl6]─

sp3 sp3d2

PBr5(s) [PBr4]+ [Br]─

sp3

PI5(s) Does not exist

P cannot accomodate 6 large sized Br & I.

So, it cannot form PX6─.
 Resonance

Phenomenon of delocalisation If a single Lewis structure cannot

of 𝞹 electrons represent a molecule

Most important parameter to Resonance structures describe the

explain the stability of certain molecule accurately
molecule
 Need of the theory

＋ ＋

Resonance Structures of O3

─ ─

Resonance Hybrid of O3 ─ 1/2 ─ 1/2

 Resonance

Molecules having Resonance

Resonance Structures (R.S.) Resonance Hybrid (R.H.)

Actual structure of different

Similar or degenerate Energy
possible structures

Does not violate the rules

Identical positions of nuclei
of covalence maxima

Same number of bonding & Most stable R.S. contributes

nonbonding electron pairs maximum towards Resonance
hybrid (R.H.)
 Resonance Structures (R.S.) and
Resonance Hybrid (R.H.)

+ +
+

_ _
─ ─
1
2
1
2

Resonance Structures Resonance hybrid of O3

of O3
 Characteristics of Resonance

Resonance structures (R.S.) are Conditions of Resonance

hypothetical

Structure should be planar

Resonance hybrid (R.H.) has its
individual identity
Occurs in adjacent parallel
p-orbitals
Bond lengths of R.H. are intermediate
to those of R.S.
 Rules for Resonance Structures

A Must have proper Lewis structures

Only π electrons or lone pairs can

B
be moved

Overall charge of the system

C
must remain the same

Bonding framework of a
D
molecule must remain intact
 Benzene

1.5
4 Å C6H6 CExcited state : 1s2 2s1 2p3

1. 3 Hybridize
4Å

⥮ ↿ ↿ ↿ ↿

2 2 2 1s2 2s1 2p3

C6H6 CGround state : 1s 2s 2p

C (Excited
↿ ↿ ↿ ↿
⥮ ⥮
and hybrid
↿ ↿ state) 3 sp2-hybrid 2p
1s2 2s 2
2p2 orbitals Unhybridized
p-orbital
 Benzene

Each carbon of benzene has one unhybridised

p-orbital

Unhybridised p-orbitals of each carbon are

parallel to each other
Benzene

Localised 𝛑 Delocalised
bonds 𝛑 bonds
 Resonance Structures and Resonance
Hybrid of Benzene

1.5 1. 3 1.3
4 4 9 Å
Å Å
 Bond order of Resonance Structures

For degenerate resonating structures:

Total
Total
Bond Order no. of bonds
no. of
between = between 2 ÷ resonance
two atoms atoms in all
structures
structures
Less Contributing Less Contributing

[ ]

C = O bond length in CO2 is less than

expected because of resonance
 Drago’s Rule

❖ Hybridization does not take place

for compounds of elements of 3rd
period onwards, bonded to a less
electronegative element like
hydrogen.
❖ It is because energy difference
between participating orbitals is
very high.
 Lewis Acid and Lewis Base

Lone pair donors are

01 also called as Lewis base

Lone pair acceptors are

also called as Lewis acid
02

H3N + H+ NH4+

Donor Acceptor
 Lewis Acids

BF3, AlCl3, BCl3 Incomplete octet

Central atom has

SiF4, PCl5, PF5
vacant d-orbitals

Mg2+, Al3+, Fe2+, Zn2+ Metal cations

Central atom is
attached to a more E.N.
CO2, SO2
atom with multiple
bonds
 Lewis Bases

Central atom has at least one

NH3, H2O, ROH, RNH2 lone pair and is surrounded
by less E.N. atom

Cl–, F–, OH–, NH2– Anions

Back Bonding
 Coordinate Bond

𝛔 - type
Coordinate
Bond

𝛑 - type
 𝛔 - Coordinate Bond

F F 𝝈-type
H

N H3N BF3
B
H
F
H Filled ‘p’ F H
F
Vacant ‘p’ ─ ＋
B N
Lewis Base Lewis Acid
F H
H
 𝛑 - Coordinate Bond

Back bonding Back bond forms

between

Atom having non bonded electron

Kind of coordinate 𝛑 bonding
pair

&

Partial double bond character Atom having vacant orbital

 𝛑 - Coordinate Bond

P P

H H F F
H F

Back Bonding Back Bonding

Because Because F has
Hydrogen lone pairs and
has no can donate to
lone pairs one empty
p-orbital of P
 CHCI3 ⇌ H+ +
-
CCI3

-
CHF3 ⇌ H+ + CF3

F atom does
Cl atom have not have
vacant d -orbital vacant
to accommodate d -orbital
electron pair

Vacant orbital

Back bonding 2p𝛑-3d𝛑 -

 BF3

B-F bond in
BF3 is found to
be shorter and
stronger than
expected due
Species Bond Length (pm) to back
bonding.
BF4− 130.7

BF3 139.6
 Order of Accepting Tendency

Lone pairs are

present already
Si > P > S > Cl

When lone
pairs are absent
Si < P < S < Cl
 Factors for Coordinate 𝛑-Bonding

Stability of 𝛑-bond

1
Stability ∝
Size of orbitals

Size of orbital increases Weak 𝜋 bond

Size of orbital decreases Strong 𝜋 bond

 Relative Stability of 𝛑-Bond

2p𝜋-2p𝜋 > 2p𝜋-3p𝜋 > 2p𝜋-3d𝜋 > 3p𝜋-3p𝜋

↑
No. of lone pairs on the
atom having vacant
orbital
BF3(2p𝜋-2p𝜋) > PF3(3d𝜋-2p𝜋)

Extent of back bonding

↑
 Backbonding

Lewis acidic strength decreases.

Lewis basic strength decreases.

Bond length decreases.

Bond angle may or may not change.

Hybridisation may or may not change.

Point to Remember!!

One atom involved

in back bonding
must be of 2nd period
Electron Deficient Compounds

Insufficient no. of
electrons to
complete octet.

Examples: BH3, BeCl2, BF3

 Case 1: Electron Deficiency in BH3

❏ Those bonds which has insufficient number of electrons

and makes them stable are known as electron deficient
bonds.

❏ BH3 is electron deficient compound. That’s why it

undergoes dimerisation by means of 3c-2e─ bonds also
known as banana bonds.

❏ Diborane (B2H6) is a dimer of BH3.

❏ In B2H6 there are two 3c-2e─ bond which are known as
banana bonds. In B2H6 there are four 2c-2e─ bond which
are known as terminal bonds.
❏ The hybridization of boron in B2H6 is sp3.
Electron Deficient Bonds

Those bonds which has insufficient

number of electrons and makes them
stable are known as electron deficient
bonds.
BH3 is electron deficient compound.
That’s why it undergoes dimerisation
by means of 3c-2e─ bonds also known
as banana bonds.
Case 2: Electron Deficiency in AlCl3

Cl Cl

Al

Cl

Incomplete Tendency to
octet of Al form dimer
 In Vapour Phase - Dimer of AlCl3 (Al2Cl6 )

sp3 - sp3 - sp3

overlap Two 3c - 4e─ bonds
 Case 3: Electron Deficiency in BeCl2

Incomplete Forms dimer &

polymer
octet of Be
to get stabilized
 In Vapour Phase - Dimer of BeCl2 (Be2Cl4)

sp2 - sp3 - sp2

Planar
overlap
Cl

Cl Be Be Cl

Cl

3c - 4e─ bond
 In Solid Phase -
Polymer of BeCl2 (BeCl2)n

sp3 - sp3 - sp3

overlap

Non
planar 3c - 4e─ bond
 Case 4: Electron Deficiency in BeH2

H Be H

Incomplete Forms dimer

& polymer
octet of Be
to get stabilized
In Vapour Phase - Dimer of BeH2(Be2H4)

sp2- s - sp2
overlap

3c - 2e-
bond Planar
 In Solid Phase - Polymer of BeH2 (BeH2)n

sp3
Non planar

sp3

sp3 - s - sp3
3c - 2e─ bond
overlap
Case 5: Electron Deficiency in ICl3

Forms dimer to minimize

repulsion between lone pairs
 In Solid Phase - Dimer of ICl3 (I2Cl6)

sp3d2 - sp3 - sp3d2

overlap Planar 3c - 4e─ bond
 Bond
Parameters
 Bond Parameters

Bond angle Bond length Bond energy Bond order

 Bond Angle

Angle between the orbitals containing

bonding electron pairs around the central
atom in a molecule/complex ion

180°
Expressed in degrees & is
spectroscopically determined
+ - - +

Gives ideas about distribution

of orbitals around the central
atom which helps in
determination of shape.
 Factors Affecting Bond Angle

120°
(1) Hybridization sp3

sp2
109.5°
As % s
character

Bond angle
180° sp
 Factors Affecting Bond Angle

(2) Steric Repulsions

Steric Repulsions Bond angle

Same central atom (2nd period), same hybridisation (sp3) &

side atoms are of 3rd period & onwards

O O O
Cl B
F Cl B
F 103° 110.13° r 112° r
 Factors Affecting Bond Angle

(3) Number of lone pairs on the central atom

As number of lone
Bond angle
pairs

Same hybridisation of the central atom

 Factors Affecting Bond Angle

(4) Electronegativity of the central atom

E.N. of
Bond angle
central atom

Same hybridization and number

of lone pairs on central atom

: :
: : : :
> >

: :
: :

: :

: :
: :
: :

: : : : : :
 Factors Affecting Bond Angle

Electronegativity of
(5) the side atoms

P P
F F Cl Cl
E.N. of 97.8° F 100.3° Cl
side atom

Bond angle
P P
Br Br I I
Same central atom, same hybridization 101° Br 102° I
& same number of lone pairs
Point to Remember!!

Regular geometry

All the side atoms are identical and no

lone pair on central atom

Bond angle not affected by

electronegativity
Example

109.5o 109.5o

109.5o 109.5o

CCl4 = SiCl4 = GeCl4 = SnCl4

 Factors Affecting Bond Angle

(6) Back Bonding

Side Central Central Side

atom atom atom atom
 Factors Affecting Bond Angle

But net effect in

BF3 Due to back bonding Bond order
repulsion is zero

Bond angle = 120o

Hybridization
N(SiH3)3 Due to back bonding changes from Bond angle
sp3 to sp2
 Bond Length

Equilibrium distance
between the nuclei of two
bonded atoms in a molecule

Factors Affecting Bond Length

Size of the bonded

Multiplicity of Bonds % s-character
atom

Number of lone pairs Electronegativity

on bonded atoms difference
 Bond Energy

Amount of energy Magnitude of

Multiplicity of bond Bond energy
required to break 1 mole
of particular type of
bonds between two
Bond Energy (kJ mol-1)
atoms in gaseous state.
C C 347

C C 611
Unit : kJ mol-1 C C 837
 Bond Energy

Bond length Bond

(for same energy
bonded atom)

Bond length Energy (kJ In group 15, 16 and 17 single bonds

Bond
(pm) mol-1) between 2nd period elements are
exceptionally weaker due to l.p - l.p.
Cl Cl 199 243
repulsions
Br Br 228 192

I I 267 151 Example :

Cl Cl > Br Br > F F > I I

 Bond Order

The number of bonds between the two

atoms in a molecule.
Shared pairs
of electrons

Lone pair of
electrons
+

Bond order = 2
 What We Know?

Types of bonds

Covalent bond Ionic bond

Sharing Transfer
of electrons of electrons
What Exists in Reality?

There exists some covalent

character
in an ionic bond
and some ionic character
in a covalent bond!
 Covalent Bond

Non-polar When 𝚫E.N. < 0.4 between

Covalent the bonded atoms

Covalent
Bond
<
Polar When 𝚫E.N. 0.4 between
Covalent the bonded atoms
 Non-polar & Polar Covalent Bond

A A E.N. of A < B
A B

Symmetrical electron cloud Asymmetrical electron cloud

H2, Cl2, N2, F2... HF, HCl, HBr, HI ...

 Polarisation

Due to Charged Act as an

polarisation ends develop electric dipole

─
𝛅+ 𝛅
H Cl
 Dipole Moment

1. Dipole moment is a measure of the separation

of charges(polarity) between the two ends of a
dipole.
2. It's magnitude is equal to the product of charge
and the distance of separation.
3. It a vector quantity.
4. It is denoted by μ.
 Dipole Moment

Formula of dipole moment is given as:

𝛍 = q ×d ─q 𝛍 +q

d
Unit = Debye d = Distance of separation (Å)

q = Magnitude of charge (e.s.u.)

 Direction and Representation

Represented by a small arrow with tail on the

positive centre and head pointing towards the
negative centre.

─
𝛍
𝛅 𝛅+
Cl H
d
 Value of Dipole Moment (𝛍)

Diatomic Molecule Polyatomic Molecule

Difference in Spatial
Bond dipole
Electronegativities arrangement
 Dipole Moment (𝛍)

In diatomic Difference in
molecules, electronegativities
𝛍 depends upon & bond length

In polyatomic
Bond dipole and spatial
molecules,
arrangement
𝛍 depends upon
Resultant Dipole Moment (R)

𝛍=P

𝛍=Q

R = (P2 + Q2 + 2PQ cos𝛉)

 Dipole Moment

Generally, out of ‘q’ and ‘d’, ‘q’ is the dominant factor.

q depends on 𝛥.E.N.

𝛥.E.N. q μ

For a non-polar molecule, For a polar molecule,

𝛍net = 0 𝛍net ≠ 0
 Dipole Moment

Diatomic molecules

Homodiatomic Heterodiatomic
(Non polar) (Polar)

𝛍net = 0 𝛍net ≠ 0

Polyatomic molecules

Spatial
Bond dipole
arrangement
 Dipole Moment

It can be zero as the two

oppositely acting bond
dipoles can cancel
each other

Net dipole moment( 𝛍net ) = 0

 Regular Geometries

B B

B
A B A
B B B
B

𝛍net = 0 𝛍net = 0
 Dipole Moment

Lone pair contributes in

dipole moment, but its
contribution can’t be
quantified as size of lone pair
is not known.

Symmetrical
Dipole Moment = 0
Molecule

Asymmetrical
Dipole Moment ≠ 0
Molecule
 Predicting Geometry Using
Dipole Moment

CI H H

C C C
Cl CI H H Cl Cl

CI H Cl

CCl4 CH4 CHCl3

𝛍=0 𝛍=0 𝛍 = 1.04 D

 Some Important Order
of Dipole Moment

CD3F > CH3F

F F

C C
D D H H
D H

Δ E.N. in C - D > Δ E.N. in C - H

 Dipole Moment of Dichlorobenzene

Ortho- Meta- Para-

dichlorobenzene > dichlorobenzene > dichlorobenzene
 What are Cis and Trans?

Cis: Similar groups Trans: Similar groups

on same side on opposite sides

𝛍net ≠ 0 𝛍net = 0
 Effect of Dipole Moment
on Boiling Point

Generally,

Dipole moment Boiling point

B.P. of cis is greater than trans

Dipole Moment and Percentage
Ionic Character

𝛍Observed
% Ionic
character = 𝛍Theoretical × 100

Experimental
𝛍Observed
value of 𝛍

Assuming 100%
𝛍Theoretical
ionic compound
 Covalent Character in Ionic Compounds

When an anion and a cation Polarisation

approach each other

Valence shell of the anion

Phenomenon of deformation
is pulled towards the nucleus
of an anion by a cation
of the cation

The shape of the anion is

deformed

Polarising power The ability of a cation to

of the cation polarise a nearby anion

Polarisability Ability of an anion

of the anion to get polarised
 Fajan’s Rule

Greater is the polarisation of an anion in a molecule,

more is the covalent character in the molecule.

Charge on Cation
1
Size of Cation

Polarization ∝ Charge on Anion

Size on Anion
(As size of cation
Covalent character increases from left to
right, Polarisation
decreases)
Example: BeCl2 > MgCl2 > CaCl2 > SrCl2 > BaCl2
 Factors affecting polarisation

For the cations of nearly the

Eg: CuCl > NaCl (Covalent character)
same size and charge,

Order of polarizing power: Pseudo inert

[Ne] 3s2 3p6 gas
Cu+
Pseudo inert gas Inert gas 3d10 configuration
>
configuration configuration
Inert gas
Na+ 1s2 2s2 2p6
configuration
 Fajan’s Rule

Cations with pseudo inert gas

configuration: (n-1)d10 ns0

More Zeff due to poor

shielding effect of d and f 01
electrons.

Polarising power
02 increases
 Polarisability of Anion

Oxyanions are generally less polarisable

because charge is present on O atom
Polarisability ∝ Charge on the anion which is very small and we need to
consider only the element which
acquires the charge (and not the
complete anion)

S2─ > SO32─ > SO42─

Cl─ < ClO2─ < ClO3─ < ClO4─

Applications of
Fajans’ Rule
 Determination of Covalent Character
in an Ionic Compound

Extent of polarisation Covalent character

LiF < LiCl < LiBr < LiI

NaF < Na2O < Na3N

 Variation in Melting Point

01 Lattice energy Fluorides (F–) of s-block

Melting metals (except BeF2) & Al3+
point of and Cl–, Br–, I– of alkali metals
ionic solids (except Li+) are dominantly
depends ionic.
upon
02 Extent of
polarisation

Melting point ∝ Lattice Energy

 Variation in Melting Point

For Cl–, Br–, I– of Li+, all

alkaline earth metals As covalent character
& Al3+, extent of in an ionic compound, the
polarisation is high. melting point decreases.

M.P. of covalent compound

Melting 1 < M.P. of ionic compound
point ∝ Extent of polarisation
 Variation in Melting Point

LiF > LiCl > LiBr > LiI

NaCl > MgCl2 > AlCl3 > SiCl4

 Intensity of Colour

Colour of some Polarisation of

compounds can be their bigger
explained by negative ions.

Bigger anions are more

Partial absorption
polarised & hence their
of visible light. SnCl2 SnI2
electrons get excited by

PbCl2 PbBr2 PbI2

 Solubility in Water

Solubility of p-block/d-block Extent of polarisation

salts & halides of Be is low is high

1
Solubility in Water ∝ Extent of polarisation

Covalent character Solubility in water

AgCl > AgBr > AgI

Fe(OH)2 > Fe(OH)3

 Solubility in Water

Ag2O > Ag2S

Thermal Stability of Ionic Compounds

❖ For uniatomic anion, as interionic distance

increases, lattice energy decreases, hence
thermal stability decreases.
❖ Be2N2 > MgN2 > CaN2 > Sr2N2> Be3N2
❖ For multiatomic anion (for compounds
having the same anion) thermal stability
increases down the group.
Molecular
Orbital
Theory
 Features of MOT

Electrons in a molecule are present

01 in the molecular orbitals (MO’s)

Atomic orbitals (AO’s) of comparable energies

& proper symmetry combine to form MO’s
02

AO is monocentric whereas
03 a MO is polycentric

Number of MO’s formed is equal to

the number of combining AO’s
04
 Features of MOT

There are two types of molecular orbitals: Bonding

05 Molecular Orbitals (BMO) and antibonding Molecular
Orbitals (ABMO).

BMO has lower energy and hence greater

stability than the corresponding ABMO 06

Electron probability distribution around a group

07 of nuclei in a molecule is given by a MO

MO’s are filled according to Aufbau principle,

Pauli’s exclusion principle & Hund’s rule
08
 Linear Combination of
Atomic Orbitals (LCAO)

BMO (Bonding ABMO (Anti Bonding

Molecular Orbitals) Molecular Orbitals)

Constructive Destructive
interference interference

ΨBMO = ΨA + ΨB ΨABMO = ΨA ─ ΨB

Where, A and B are atoms

Molecular Orbitals

Bonding
Molecular
Orbital

AntiBonding
Molecular
Orbital
 Electron Density in BMO

Electron density
2
Ψ increases in the
internuclear region.

H H

BMO
 Electron Density in ABMO

Ψ2 Electron density
decreases in the
internuclear region.

H H

ABMO
 Linear Combination of Atomic Orbitals

Bonding Molecular
01
Orbital (BMO)

Types of MO’s

Antibonding Molecular
02
Orbital (ABMO)
 Difference between BMO and ABMO

Bonding Antibonding Bonding Molecular Antibonding

Molecular Molecular Orbital Orbital (BMO) Molecular Orbital
Orbital (BMO) (ABMO) (ABMO)

Lower in energy as Higher in energy as

MO formed by the MO formed by the compared compared
addition of Atomic subtraction of to atomic orbital to atomic orbital
orbitals atomic orbitals
Electron density Electron density
increases in the decreases in the
𝛹BMO = 𝛹A + 𝛹B 𝛹ABMO = 𝛹A - 𝛹B internuclear region internuclear region

Formed by Formed by May or may not have Always has a nodal

constructive destructive a nodal plane plane
interference interference Represented by
(Stabilized MO) (Destabilized MO) Represented by
𝞂*1s, 𝞂*2pz, 𝛑*2px,
𝞂1s, 𝞂2pz, 𝛑2px, 𝛑2py
𝛑*2py
 𝞂 and 𝛑 Molecular Orbitals

𝞂 Head on 𝛑 Sideways

Symmetrical around Asymmetrical around

the bond axis the bond axis
 Shapes of MOs Formed by s-orbitals

When two orbitals combine (Constructive

in same phase then + Interference)
constructive interference
take place.
s s σs
When two orbitals combine
out of the phase then
destructive interference
take place.
(Destructive
- Interference)

s s σ*s
 Molecular Orbital Energy Diagram

H2 molecule

Energy σ*1s

1s 1s
Atomic Atomic
Orbital Orbital
of hydrogen σ1s of hydrogen
Molecular
Orbitals of H2
 Shapes of MO’s: 𝞂2pz

_ _ In Phase _ _
+ + + +

2pz 2pz 𝞂2pz

Out of Phase
_ + + _ + _ + _ +

2pz 2pz 𝞂*2pz

Shapes of MO’s
 Shapes of MO’s

In Phase
+
+
_

2px 2px 𝛑2px

Out of Phase
+

2py 2py 𝛑*2py

 Gerade & Ungerade Molecular Orbitals

On moving equal distance in

the opposite direction from the
centre of the MO, if the sign of
𝛹 Gerade orbital
𝛔, 𝛑*
(𝛹g)

is not the
is the same
same
Ungerade orbital
𝛔*, 𝛑
(𝛹u)

Gerade Ungerade
 Molecular Orbital Diagram for > 14
Electron System
For
molecules 𝛔*2pz
having > 14
electrons 𝛑*2px 𝛑*2py

2p 2p (𝛔1s) < (𝛔*1s) < (𝛔2s) < (𝛔*2s)

𝛑2px 𝛑2py
< (𝛔2pz) < [𝛑2px = 𝛑2py] <
Energy

𝛔2pz

[𝛑*2px = 𝛑*2py] < (𝛔*2pz)

𝛔*2s
2s 2s
𝛔2s

𝛔*1s
1s 1s
𝛔1s
 Molecular Orbital Diagram for ≤ 14
Electron System

𝛔*2pz
For molecules
having ≤ 14 𝛑*2px 𝛑*2py
electrons (𝛔1s) < (𝛔*1s) < (𝛔2s) <(𝛔*2s)
2p 2p
𝛔2pz
< [𝛑2px = 𝛑2py] < (𝛔2pz)
Energy

𝛑2px 𝛑2py
< [𝛑*2px = 𝛑*2py] < (𝛔*2pz)
𝛔*2s
2s 2s
𝛔2s

𝛔*1s
1s 1s
𝛔1s
 s & p-Mixing

Modifications in the
energies of MO’s due to s
and p - mixing.

Also known as symmetry

contribution.
 Electronic Configuration (E.C.)

B - 1s2 2s2 2p1 (5 electrons)

For B2 molecule, 10 electrons (< 14 electrons)

E.C. of B2 (𝛔1s)2 (𝛔*1s)2 (𝛔2s)2 (𝛔*2s)2 [(𝛑2px)1 = (𝛑2py)1]

 What Does MOT Tell?

Bond Length

Bond Order Stability

Existence of a Molecule

Applications Magnetic Behaviour

Color
 Bond Order

One half the difference between the number

of electrons present in the BMO & the ABMO

Bond Order 1 1
(B.O.) = 2
(Nb) ─
2
(Na)

Number of electrons
Na
in ABMO

Number of electrons
Nb
in BMO
 Existence of Molecules

Bond Order

Zero Negative

Molecule does not exist

Thus, He2 does not exist!!!

 Calculation of Bond Order

Shortcut to find the bond order of

homonuclear diatomic molecules

─1 +1

Number of
10 11 12 13 14 15 16 17 18
electrons

Bond order 1 1.5 2 2.5 3 2.5 2 1.5 1

─0.5 ─0.5
Bond Order and Stability of Molecules

∝ Bond Strength

∝ Stability
Bond
Order
1
∝
Bond length

∝ Bond Dissociation
Enthalpy
Species with the Same Bond Order

If the bond order is

01 same for two species

The one with higher

number of electrons in 02
ABMO is less stable.

And the one with higher

03 number of electrons in
BMOs is more stable.
 Magnetic Behaviour

Generally,
Magnetic Nature

If the total
number of electrons
present in the species is
odd, the species is One or more MO’s All the MO’s are
paramagnetic are singly occupied doubly occupied

Examples : O3─ , NO2, NO, ClO2 Paramagnetic Diamagnetic

 O O2 O

O2 molecule
σ*2p
z

𝜋*2p 𝜋*2p
x y

2p 2p

Energy
𝜋2p 𝜋2p
x y

σ2p
z

σ*2s

2s 2s

σ2s
Atomic Molecular Atomic
Orbitals Orbitals Orbitals
Point to Remember!!

An unpaired electron acts as a magnetic dipole

Magnetic
Moment (𝝻)
= √ n(n+2) B.M.

n = Number of unpaired electrons

B.M. = Bohr Magneton

 HOMO and LUMO

Highest Lowest
Occupied Unoccupied
Molecular Molecular
Orbital Orbital

HOMO LUMO
 MO Diagram
of
Heteronuclear
Diatomic
Molecules
 MO Diagram of Heteronuclear
Diatomic Molecules

Heteronuclear
molecules

Atoms of Atoms of group

adjacent groups difference ≥ 2

MO diagram similar MO diagram different

to homonuclear from homonuclear
molecules molecules
 Heteronuclear Diatomic Molecules

Experimentally the bond orders of NO and O2+ are the same.

Bond
Order
= 2.5

Paramagnetic

Experimentally the bond orders of CN─ and N2 are the same.

Bond Order = 3

Diamagnetic
 Heteronuclear Diatomic Molecules

Experimentally the bond orders of CO and N2 are the same.

1𝞂+2𝛑
Bond Order = 3 bonds

Diamagnetic
 Bond Order

Isoelectronic molecules
and ions have identical bond
order.

Examples:
N2 & CO: Bond order = 3
Metallic
Bonding
 Metallic Bonding

Formed between metal

(electropositive element) and metal
(electropositive element).
Electron sea model : Metal kernels
occupy lattice positions in the crystal
structure of a metal and are
embedded is a gas of free valence
electrons.
Point to Remember!!

Many mechanical properties of metals can be

related to the strength of metallic bond

Melting point (M.P.) & hardness

Strength
M.P. & hardness of metallic
∝
of metals bond
 Band Theory

Overlap of atomic
orbitals in solids gives
rise to bands of energy
levels
 Band Theory

ABMO

E Na2 1 1

3s1 3s1 ⥮ BMO

 Band Theory

ABMO

E Na3 1 1 1 1 Non bonding MO

3s1 3s1 3s1

⥮ BMO
 Band Theory

ABMO

E Na4 1 1 1 1
⥮
3s1 3s1 3s1 3s1
BMO
⥮
Atom Atom Atom Atom
1 2 3 4
 Band Theory

MO’s
Empty

AO’s

ABMO

E Nan 1 1 1

3s1 3s1 3s1 BMO

Atom Atom Atom
1 2 n
Filled with electrons
 Band of Orbital In Crystal of Sodium

Conduction
p-band
band
3p
E

1
Valence band s-band
3s
 Band Theory

Highest energy electrons of the

metallic crystals occupy either a
partially filled band or a filled band
that overlaps with an empty band.

These filled/ partially filled bands

and empty bands are known as
valence band and conduction
band respectively.
 Band Gap

Energy difference between the valence

band and the conduction band.

For conductors: No energy gap

For insulators: Large energy gap

For semiconductors: Small

energy gap
 Intermolecular Forces

Attractive Repulsive
 Attractive Forces

Ion-Dipole Instantaneous
Dipole-Dipole
Attraction Dipole-Induced Dipole
Attraction
Attraction

Dipole-Induced Dipole Ion-Induced Dipole

Attraction Attraction
 van Der Waals Forces

van der Waals forces

Weak chemical
forces

Dipole-dipole Dipole-induced
Forces holding two Dispersion forces
forces dipole forces
or more
molecules together
Debye London
Keesom forces
forces forces
 Dipole-Dipole Attraction

Exists between oppositely charged

ends of permanent dipoles
Attraction
Repulsion
Dipole -Induced Dipole Attraction

It is a weak attraction, when a

polar molecule induces
a dipole in an atom or in a
nonpolar molecule by
disturbing the arrangement of
electrons in the non-polar
species.
 Factors Affecting Boiling Point

Boiling Point ∝ van der Waals forces

Boiling Point ∝ Molecular mass

If molecular mass is same, then factor

responsible is molecular surface area.

van der Waals Force ∝ Surface area.

Note!!

Polar molecules can

interact via London
Forces also.
 Ion-Dipole Attraction

Electrostatic Polar Molecule

Ion Force (Dipole)

Strength of attraction is directly

proportional to

(1) Charge density on the ion

Dipole moment of the

(2) polar molecule
Ionic Compounds in Polar Solvents

NaCl in H2O

Na(OH2)x＋ Cl(H2O)y─
H2O
 Ion-Induced Dipole Attraction

Electrostatic Non-Polar Molecule

Ion
Force (Induced Dipole)

Formation of Polyhalide Ions (X3-)

(Ion) (Non-polar)
 Interaction Energy v/s Distance

Type of 1 Type of
Interaction energy ∝ Interaction energy ∝ 1
interaction rx interaction rx

1 Ionic-Induced 1
Ionic bond
r Dipole r4

1 Dipole-Induced 1
Ion-dipole
r2 dipole r6
1 1
Dipole-dipole London Forces
r3 r6
 Strength of Intermolecular Forces

Ion-dipole attraction

Dipole-dipole attraction

Ion-induced dipole attraction Strength

Dipole-induced dipole attraction

Instantaneous dipole - induced dipole attraction

Strongest Dipole-Dipole
interaction

Hydrogen Bonding
 Hydrogen Bond

Displacement
of electrons
towards X

Polar molecule having electrostatic force of

𝛅+ 𝛅-
attraction
H X
Hydrogen More EN
atom
Represented
by a dotted
line
 Hydrogen Bond

Special case of dipole-dipole

(1) attraction

Molecules with H atom attached

(2) to a highly electronegative atom

Strength of the H bond is

determined by the coulombic
interaction b/w the lone pair of the
E.N. atom & H atom.
Factors Affecting Strength of
H - bonding

Higher electronegativity
difference

Greater 𝛅+ charge on
H-atom

Strength of H-bonding
 Factors Affecting Strength of
H - bonding

Ease of donation of
Strength of H-bonding
lone pair of E.N. atom

N > O > F

Decreasing tendency
to donate lone pair
Point to Remember!!

To compare strength of H-bond

First check Δ E.N. and then

tendency to donate lone pair
 Symmetrical Hydrogen Bonding

Very strong H-bonding occurs in the alkali metal

hydrogen fluorides of formula M[HF2]

-
x y

Bond lengths: x = y = 113 pm

Bond energy
of both H-F = 163 kJ/mol
 Types of Hydrogen Bonding

Hydrogen Bonding

Intermolecular Intramolecular

Between two or Within a

more molecules molecule
Examples of Intermolecular
Hydrogen Bonding

𝛅+ 𝛅-

𝛅- 𝛅+

Acetic Acid
 Intermolecular
H - Bonding

Homo Hetero
Intermolecular Intermolecular

𝛅-
𝛅+
𝛅+ -
𝛅

2
𝛅+

𝛅-

Water Alcohol in Water

Conditions for the Formation of
Intramolecular Hydrogen Bond

Ring formed as a result of

(1) H bonding should be planar

5 or 6 membered ring should be

(2) formed

Minimum strain should be there

(3) during ring closure
 Intramolecular H-Bonding

Examples
𝛅+

𝛅-

o-Nitrophenol
Point to Remember!!

Cl usually doesn’t form H - bond due to their low charge density

𝛅+

𝛅-

𝛅-
𝛅+

Chloral hydrate (CCl3CH(OH)2)

 H-Bonding Dependency on
Physical State of Compounds

Extent of H–bonding
depends on the physical
state of the compound.

Gaseous state < Liquid state < Solid state

 Solubility

Viscosity
Effect of
H-Bonding on
Boiling Point
Physical
Properties
Physical State

Acidic and Basic

Strength
 Few organic compounds (Non-polar)
01 are soluble in water (Polar solvent)
due to H-bonding.
Example: Alcohol in water.

C2H2 is highly soluble in acetone

Solubility 02 due to H-bonding but not in
water.

Intramolecular hydrogen bonding leads

03 to chelate formation, so the solubility of
that species involved in intramolecular
H-bonding in water decreases.
 Order of Boiling Point

SbH3 > NH3 > AsH3 > PH3

H2O > H2Te > H2Se > H2S

HF > Hl > HBr > HCl

 Why does Ice Floats over Water?

Extensive network of H bonds

Ice has cage like structure

with vacant space

H2O (s) is less dense than H2O (l)

 Did You Know?

D2O (s) sinks in H2O (l)

E.N. of D is less than H

D forms stronger
H-bond

Density: D2O (s) > H2O (l)

 Clathrates

appropriately sized
Species formed by into the voids
gas molecules
entrapment of of ice
(e.g.: Xe, Kr etc.)

Ar.6H2O

Noble Gas
Kr.6H2O
Clathrates

Xe.6H2O
 Clathrates

𝛅+ 𝛅+

𝛅+ 𝛅+

𝛅- 𝛅-
+
𝛅
𝛅+
𝛅- 𝛅-

𝛅+
𝛅+
𝛅- 𝛅-
𝛅+ 𝛅+

𝛅+ 𝛅+

Ar.6H2O