CHAPTER 4

CHEMICAL BONDING

Chemical bond is the force that

holds two atoms together in a
molecule or compound
Valence electrons play an
important role in the formation of
chemical bonds

CHAPTER 4
CHEMICAL BONDING
4.1 Lewis Structure
4.2 Molecular Shape and Polarity
4.3 Orbital Overlap and Hybridization
4.4 Intermolecular Forces
4.5 Metallic Bond

4.1 Lewis Structure

4.1.1

Lewis Symbol

A Lewis symbol consists of:

the symbol of an element
dots or cross is used to represent the
valence electrons in an atom of the
element.

Example
The Lewis symbol of atom

G ro u p

13

14

15

16

17

18

V a le n c e
e le c t ro n

L e w is d o t
sy m b o l

Elements in the same group have the

same valence electronic
configurations
similar Lewis symbols.

4.1.2

Octet Rule

Octet rule states that atoms tend to form

bonds to obtain 8 electrons in the valence
shell
Atoms combine to achieve stablility

to have the same electronic

configuration as a noble gas

Atoms achieve noble gas

configuration through:
i) transferring electrons
ii)
sharing electron
Bond formation involve transferring or
sharing of only valence electrons

Electronic Configuration of Cations and

Anions
1)Noble gas configuration
Group 1, 2 and 13 elements donate valence
electrons to form cations with noble gas
configurations
Example:
Na : 1s22s22p63s1
Na+ : 1s22s22p6 (isoelectronic with Ne)
Ca : 1s22s22p63s23p64s2
Ca2+ : 1s22s22p63s23p6 (isoelectronic with Ar)

Group 15, 16 and 17 elements accept

electrons to form anions with noble gas
configurations
Example:
O : 1s22s22p4
O2 : 1s22s22p6
(isoelectronic with neon)
Cl : 1s22s22p63s23p5
Cl : 1s22s22p63s23p6
(isoelectronic with Ar)

2)

Pseudonoble gas configuration

d block elements donate electrons

from 4s orbitals to form cations with
pseudonoble gas configuration.
Example:
Zn : 1s22s22p63s23p64s23d10
Zn2+ : 1s22s22p63s23p63d10
(pseudonoble gas
configuration )

3) Stability of the half-filled orbitals

d block element can also donate electrons
to achieve the stability of half-filled orbitals
Example:
Mn : 1s22s22p63s23p64s23d5
Mn2+
: 1s22s22p63s23p63d5
(stability of half-filled 3d orbital )
Fe : 1s22s22p63s23p64s23d6
Fe3+ : 1s22s22p63s23p63d5
(stability of half-filled 3d orbital)

4.1.3 Formation of the bonds

using Lewis Symbols
i.Ionic (electrovalent) bond
ii.Covalent bond
iii.Dative (coordinate) bond

4.1.3.1

Ionic bond (Electrovalent

bond)

Ionic bond (electrovalent bond) is

an electrostatic attraction between
positively and negatively charged
ions.
Ionic compounds are formed when
electrons are transferred between
atoms (metal to nonmetal) to give
electrically charged particles that
attract each other .

Example 1: NaCl

Sodium, an electropositive metal, tends to

remove its valence electron to obtain noble
gas electronic configuration (Ne)

Chlorine, an electronegative element, tend to

accept electron from Na to obtain noble gas
electronic configuration (Ar)

The electrostatic forces between Na+ and

Cl- produce ionic bond
These two processes occur simultaneously

Example 2: CaCl2
Ca: 1s2 2s2 2p6 3s2 3p6 4s2
(Has two electrons in its outer shell)
Cl: 1s2 2s2 2p6 3s2 3p5
(Has seven outer electrons)

Calcium Chloride
If Ca atom transfer 2 electrons, one to each
chlorine atom, it become a Ca2+ ion with the stable
configuration of noble gas.
At the same time each chlorine atom to achieve
noble gas configuration gained one electron
becomes a Cl- ion to achieve noble gas
configuration.
The electrostatic attraction formed ionic bond
between the ions.

Ionic bond

(Formed by transfer of electrons)

Calcium Chloride
+

Example 3: LiF
+

Lewis structure and formation of ionic compounds

1) CaCl2
+

2) MgO
+

3) CaBr2
+

 Ionic bond is very strong, therefore ionic

compounds:
1. Have very high melting and boiling
points
2. Hard and brittle
3. Can conduct electricity when they
are in molten form or aqueous
solution because of the mobile ions

Exercises:

By using Lewis structure, show how the

ionic bond is formed in the compounds
below.
( a ) KF
( b ) BaO
( c ) Na2O

4.1.3.2 Covalent Bond

Definition of covalent bond

i. Chemical bond in which two or more

electrons are shared by two atoms.
ii. The electrostatic force between the electrons
being shared the nuclei of the atoms.
Why should two atoms share electrons?

To gain stability by having noble gas

configuration (octet)

Example

7e-

F F

7e-

8e- 8e-

Lewis structure of F2
single covalent bond

lone pairs

F F

lone pairs

lone pairs

single covalent bond

lone pairs
9.4

Covalent compounds:
Compounds may have these covalent
bonds:
i. Single bond
ii. Double bond
iii. Triple bond.

Lewis structure of water

H + O+ H

H O H
2e- 8e-

2e-

or
single covalent bonds

Double bond two atoms share

two pairs of electrons

O
8e-

8e-

8e-

double bonds

or

double bonds

Triple
bond

two
atoms
share
+
three pairs of electrons

N
8e-

or

8e-

triple bond

triple bond

4.1.3.3 Coordinate Covalent Bond

(Dative Bond)
Dative bond is a bond in which the pair
of shared electrons is supplied by one of
the two bonded atoms
Involve overlapping of a full orbital and
an empty orbital

Requirement for dative bonds:

i. Donor atoms should have at
least
one lone pair electrons
ii. The atoms that accepts these
electrons should have empty
orbitals.

i.Single bond
i.Double bond
i.Triple bond

Steps in Writing Lewis Structures

1. Count total number of valence e- of atoms involved.
2. Add 1 for each negative charge. Subtract 1 for each
positive charge.
3. Draw skeletal structure of the compound. Put least
electronegative element in the center.
4. Complete an octet for all atoms except hydrogen
5. If structure contains too many electrons, form double
and triple bonds on central atom as needed.

Example
Draw the Lewis structure for each of the
following compounds:
i. HF
ii. CH4
iii. CHCl3
iv. NH3
v. H2O

Total no. of valence

electrons
H: 1e
F: 7e
Total :
8e

Number of electrons
C : 4e
4H: 4e
Total : 8e

Center atom: N

Count electrons:
C : 4e
H : 1e
3Cl: 21e
Total: 26 e

C ount num ber of

e le c t r o n s
N :
3H :
T o ta l :

5e
3e
8e

4.1.5 Bond Length

Compare the bond length between single,
double and triple bond
Bond length :

The distance between nuclei of the atoms involves in the

bond
C

1.54

C C

1.34 1.20

As the number of bonds between the carbon increase, the

bond length decreases because C are held more closely
and tightly together
As the number of bonds between two atoms increases, the
bond grows shorter and stronger

The sum of formal charge

on each atom should equal:
i.zero for a molecule
ii.the charge on the ion for a
polyatomic ion
Formal charge is used to
find the most stable Lewis
structure

EXAMPLE
1) Draw all the possible Lewis structure
of COCl2.
2) Predict the most plausible structure.

SOLUTION
1)

2)

The most plausible structure is

(2)

Formal charge is determined

before completing a Lewis
structure to predict the most
stable structure because formal

EXERCISE 1

Draw the possible Lewis

structures for HNO2.
Determine the most plausible
Lewis structures for HNO2.

EXERCISE 2

Suggest the possible Lewis

structure for H2SO4. Explain
your answer.

EXERCISE 3
1) HCN
1)CO2
1)SCN

Three conditions:

1) Incomplete octet
2) Expanded octet
3) Odd no. electron

Occurs when central atom has less

than 8 electrons.
Elements that can form incomplete
octet are:
Boron,B , Beryllium, Be &
Aluminium, Al
This is due to elements being
relatively small in size but having high
nuclear charge.

Occurs when central atom has more

than 8 electrons.
Formed by non-metals that have d
orbitals
OR
Non-metals of the 3rd, 4th, 5th.rows
in the periodic table

Nitrogen may form compounds

that contain odd number
electrons.
Example:
Nitric oxide, NO
Nitrogen dioxide, NO2

The use of two or more Lewis

structures to represent a particular
molecule.
Requirement:
Molecules/ions must have multiple
bonds and lone pairs electrons at
the terminal atoms.

RESONANCE STRUCTURE FOR NO3

EXERCISE:
Write Lewis structures of the
following compounds/ ions:
CCl4

CO32-

HCN

PCl3

HNO3

PO43-

C2 H4

C2H2

CH2Cl2

ICl

NH4+

NF3

H2 S

N2 H4

PH3

CS2

NO2-

XeF4

NH3

HCOOH

SO42-

ICl4-

SF6

O3

NO2

4.2 MOLECULAR SHAPE

AND POLARITY

L E A R N IN G O U T C O M E S
A t th e e n d o f th e le s s o n , s tu d e n ts s h o u ld
b e a b le to ;
1.
2.
3.
4.
5.
63

E x p la in v a l e n c e s h e ll e le c t r o n r e p u ls io n t h e o r y .
(V S E P R )
D r a w t h e b a s ic m o le c u la r s h a p e s : lin e a r , t r ig o n a l
p la n a r , t e t r a h e d r a l , t r ig o n a l b ip y r a m id a l a n d
o c t a h e d r a l.
P r e d ic t a n d e x p l a in t h e s h a p e s o f m o le c u le a n d
b o n d a n g le s in a g iv e n s p e c ie s .
E x p la in b o n d p o la r it y a n d d ip o le m o m e n t .
D e d u c e t h e p o la r it y o f m o le c u le s b a s e d o n t h e
s h a p e s a n d t h e r e s u lt a n t d ip o le m o m e n t

4.2 MOLECULAR SHAPE

AND POLARITY
i.
ii.
iii.

64

VSEPR theory
5 basic shapes
polarity

Molecular shape:

Introduction

shows the 3-dimensional arrangement

of atoms in a molecule
Predicted by using Valence Shell
Electron Pair Repulsion (VSEPR) theory

65

4.2.1 VSEPR
The Valence-Shell Electron Repulsion
theory states that:
The valence electron pairs around
the central atom are oriented as far
apart as possible to minimize the
repulsion between them.

66

The repulsion may occur either between:

a) bonding pair & another bonding pair
b) bonding pair & lone pairs or
c) between lone pair & another lone
pairs
67

The strength of repulsion:

The order of repulsive force is:
Lone pairlone pair
repulsion

> Lone pair-bonding > Bonding pair-bonding

pair
repulsion
pair repulsion
Decrease of the repulsion force

Note:
The electron pairs repulsion will determine the
orientation of atoms in space
68

4.2.2 Shape of a molecule

Basic shapes are based on the repulsion
between the bonding pairs.

69

Tips to determine the molecular shape :

Step 1
Draw Lewis structure of the molecule
Step 2
Consider the number of bonding pairs
Step 3
Place bonding pairs as far as possible to
minimize repulsion.

A.

Molecules with 2 bonding pairs

Example: BeCl2

shape

Lewis structure
Be : 2e

180

2Cl :14e
Total : 16 e
..
..
Cl:
Cl Be
..

..

:
70

Linear

B.

Molecules with 3 bonding-pairs

Example: BCl3
Repulsive forces
Lewis structure
between pairs are the
B: 3e
same
3Cl : 21e

Total: 24e
:

120

..

..
Cl :
..

..

:
71

..
Cl

..

Cl

Trigonal planar

C. Molecules with 4 bonding pairs

Example: CH4
Lewis structure

Equal repulsion
between bonding pairs
equal angle

H
H

109.5

H
Tetrahedral
72

D. Molecules with 5 bonding pairs

Example: PCl5
Lewis structure
:

90

..

..

..

..

Cl

73

..
Cl :

120

..

..
Cl

..
Cl :
..

..

Cl

Shape:

Trigonal bipyramidal

E. Molecules with 6 bonding pairs

Example: SF6
Lewis structure
S :
6e
6F : 42e
Total
: 48e

S
F
F

74

F
F

Octahedral
90o
90o

2 electron pairs in the valence shell

of central atom:
Class of

Number

Number

molecules

of bonding

of lone

pairs

pairs

AB2

Shape

180

Linear
75

3 electron pairs in the valence shell

of central atom:
Class of

Number

Number

molecules

of bonding

of lone

AB3

pairs
3

pairs
0

Shape

120

76

4 electron pairs in the valence shell

of central atom:
Class of

Number

Number

molecules

of bonding

of lone

AB4

pairs
4

pairs
0

Shape

109.5o

77

5 electron pairs in the valence shell

of central atom:
Class of

Number

Number

molecules

of bonding

of lone

AB5

pairs
5

pairs
0

Shape

90

120

78

6 electron pairs in the valence shell

of central atom:
Class of

Number

Number

molecules

of bonding

of lone

AB6

pairs
6

pairs
0

Shape

90

90

79

4.2.3 Effect of lone pairs on

molecular shape
The geometries of molecules and
polyatomic ions,
ions with one or more lone
pairs around the central atom can be
predicted using VSEPR.
The molecular geometry is determined
by the repulsions of electron pairs in
the valence shell of the central atoms.
atoms
80

 Repulsion between electron

pairs decreases in the order of:
Lone pairlone pair
repulsion

> Lone pairbonding

pair repulsion

> Bonding pairbonding pair

repulsion

Stronger to weaker repulsion

81

 Electrons in a bond are held by the

attractive forces exerted by the nuclei of
the two bonded atoms therefore, they take
less space of repulsion.
Lone- pair electrons in a molecule occupy
more space; therefore they experience
greater repulsion from neighboring lone pairs
and bonding pairs

82

Number of electron pair : 3

Example : SO2
Class of molecules : AB2E
Molecular shape : Bent / V-shaped

83

Number of electron pair : 4

Example : NH3
Class of molecules : AB3E
Molecular shape : Trigonal pyramidal

84

Number of electron pair : 4

Example : H2O
Class of molecules : AB2E2
Molecular shape : Bent / V-shaped

85

Number of electron pair : 5

Example : SF4
Class of molecules : AB4E
Molecular shape : Distorted tetrahedron /
seesaw

86

Number of electron pair : 5

Example : ClF3
Class of molecules : AB3E2
Molecular shape : T-shaped

87

Number of electron pair : 5

Example : I3 Class of molecules : AB2E4
Molecular shape : Linear

88

Number of electron pair : 6

Example : BrF5
Class of molecules : AB5E
Molecular shape : Square pyramidal

89

Number of electron pair : 6

Example : XeF4
Class of molecules : AB4E2
Molecular shape : Square planar

90

Shape of molecules which the central

atom has one or more lone pairs

91

Class of

Number

Number

molecules

of bonding

of lone

AB2E

pairs
2

pairs
1

Shape

Bent / V-shaped

4 electron pairs in the valence shell

of central atom:

92

Class of

Number

Number

molecules

of bonding

of lone

AB3E

pairs
3

pairs
1

Shape

Trigonal pyramidal

4 electron pairs in the valence shell

of central atom:
Class of

Number

Number

molecules

of bonding

of lone

AB2E2

pairs
2

pairs
2

Shape

Bent / V-shaped
93

Bond angle : < 109.5o

5 electron pairs in the valence shell

of central atom:
Class of

Number

Number

molecules

of bonding

of lone

AB4E

pairs
4

pairs
1

Shape

Distorted
94

tetrahedral

5 electron pairs in the valence shell

of central atom:

95

Class of

Number

Number

molecules

of bonding

of lone

AB3E2

pairs
3

pairs
2

Shape

T-shaped

5 electron pairs in the valence shell

of central atom:

96

Class of

Number

Number

molecules

of bonding

of lone

AB2E3

pairs
2

pairs
3

Shape

Linear

6 electron pairs in the valence shell

of central atom:
Class of

Number

Number

molecules

of bonding

of lone

pairs

pairs

AB5E

97

Shape

Square pyramidal
o

5 electron pairs in the valence shell

of central atom:

98

Class of

Number

Number

molecules

of bonding

of lone

AB4E2

pairs
4

pairs
2

Shape

Square planar
Bond angle : 90o

99

COMPARISON OF BOND ANGLE

IN CH4, NH3 AND H2O

109.5o

100

107.3o

104.5o

a) CH4
Has 4 bonding pairs electrons.
The repulsion between the bonding pairs
electrons are equal.
equal
The bond angles are all 109.5o
101

b) NH3
has 3 bonding pairs electron and 1 lone pair
electron.
according to VSEPR, lone pair - bonding pair >
bonding pair - bonding pair repulsion.
repulsion
Lone- pair repels the bonding-pair more strongly,
strongly
the three NH bonding-pair are pushed closer
together, thus HNH angle in ammonia become
smaller, 107.3o.
102

c) H2O
Has 2 bonding pairs electrons and 2 lone pair
electrons.
According to VSEPR, lone pair lone pair >
lone pair bonding pair > bonding pair
bonding pair repulsion.
repulsion
Lone-pair tend to be as far from each other as
possible.
Therefore, the two OH bonding-pairs are pushed
toward each other.
Thus, the HOH angle is 104.5o.
103

4.2.4 POLAR AND NONPOLAR

MOLECULES
A quantitative measure of the polarity of a bond is

its dipole moment ( ).

= Qr

Where : = dipole moment

Q = the product of the charge from
electronegativity
r = distance between the charges.
Dipole moments are usually expressed in debye units(D)
104

E.g : Polarity of HF
Hydrogen fluoride is a covalent molecule with
a polar bond.
F atom is more electronegative than H atom,
so the electron density will shift from H to
F.
The symbol of the shifted electron can be
represented by a crossed arrow to indicate
the direction of the shift.
H
105

The consequent charge separation can be

represented by :
+ : partial positive charge
- : partial negative charge

106

 Diatomic molecules containing atoms of

different elements (e.g. : HCl, NO and CO)
have dipole moments and are called polar
molecules.
Diatomic molecules containing atoms of the
same element (e.g. : H2, N2 and Cl2) do not
have dipole moments and are called nonpolar
molecules.
107

For polyatomic molecules, the polarity of the

bond and the molecular geometry determine
whether there is a dipole moment.
Even if polar bond are present, the molecules
will not necessarily have a dipole moment.

108

Example
Predict the polarity of the following molecules:

Carbon dioxide, CO2

Carbon tetrachloride, CCl4
Chloromethane, CH3Cl
Ammonia, NH3

109

(a) Carbon dioxide, CO2

- molecular geometry : linear

- oxygen is more electronegative than carbon,
- Dipole moment can cancell each other
- has no net dipole moment ( = 0)
- therefore CCl4 is a nonpolar molecule.
110

(b) Carbon tetrachloride, CCl4

- molecular geometry : tetrahedral

- Chlorine is more electronegative than carbon,
- Dipole moment can cancell each other
- has no net dipole moment ( = 0)
- therefore CCl4 is a nonpolar molecule.
111

( c) Chloromethane, CH3Cl

- molecular geometry : tetrahedral

- Cl is more electronegative than C, C is more
electronegative than H
- Dipole moment cannot cancell each other
- has a net dipole moment ( 0)
- therefore CH3Cl is a polar molecule.
112

(d ) Ammonia, NH3

- molecular geometry : tetrahedral

- N is more electronegative than H,
- Dipole moment cannot cancell each other
- has a net dipole moment ( 0)
- therefore NH3 is a polar molecule.
113

Factors
polarity

that affected the

of molecules

molecular geometry
electronegativity of the bonded atoms.

114

BOND
NON-POLAR
POLAR
NON-POLAR
MOLECULES
NON-POLAR
MOLECULES
Symetrical molecules
- basic molecular shape with the
same terminal atom
- molecules with lone pairs linear
(from trigonal bipyramidal) and
square planar with the same
terminal atom
115

POLAR
MOLECULES
Non-symetrical molecules
- basic molecules with different
terminal atom
- molecules with lone pairs except
linear and square planar

Exercises :
Predict the polarity of the following molecules:

SO2 ; HBr ; SO3 ; CH2Cl2 ; ClF3 ; CF4 ; H2O ;

XeF4 ; NF3 ; Cis-C2H2Cl2 ; trans-C2H2Cl2

116

4.3 ORBITAL OVERLAP AND

HYBRIDIZATION

1. Formation Covalent Bond

2. Formation Hybrid orbitals
3. Orbital Overlapping
117

Objectives
At the end of this subtopic, students should be
able to:
1. Draw and describe the formation of sigma(
and pi() bonds from overlapping of orbitals.
2. Draw and explain the formation of hybrid
orbitals of a central atom: sp, sp 2, sp3, sp3d, sp3d2
using appropriate examples.
3. Draw orbitals overlap and label sigma( and
pi() bonds of a molecule.
118

4.3.1

Valence Bond theory

explains the formation of covalent bonds

and the molecular geometry outlined by
the VSEPR.
States that a covalent bond is formed
when the neighboring atomic orbitals
overlap.
Overlapping may occur between:
a) orbitals with unpaired electrons
b) an orbital with paired electrons and
another empty orbitals (dative bond)
119

Example:
H

The s-orbital of the

Hydrogen atom

Change in electron
density as two hydrogen
atoms approach each
other.
High electron density
as the orbitals
overlap
120

(covalent bond
formed)
10.3

FORMATION OF COVALENT BOND

Valence bond theory - Covalent bond is formed
when two neighbouring atomic half-filled orbitals
overlap.
Two types of covalent bonds are

a) sigma bond ()
b) pi bond ()

121

a) bond
formed when orbitals overlap along its
internuclear axis (end to end overlapping)
Example:
i. overlapping s orbitals

122

H H

bond

ii.

Overlapping of s and p orbitals

Px orbital
H

bond

123

 iii. Overlapping of p orbitals

bond

124

b) bond
Formed when two p-orbitals of the same
orientation overlap sideways
y

125

bond

bond
126

Formation of bonds in a molecule

Covalent bonds may form by:
a) overlapping of pure orbitals
b) overlapping of hybrid orbitals

127

Overlapping of pure orbitals

Example :
i.
O2
ii.

128

N2

O2
Consider the ground state configuration:
O : 1s2 2s2 2p4

Two unpaired electrons to be

used in bonding.

y
1s

2s

2p

Overlapping occurs
between the p-orbitals of
each atom

129

130

N2

131

4.3.2

Formation Hybrid orbitals

Overlapping of hybrid orbitals and the pure orbitals

occur when different type of atoms are involved in
the bonding.

Hybridization of orbitals:
mixing of two or more atomic orbitals to form a new
set of hybrid orbitals

The purpose of hybridisation is to produce new

orbitals which have equivalent energy

Number of hybrid orbitals is equal to number of

pure atomic orbitals used in the hybridization
process.

132

Hybridization
Hybrid orbitals have different shapes
from original atomic orbitals
Types of hybridisation reflects the
shape/geometry of a molecule
Only the central atoms will be involved
in hybridisation

133

10.4

Hybridization of orbitals
i. sp
ii. sp2
iii. sp3
iv. sp3d
v. sp3d2
134

sp3 hybridization
one s orbital and three p orbitals are mixed to
form four sp3 hybrid orbitals
the geometry of the four hybrid orbitals is
tetrahedral with the angle of 109.5o .

135

sp3 hybrid
Mixing of s and three p orbitals
sp3

sp3

sp3
sp 3

136

Example:
1)

CH4

Lewis structure :
Valence orbital diagram ;
H:
C ground state :
C

excited

hybrid

:
:

Orbital Overlap :
Molecular Geometry :

137

Example : Methane, CH4

Ground state : C : 1s2 2s2 2p2
1s

2s

Lewis Structure

H
H C H
H

2p

Excitation: to have 4
unpaired electrons

H
sp3

Excited state :
1s

2s

2p

sp hybrid
3

shape: tetrahedral
138

sp3

sp3
sp

Fig. 10.8

sp3-Hybridized C atom in CH4

sp3
1s

sp3

sp3
sp3
1s

139

1s

Example 2 :

NH3
Lewis structure :
Valence orbital diagram ;
H:
N ground state :
N

excited

hybrid

:
:

Orbital Overlap :
Molecular Geometry :
140

Fig. 10.9

sp3

1s

sp3

sp3
sp3

1s
141

1s

Example:
3) H2O
Lewis structure :
Valence orbital diagram;
O ground state :
O

hybrid

Orbitals overlap:

142

sp2 hybridization
one s orbital and two p orbitals are
mixed to form three sp2 hybrid
orbitals
the geometry of the three hybrid
orbitals is trigonal planar with the
angle of 120o .

143

Fig. 10.12

px

sp2

py

144
one
s orbital + two p
orbitals

sp2
three sp2
orbitals

sp2

 simplified drawing of sp2 orbitals:

Shown together
(large lobes
only)

145

Example:
1) BF3
Lewis structure :
Valence orbital diagram;
F:
B ground state :
B

excited

hybrid

:
:

Orbital overlap:
146

Example: BF3
Pure p orbital

sp2

sp2

F : 1s22s22p5
sp2

Shape : trigonal planar

147

Example:
2) C2H4
Lewis structure :
Valence orbital diagram;
C ground state :
C

excited

hybrid

:
:

Orbital overlap:
148

Fig. 10.16a-c

bonds

bond
149

150

10.5

sp hybridization
one s orbital and one p orbital are
mixed to form two sp hybrid orbitals
the geometry of the two hybrid
orbitals is linear with the angle of
180o

151

Types of hybrid orbitals

Formation of sp Hybrid Orbitals

sp

sp

Produces linear
shape

152

10.4

Example:
1) BeCl2
Lewis structure :
Valence orbital diagram;
Cl :
Be ground state :
Be

excited

Be

hybrid

:
:

Orbital overlap:
153

Fig. 10.11

154

Example:
2) C2H2
Lewis structure :
Valence orbital diagram;
C ground state :
C

excited

hybrid

:
:

Orbital overlap:
155

Fig. 10.19a-c

156

Example:
3) CO2
Lewis structure :
Valence orbital diagram;
O:
C ground state :
C

excited

hybrid

:
:

Orbital overlap:
157

sp3d hybridization
one s orbital, three p orbitals and
one d orbital are mixed to form five
sp3d hybrid orbitals.
the geometry of the five hybrid
orbitals is trigonal bipyramidal with
the angle of 120o and 90o

158

 simplified drawing of sp3d orbitals:

159

Example:
1) PCl5
Lewis structure :
Valence orbital diagram;
Cl :
P ground state :
P

excited

hybrid

:
:

Orbital overlap:
160

Example:
2) ClF3
Lewis structure :
Valence orbital diagram;
F:
Cl ground state :
Cl

excited

Cl

hybrid

:
:

Orbital overlap:
161

sp d hybridization
3

one s orbital, three p orbitals and

two d orbitals are mixed to form six
sp3d2 hybrid orbitals
the geometry of the six hybrid orbitals
is octahedral with the angle of 90o

162

 Simplified drawing of sp3d2 orbitals:

163

Example:
1) SF6
Lewis structure :
Valence orbital diagram;
F:
S ground state :
S

excited

hybrid

:
:

Orbital overlap:
164

Example:
2) ICl5
Lewis structure :
Valence orbital diagram;
Cl :
I ground state :
I

excited

hybrid

:
:

Orbital overlap:
165

How do I predict the hybridization of the central atom?

Count the number of lone pairs AND the number
of atoms bonded to the central atom
No of Lone Pairs
+
No of Bonded Atoms

Hybridization

Examples

sp

BeCl2

sp2

BF3

sp3

sp3d

PCl5

sp3d2

SF6

166

CH4, NH3, H2O

10.4

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or

display.

167

Exercise:
For each of the following, draw the
orbital overlap to show the formation
of covalent bond
a) XeF2
b) O3
c) ICl4
d) OF2
168

4.4 Intermolecular
forces

LEARNING OUTCOMES
At the end of the lesson, students
should be able to;
1.

2.
3.

1.

Describe intermolecular forces

i. van der Waals forces :
- dipole-dipole interactions or permanent
dipole
- London forces or dispersion forces
ii. Hydrogen bonding
Explain factors that influence the strength of van der Waals
forces
Explain the effects of hydrogen bonding on
i. boiling point
ii. Solubility
iii. Density of water compared to ice
Explain the relationship between :
i. intermolecular forces and vapour pressure
ii. Vapour pressure and boiling point

4.4 Intermolecular
forces
4.4.1
Types of intermolecular
forces
4.4.2The effect of
intermolecular
forces
the physical
properties.

on

171

Intermolecular Forces
Intermolecular forces are the
attractive forces between
molecules

172

Effects of
intermolecular forces
on
physical
properties

Have effects on these physical

properties:
a) boiling point
b) melting point
c) solubility
d) density
e) electrical conductivity

173

Intermolecular Forces
Van der Waal
Forces

Between
covalent
molecules

Hydrogen
Bond
Between
covalent
molecules
with H
covalently
bonded to
F, O or N
174

4.4.1.1
van der
Waal Forces

Forces that act between covalent

molecules
Three types of interaction:
i. Dipole-dipole attractive
forces
- act between polar molecules
ii. London Dispersion forces
- act between non-polar
molecules

175

Dipole-dipole forces
(permanent dipole forces)
Exist in polar covalent compounds
Polar molecules have permanent dipole due
to the uneven electron distributions
Example:
-

Cl

Chlorine is more
electronegative,
thus it has higher
electron density

Cl

Dipole-dipole forces; the

partially positive end attracts
the partially negative end
176

4.4.1.2. London
Dispersion Forces
attractive forces that exist between nonpolar molecules
result from the temporary
(instantaneous) polarization of
molecules
The temporary dipole molecules will be
attracted to each other and these
attractions is known as the London
Forces or London Dispersion forces
177

The formation of London

forces
At any instant, electron distributions
in one molecule may be
unsymmetrical.
The end having higher electron
density is partially negative and the
other is partially positive.
An instant dipole moment that exists
in a molecule induces the
neighboring molecule to be polar.

178

Example:
London forces in
Electrons in a molecule
Br2

move randomly about the

nucleus

Br

At any instant, the

electron density might
be higher on one side
+

Br

Temporary
dipole molecule

Br

Br

Br

Br

The temporary dipole

molecule induce the
neighboring atom to
be partially polar

London forces

179

Factors that influence the

strength of the van der Waals
forces.
The molecular size/molecular mass
Molecules with higher molar mass have
stronger van der Waals forces as they tend to
have more electrons involved in the London
forces.
Example:
CH4 has lower boiling point than C2H6
Note:
However if two molecules have similar
molecular mass, the dipole-dipole interaction
will be more dominant.
Example: H2S has higher boiling point than

180

4.4.1.3 Hydrogen
intermolecular bond
Dipole-dipole interaction that acts between a
Hydrogen atom that is covalently bonded to
a highly electronegative atom ; F, O ,N in one
molecule and F,O or N of another molecule.
Example:

Hydrogen
intermolecular bond
181

Other examples:
NH3 liquid

H2O

..
H

Hydrogen
intermolecular bond

..
N
H

..
H

..

..

..

..

Hydrogen
intermolecular bond

Covalent bond

..

..

..
H

Hydrogen
intermolecular bond

182

Consider ethanol, CH3OH

CH3OH

CH3OH and methane

Hydrogen bond
..
..
H
O
O

..
O

..

in

Not a hydrogen
bond

..

..

H is not
bonded to
either F, O
or N

C
H

183

Example: H2O

___ covalent bond

----- hydrogen bond

H
O H

H
O H

O H

H
O H

184

185

Properties of compounds
with Hydrogen
intermolecular forces
Boiling point
Have relatively high boiling point than
compounds having dipole-dipole forces
or London forces
- the Hydrogen bond is the strongest
attraction force compared to the dipoledipole or the London forces.
186

Solubility
A. Dissolve in polar solvent
The molecules that posses
Hydrogen bonds are highly polar.
They may form interaction with
any polar molecules that act as
solvent.
B. Dissolve in any solvent that can
form Hydrogen bonds
187

Example

..

NH3 dissolves in water because it can form

Hydrogen intermolecular bond with water.

..

Hydrogen bond

..

..

N
H

188

Problem:
Explain the trend of boiling point given by the
graph below:
T/oC
HF

HBr

HI

HCl

Molecular mass

189

Answer
HF can form hydrogen bonds between molecules
while HCl, HBr and HI have van der Waals forces
acting between molecules. Hydrogen
intermolecular bond is stronger that the van der
Waals forces. More energy is required to break the
Hydrogen bond.
Boiling point increases from HCl to HI. The strength
of van der Waals forces increases with molecular
mass. Since molecular mass increases from HCl to
HI, thus the boiling point will also increase in the
same pattern.
190

The effect of Hydrogen bond

on water molecules
The density of water is relatively high
compared to other molecules with similar
molar mass.
Reason:
Hydrogen intermolecular bonds are
stronger than the dipole-dipole or the
London forces. Thus the water molecules
are drawn closer to one another and
occupy a smaller volume.
191

Density
Ice (solid H2O) has lower
density compared to its
liquid. Refer to the structure
of ice

Ice form tetrahedral arrangement

Hydrogen bond takes

one of the tetrahedral
orientation and occupy
some space

193

 H2O(l) is denser than H2O(s) because

the hydrogen bond in ice arrange the
H2O molecules in open hexagonal crystal
H2O molecules in water have higher
kinetic energy and can overcome the
hydrogen bond
V-shaped water molecules slide
between each other.

194

195

196

Fig. 11.13

197

Boiling points of substance

with Hydrogen
intermolecular bonds

The boiling points of these substances are

affected by:
a)
the number of hydrogen bonds per
molecule
b)
the strength of H intermolecular
forces which directly depends on
the polarity of the hydrogen bond
Example:
Explain the trend of boiling points given below:
The order of the increase in boiling point is:
H2O > HF > NH3 > CH4
198

Answer:
by looking at the polarity of the bond, we have
(Order of polarity: HF > H2O > NH3)
but H2O has the highest boiling point.
For H2O, the number of hydrogen bonds per molecule
affects the boiling point.
Each water molecule can form 4 hydrogen bonds with
other water molecules. More energy is required to
break the 4 Hydrogen bonds.
HF has higher boiling point than NH3 because F is
more electronegative than Nitrogen.
CH4 is the lowest - it is a non polar compound and
has weak van der Waals forces acting between
molecules.
199

Effects of intermolecular forces on

physical properties
1) Boiling point
For molecules with similar size, the order of
intermolecular strength:
Hydrogen bond > dipole-dipole forces >
London dispersion forces
Strength of intermolecular forces
boiling point

200

201

Why boiling point H2O > HF

and HF > NH3?
Fluorine is more electronegative than
oxygen, therefore stronger hydrogen
bonding is expected to exist in HF liquid than
in H2O.
However, the boiling point of H2O is higher
than HF because each H2O molecules has
4 hydrogen bonds.
202

 On the other hand, H-F has only 2 hydrogen

bonds.
Therefore the hydrogen bonds are stronger
in H2O rather than in H-F.

203

Boiling point HF > NH3

Fluorine is more electronegative than
nitrogen ,thus the hydrogen bonding in H-F
is stronger than H-N.

204

Vapour Pressure
Molecules can escape from the surface of liquid
at any temperature by evaporation

in a closed system :

vapour molecules which leaves the

surface cannot escape from the
system
the molecules strike the container wall
and exert some pressure

Fig. 11.34

 The pressure exerted by those molecules is

called vapour pressure (or maximum vapour
pressure)

Vapour pressure is the pressure exerted

by a vapour in equilibrium with its liquid
phase.

In a close system
.

Liquid molecules vapourise

Molecules have enough energy to

overcome intermolecular forces

Vapour molecules are trapped

in the close container
Volume of liquid becomes less

Rate of vaporisation is faster

than the rate of condensation

Some of the vapour molecules may

collide and lose their energy. They
re-enter the liquid surface

System reaches equilibrium

dynamic equilibrium
Volume of liquid remains
constant

Rate of vapourisation is equal to

the rate of condensation
Pressure exerted by the vapour
molecules is known as the vapour
pressure

Dynamic equilibrium and vapour

pressure
Number of liquid
molecules leaving the
surface is the same as
the number of vapour
molecules entering
the liquid surface.

The vapour pressure

at this stage is
constant and known
as the equilibrium
vapour pressure.

Dynamic equilibrium is reached when:

Rate of evaporation = rate of condensation
Note:
Equilibrium vapour pressure = saturated vapour pressure
= vapour pressure

Factors that affects vapour

pressure

i. Intermolecular forces

Molecules with weak intermolecular forces can easily

vapourise. More vapour molecules will be present and
exert higher pressure.

the weaker intermolecular forces the higher is

the vapour pressure.
ii. Temperature
Heating causes more molecules to have high kinetic
energies that are higher than their intermolecular forces.
More liquid molecules will form vapour.
vapour pressure increases with temperature.

Fig. 11.35

Boiling the process

Increasing the temperature will increase in the vapour
pressure.
As heat is applied, the vapour pressure of a system
will increase until it reaches a point whereby the
vapour pressure of the liquid system is equal to the
atmospheric pressure.
Boiling occurs and the temperature taken at this point
is known as the boiling point.
At this point, the change of state from liquid to gas
occurs not only at the surface of the liquid but also in
the inner part of the liquid.
Bubbles form within the liquid.

 Boiling Point:
the temperature at
which the vapour pressure of a liquid is
equal to the external atmospheric
pressure.
Normal Boiling Point: the temperature
at which a liquid boils when the external
pressure is 1 atm (that is the vapour
pressure is 760 mmHg)

Factors affecting the boiling point:

1.

Intermolecular forces

A substance with weak intermolecular

forces can easily vapourise and the system
requires less heat to achieve atmospheric
pressure, thus it boils at a lower temperature.
2.
Atmospheric pressure
When the external atmospheric pressure is
low, liquid will boil at a lower temperature.

4.5

Metallic bond

L E A R N IN G O U T C O M E S
A t th e e n d o f th e le s s o n , s tu d e n ts s h o u ld b e
a b le to ;
1.
2.

3.
4.

E x p la in t h e f o r m a t io n o f m e t a llic b o n d b y u s in g
e le c tr o n s e a m o d e l.
R e la t e m e t a llic b o n d t o t h e p r o p e r t ie s o f m e t a l:
i. m a lle a b ilit y
ii. D u c t ilit y
iii. E le c t r ic a l c o n d u c t iv it y
iv . T h e r m a l c o n d u c t iv it y
E x p la in t h e f a c t o r s t h a t a f f e c t th e s t r e n g th o f m e ta llic
bond
R e la t e t h e s t r e n g t h o f m e t a llic b o n d to b o ilin g p o in t

Metallic bond
An electrostatic force between
positive charge metallic ions and the
sea of electrons.
Bonding electrons are delocalized
over the entire crystal which can be
imagined as an array of the ions
immersed in a sea of delocalized
valence electron.
217

Metallic bonds
Positive
ions are
immersed in
the sea of
electrons

Free
moving
electrons

218

Electrostatic force in a
metal
Metallic Bond (Electron-sea Model)
Metals form giant metallic structure
Each positive ion is attracted to the
sea of electrons.
These atoms are closely held by the
strong electrostatic forces acting
between the positive ions and the sea
of electrons.
These free moving electrons are
responsible for the high melting point
of
metals
and
the
electrical
conductivity.
219

Physical properties of metals

metals have high melting point
high energy is required to overcome these
strong electrostatic forces between the
positive ions and the electron sea in the
metallic bond
+ e + e + e
e + e +
e
e
e

+
+

e
e

+ e + e
+ e +
e
+

+ e + e

Metallic bonds formed

by the electrostatic
forces exist between
positive ions and the
free moving electrons

220

The strength of the

metallic bonds
The strength of the metallic bond
increases with the number of valence
electrons and the size of ions.
The smaller the size of positive ions the
greater is the attractive force acting
between the ions and the valence
electrons

221

Boiling points in metals

Mg

Na
e

+1

+1
e
+1

e
+1

+1
e

e
+1

+1

+1

e
e
+1 +1

+1
e

+1

+1
e

+1

+1

e
e
e
+1 +1 +1

Has one valence electron

the electrostatic force acting
between positive ions and
free moving electrons form
metallic bonds

ee ee ee ee ee
+2 +2 +2 +2 +2
ee ee ee ee ee
+2 +2 +2 +2 +2
ee ee ee ee ee
ee
+2 +2 +2 +2 +2

ee ee ee
+2 +2 +2
ee ee ee
+2 +2 +2
ee ee ee
+2 +2 +2

Has 2 valence electrons

Stronger metallic bond due to the
size of Mg being smaller than Na
and the strong electrostatic force
between +2 ions and the two
valence electrons,

Mg has higher boiling point than Na

222

Example:
Explain the difference in the
boiling point of the two metals
given:
Magnesium 11300 oC
Aluminum 24500 oC

223

Answer
The cationic size of Al is smaller
compared to magnesium and its
charge is higher (+3).
Mg has two valence electrons
Al has three valence electrons
involved in the metallic bonding.
The strength of metallic bond in
Aluminium is greater than that of
Magnesium
Al has higher boiling point
224

The strength of metallic bond is

directly proportional to the boiling
point.
The stronger metallic bond,the
higher the boiling point.

225