CHAPTER 4 :

CHEMICAL BONDING

4.1 LEWIS STRUCTURE

1
 LECTURE 1

Learning outcomes:

(a) Write the Lewis symbol for an

atom.

(b) State the octet rule and describe

how atoms obtain the octet
configuration.

2
Valence electrons are the outer shell electrons
of an atom.The valence electrons are the
electrons that participate in chemical bonding.
Group e- configuration # of valence e-
1 ns1 1
2 ns2 2
13 ns2np1 3
14 ns2np2 4
15 ns2np3 5
16 ns2np4 6
17 ns2np5 7
3
 Lewis symbol

• Consist of the symbol of an element

• One dot or one cross for each valence
electron in an atom of the element
• Element in the same group have similar
outer electron configuration
– Similar Lewis symbol
– Example ;
– Li and X Na
4
Group 1 2 13 14 15 16 17 18

Valence 1 2 3 4 5 6 7 8
electron

Lewis .. . . ..
: Be : B . : C: . N. : O. : F: :Ne:
symbol Li.
. .. .. ..

5
Lewis Symbols

6
 OCTET RULE

-Atoms combine in order to achieve a more stable

electronic configuration.

-Maximum stability results when an atom is

isoelectronic with a noble gas.

- Atom can achieve noble gas configuration

through :
( a) transfer of electron (gaining or losing)
( b) sharing of electron 7
 THE ELECTRON
CONFIGURATION OF IONS
Ions have stable electronic configuration of
either:

The noble gas configuration

Pseudonoble gas configuration
Half-filled orbitals
The inert pair effect
8
 (a) Noble gas configuration

Group 1, 2 and 13 elements transfer

valence e- to form cation with noble gas
configuration.

Example
Na : 1s22s22p63s1
Na+ : 1s22s22p6 ( isoelectronic with neon )

Mg : 1s22s22p63s2
Mg2+: 1s22s22p6 ( isoelectronic with neon )
9
Group 15, 16 and 17 elements accept e to
form anion with noble gas configuration.

Example
O : 1s22s22p4
O2- : 1s22s22p6 ( isoelectronic with neon )

F : 1s22s22p5
F- : 1s22s22p6 ( isoelectronic with neon )

10
(b) Pseudo noble gas configuration

-For d block elements, e from 4s orbital will

be transferred first before the 3d electrons.

-d block elements donate electrons to achieve

pseudonable gas configuration

Example :
Zn : 1s22s22p63s23p64s23d10
Zn2+ : 1s22s22p63s23p63d10
( pseudonoble gas configuration )
11
• Pseudo means false
• So, pseudonoble gas means that the atom
has similar electron configuration with noble
gases
• The valence electron configuration needed
is either ns2np6nd10 or ns2np6nd10nf14

12
(c) Half-filled orbital

-d block element can also donate or receive

electron to achieve half-filled orbitals which is
stable

Example :
Mn : 1s22s22p63s23p64s23d5
Mn2+ : 1s22s22p63s23p63d5
( stability of the half-filled orbital)

Fe : 1s22s22p63s23p64s23d6
Fe3+ : 1s22s22p63s23p63d5 13
( stability of the half-filled orbital)
(d) The inert pair effect

- elements Group 13 and 14 in Period 5 or 6

form cations with configuration of,
ns2np6nd10(n+1)s2
- This is named the inert pair effect.

Example :
Sn : [ Kr ] 4d105s25p2
Sn2+ : [ Kr ] 4d105s2

( the inert pair effect )

14
 LECTURE 2
Learning outcomes:
(c) Describe the formation of the
following bonds using Lewis symbol.
i. Ionic or electrovalent bond
ii. Covalent bond
iii. Dative or coordinate bond
(d) Draw Lewis structure of covalent species
with single, double and triple bonds.
(e) Compare the bond length between single,
double and triple bonds. 15
 Ionic or electrovalent bonding

 Electrostatic attraction force between

positive ion (cation) with negative ion
(anion)
 eg . Formation of NaCl .
Na – e- Na+ Na+Cl-
(metal) (cation) Ionic bond

Cl + e- Cl-
(non-metal) (anion)
16
The formation of electrovalent bonds,

1. An ionic bond is formed by the electrostatic forces.

2. Ionic bond formed between 2 ions with different

charge and through electron transfer.

3. Metal elements will donate electron while nonmetal

elements receive electron to achieve stability.

4. This happen because metals are more electropositive

while non metals more electronegative.

17
Example :

Na Na+ + e-
1s22s22p63s1 1s22s22p6
(obey the octet rule)

Cl + e- Cl-
1s22s22p63s23p5 1s22s22p63s23p6
(obey the octet rule)

18
 Formation can be described by Lewis
structure – valence e- represented as
dot or cross.

+ -
xx xx
Na• x Cl xx Na •x Cl xx
xx xx
(formation of
NOTE: electrovalent bond )
Remember to show arrow
from donater to accepter!!!
19
Properties of electrovalent
compound
Solid at room temperature
High melting/ boiling point
Soluble in water
Molten ionic compounds conduct
electricity because they contain
mobile ions ( cations & anions)

20
Excercise (ionic bond):

Draw Lewis structure for the formation of following

ionic compounds.

a) KF . ..
K . +  F  [ K ]+ [  F  ]-
.. ..
-When K and F atoms come in contact with each other,
the outer 2s1 valence electron of K is transferred
to F atom.
21
b) BaO
. ..
Ba + O  [ Ba ]2+ [  O  ]2-
. ..

When Ba and O atoms come in contact with each

other, 2 e of 2s orbital of Ba are transferred to O.

c) Na2O
Na . . ..
+ O 2[ Na ]+ [  O  ]2-
. ..
Na .
22
 Covalent Bond

Formed by sharing 1 or more pairs of

valence electrons between nonmetal
atoms (group 14 , 15 , 16 , 17 ,18)

23
 Why should two atoms share electrons?

F + F F F
7e- 7e- 8e- 8e-

Lewis structure of F2

single covalent bond lone pairs F F lone pairs

single covalent bond

lone pairs F F lone pairs

24
 Coordinate covalent or dative
bond
Defination: A bond in which the pair of
electrons is supplied by one of the two
bonded atoms
Eg: hydroxonium ion, H3O+
.. +
:O: + H+ O
H H H H
H
25
Eg : F3BNH3 molecule
BH3 + NH3 H3BNH3

F F
..
B + N B
H
F F H F F
H
N
H H
H
26
 Single Bond
• A covalent bond formed when 2 atoms
share a pair of electrons
• Represent by dash (-) between 2 atom
• A single bond is made up of a sigma (σ)
bond
• Example: HCl and HF

27
 Double Bond
• A covalent bond formed when 2 atoms
share 2 pairs of electrons
• Represent by double dash (=) between 2
atoms
• A double bond is made up of sigma bond
(σ) and pi bonds (π)
• Example: O2

28
 Triple bond
• A covalent bond formed when 2 atoms
share 3 pairs of electrons
• Represent by triple dash (Ξ) between 2
atoms
• A triple bond is made up of 1 sigma bond
(σ) and 2 pi bonds (π)
• Example : N2

29
Lewis structure of water single covalent bonds

H + O + H H O H or H O H
2e-8e-2e-

Double bond – two atoms share two pairs of electrons

O C O or O C O
8e- 8ebonds
double - 8e- double bonds

Triple bond – two atoms share three pairs of electrons

N N or N N
8e-8e
triple -
bond
triple bond
30
Comparison of the bond length between
single, double and triple bonds.

• Multiple bonds are shorter than

single covalent bonds.
• Bond length is defined as the
distance between the nuclei of
two covalently bonded atoms in
a molecule. Refer figure given.

31
• For a given pair of atoms such as
carbon and nitrogen, triple
bonds are shorter than double
bond, which, in turn are shorter
than single bond. Refer table
given.

32
 74pm 161pm

H2 HI
Figure : Bond length in H2 and HI

33
Bond Type Bond Bond Type Bond
length(pm) length(pm)
C-H 107 C-O 143
C=O 121 C-C 154
C=C 133 C≡C 120
C-N 143 C=N 138
C≡N 116 N-0 136
N=O 122 O-H 96

Table : Comparison of the bond length

34
 LECTURE 3

Learning outcomes:
f) Determine the formal charge and the
most plausible Lewis structure.
g) Explain the exception to the octet
rule: incomplete octet, expanded
octet and odd number electrons.
h) Explain the concept of resonance
using appropriate examples.
35
36
 formal charge = valence e – (no. lone pair e +
½ no. bond-pair e)

.. ..
C O Cl: formal charge C = 4-[4+½(4)] = -2
.. ..
:Cl: formal charge O = 6-[0+½(8)] = 2
..
formal charge Cl = 7-[6+½(2)] = 0
structure A
Formal charge Cl = 7-[6+½(2)] = 0

37
formal charge = valence e – (no. lone pair e +
½ no. bond-pair e)

.. ..
:O: C Cl: formal charge C = 4-[0+½(8)] = 0

:Cl:
.. formal charge O = 6-[6+½(2)] = -1

formal charge Cl = 7-[4+½(4)] = +1

Structure B formal charge Cl = 7-[6+½(2)] = 0

38
 formal charge = valence e – (no. lone pair e +
½ no. bond-pair e)
eg :
..
:O
.. C Cl:
.. formal charge C = 4-[ 0+½(8)] = 0

:Cl:
.. formal charge O = 6-[4+½(4)] = 0

formal charge Cl = 7-[6+½(2)] = 0

Structure C
formal charge Cl = 7-[6+½(2)] = 0

39
Conclusion …
Refer to the obtained formal charge,
the most plausible structure is…

Figure C

40
Exercise 1:
Calculate the formal charge for
each atoms of NOCl molecule
Answer

41
Exercise 2:
Draw the right Lewis structure
of CO2.

Answer

42
Exception to the octet rule
 In octet configuration , atom should
have e configuration of noble gas
But…there’s an exception
* incomplete octet
* expanded octet
*odd electron molecule

43
 Incomplete octet

Elements in groups 2 & 13

Period 2
Less metallic character
Do not donate e but share e
 Central atom have less than 8 e (not achieve
octet configuration)

44
Eg : BeCl2
... .. .. ..
: Cl
.. + Be . ..:
+ Cl :Cl
.. . Be . Cl
..:
Be shared e with Cl (covalent bond) but in
BeCl2 molecule Be only have 4 e in the
outer shell (less than 8 e, does not achieve
octet configuration)

45
 Expanded Octet

 Involves period 3 and onwards (non

metals)
 Has d orbital that involves in bonding
Central atoms having 10 or even 12
valence e.

46
eg : SF6 S shared e with F (covalent
F bond) but in SF6
molecule S have 12 e in
F F the outer shell (more
S
than 8 e, does not obeys
F F octet rule)
F

47
 PF5
F
F
F P
F
F
P shared e with F (covalent bond) but
in
PF5 molecule P have 10 e in the outer
shell
(more than 8 e, does not obeys octet
rule) 48
 Odd electron molecule
• Molecule with odd no. of e, complete pairing is
impossible and an octet around each atom
cannot be achieved
• Mostly from an odd numbered group
( Nitrogen- Group 15, Chlorine-Group 17)
• Example : nitric oxide (NO) and nitrogen dioxide
(NO2) :
•• •• •• •+ •• -
N=O O=N-O

••
• •• •• ••
• Since we need even no. of electrons for complete
pairing (to reach 8)
• The octet rule cannot be satisfied for all the
49
atoms in any of these molecule
 -Same atomic structure but different
arrangement of e
- Resonance structure : 2 or more Lewis
structure for single molecule that cannot be
represented with 1 accurate Lewis structure
Eg:
Sulphur dioxide, SO2

.. .. .. .. ..S ..
: ..O S ..O ..O ..O :
50
 eg : C6H6

 In resonance structure, double bond

and single bond are equal in length.

51
A resonance structure is one of two or more Lewis structures
for a single molecule that cannot be represented accurately by
only one Lewis structure.

+ - - +
O O O O O O

What are the resonance structures of the

carbonate (CO32-) ion?

- - - -
O C O O C O O C O

O O O 52
- -
NO3-

53
54
Answer to exercise 1:
Calculate the formal charge for each atoms
NOCl molecule
Formal charge Atom
F.C = 6 – [4+ ½ (4)]
O= =6–6=0
F.C = 5 – [2 + ½ (6)]
=N- =5–5=0
F.C = 7 – [6+ ½ (2)]
- Cl =7–7=0

55
Answer to Exercise 2:
Draw the right Lewis structure of CO2.

2 possible structures of CO2.

Structure CO2 Formal charge
A .. :O≡ FC = 6 – [ 2 + ½ ( 6 ) ]
: O ≡ C –O : =6–5
.. =1
≡ C- FC = 4 – [ 0 + ½ ( 8 ) ]
=4–4
=0
..
- O: FC = 6 – [ 6 + ½ ( 2 ) ]
.. =6–7
= -1 56
 .. .. ..
B O=C=O O= FC = 6 – [ 4 + ½ ( 4 ) ]
.. .. .. =6–6
=0
=C= FC = 4 – [ 0 + ½ ( 8 ) ]
=4–4
=0

Conclusion: Structure B is the most plausible Lewis

structure because the formal charges for
each atoms for this structure is zero.

57
4.2 MOLECULAR SHAPE
AND POLARITY

LECTURE 4
LECTURE 5

58
 At the end of this lesson, students
should be able to :
(a) Explain Valence Shell Electron Pair
Repulsion theory (VSEPR)
(b) Draw the basic molecular shapes: linear,
trigonal planar, tetrahedral, trigonal
bipyramidal and octahedral.
(c) Predict and explain the shapes of
molecule and bond angles in a given
species.
59
 .. ..
:F.. - N - F: Lewis structure
..
:F:
..

No. of e surrounding a central atom

Assumption: e pairs/bonding pair in the

valence shell repel one
another

Study of
VSEPR!! molecular Gives the position
geometry of all atoms 60
- The 3D arrangement of atoms in a molecule.
- affects physical and chemical properties.
- predicted by using Valence Shell Electron Pair
Repulsion (VSEPR) model.

- The study of molecular geometry

states “The valence electron pairs surrounding a
central atom repel one another. Thus, the orbital
containing those electron pairs are oriented to be
as far apart as possible”.
61
Divide molecules into 2 categories:

 Central atom has No Lone Pairs

.. ..
O=C=O
.. ..
 Central atom has ≥1 Lone Pairs
.. .. ..
:F-N-F:
.. ..
:F:
..
62
BASIC MOLECULAR SHAPE

• Linear
• Trigonal Planar
• Tetrahedral
• Trigonal bipyramidal
• Octahedral

63
 # of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear

B B

64
 •Bond angle = 180°

Cl Be Cl •Atoms arranged in a
straight line
2no
atoms
lone pairs
bondedon to
central
central
atom
atom •Eg: BeCl2, HgCl2 65
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear

trigonal trigonal
AB3 3 0
planar planar

66
 120°
•Bond angle = 120°
•Central atom has 3 terminal atoms
•Eg: BF3 67
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear

trigonal trigonal
AB3 3 0
planar planar
AB4 4 0 tetrahedral tetrahedral

68
•Bond angle = 109.5°
•Central atom has 4 terminal atoms
69
•Eg: CH4
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear

trigonal trigonal
AB3 3 0
planar planar
AB4 4 0 tetrahedral tetrahedral
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal

70
•Bond angle = 90°, 120°
•Central atom has 5 terminal atoms
71
•Eg: PCl5
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear

trigonal trigonal
AB3 3 0
planar planar
AB4 4 0 tetrahedral tetrahedral
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
AB6 6 0 octahedral octahedral

72
•Bond angle = 90°
•Central atom has 6 terminal atoms
73
•Eg: XeF6
-Geometry of molecule is more complicated if
the central atom has both lone pairs and
bonding pairs.

-3 types of repulsive forces:

 those between bonding pairs
 those between lone pairs
 those between a bonding
pair & lone pair
74
bonding-pair vs. bonding lone-pair vs. bonding < lone-pair vs. lone pair
pair repulsion < pair repulsion repulsion 75
 # of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

trigonal trigonal
AB3 3 0
planar planar
trigonal
AB2E 2 1 bent
planar

76
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB4 4 0 tetrahedral tetrahedral

trigonal
AB3E 3 1 tetrahedral
pyramidal

77
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB4 4 0 tetrahedral tetrahedral

trigonal
AB3E 3 1 tetrahedral
pyramidal

AB2E2 2 2 tetrahedral bent

O
H H

78
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
trigonal distorted
AB4E 4 1
bipyramidal tetrahedron

79
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
trigonal distorted
AB4E 4 1
bipyramidal tetrahedron
trigonal
AB3E2 3 2 T-shaped
bipyramidal
F

F Cl

F
80
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB6 6 0 octahedral octahedral

octahedral square
AB5E 5 1
pyramidal
F
F F
Br
F F

81
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
trigonal distorted
AB4E 4 1
bipyramidal tetrahedron
trigonal
AB3E2 3 2 T-shaped
bipyramidal
trigonal
AB2E3 2 3 linear
bipyramidal
I

I
82
I
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB6 6 0 octahedral octahedral

octahedral square
AB5E 5 1
pyramidal
octahedral square
AB4E2 4 2
planar
F F
Xe
F F

83
84
85
86
Predicting Molecular Geometry
1. Draw Lewis structure for molecule.
2. Count number of lone pairs on the central atom and
number of atoms bonded to the central atom.
3. Use VSEPR to predict the geometry of the molecule.

e.g: What are the molecular geometries of SO2 and SF4?

O S O F

AB2E AB4E
F S F
distorted
bent tetrahedron
F
87
Excercise:
Use the VSEPR model to predict the geometry of the
following molecules and ions:
a)C2H4 b) OF2

c) AlCl-4 d) AsH3

88
Lecture 6

89
 Learning Outcomes
At the end of the lesson the students should be able to:

1. Explain bond polarity and dipole moment.

2. Deduce the polarity of molecules based on the shapes and the resultant
dipole moment.

90
When a negatively charged rod is brought close to a thin stream of water,
deflection occurs.

91
Polar bond
A bond between atoms of different electronegativities in which the
distribution of the density of the bonding electron pair is asymmetrical.

92
Patterns of electronegativity in the Periodic Table

The most electronegative element is fluorine.

Electronegativity always increase towards fluorine

in the Periodic Table.

93
Polar molecule

A dipole molecule in which the positive

and negative pole can be distinguished
(because of the separation of the charge).

Example:

 + 
O = C = O polar or nonpolar?

94
 Polar Molecules

electron rich
electron poor
region
region

H F

+ 

95
Dipole moment (µ)?

- A measure of molecular polarity

m=qxr

q = charge (coulomb)
r = the distance between charges (m)
1 D = 3.36 x 10-30 C m

- A polar molecule has µ ≠ 0

Non-polar molecule has µ = 0

96
•The direction of polarity of a polar bond can be symbolised by a vector
quantity
( ).

•The crossed end of the arrow is the positive end and the arrow head is
the negative end.

H  Cl

97
Example:

+ 
H  Cl µ≠0

 + 
O = C = O µ=0

98
 Covalent bond between same atoms

 Covalent bond between atoms of the same

element is nonpolar
→ nonpolar molecule.

 Bonding electrons are shared equally.

Example:

F2 : F─F
O2 : O─O
O3 : O─O─O
N2 : N─N 99
 Covalent bond between different atoms

 Covalent bond between different atoms

is polar.
- bonding electrons closer to the more
electronegative atom.

 However, molecules could be polar or

nonpolar, depending on its shape.

100
Determining polar and nonpolar molecules

Use the three-step approach outlined below :

 Use electronegativity values to predict bond
dipoles.
 Use the VSEPR method to predict the
molecular shape.
 From the molecular shape, determine
whether bond dipoles cancel to give a non-
polar molecule or combine to produce a
(resultant dipole moment) for the molecule.

101
Molecules with different atoms & asymmetrically arranged are polar.

Example:

+ 
H  Cl

102
 Molecules with different atoms, symmetrically
arranged but having µ = 0 are nonpolar.
Example:

In CCl4, each bond is polar.

The molecule as a whole, however, is nonpolar
103
Example:

In SF6, each bond is polar.

The molecule is nonpolar

104
 Molecules with different atoms, symmetrically
arranged but having µ ≠ 0 are polar.

Example:

The molecule is polar because µ ≠ 0 .

The dipole moment arises because the difference
in electronegativity.
105
Example: Chloromethane ( CH3Cl)

Cl

C
H
H

The molecule is polar because µ ≠ 0 .

The dipole moment arises because the difference
in electronegativity.
106
 Molecules with lone pairs on the central atom

Let us consider
the molecules in
which there are
lone pairs on the
central atoms.

Note: Molecules which have lone

pairs are usually polar.
107
Example: Ammonia
( effect of lone pairs )



Net dipole
moment
m  0

N
H H
H
108
109
 Which of the following molecules have a dipole
moment?
H2O, CO2, SO2, and CH4
S

O
dipole moment
dipole moment polar molecule
polar molecule
H

C
O C O H
H
no dipole moment H
nonpolar molecule no dipole moment
nonpolar molecule
110
Exercise 1
Indicate the direction in which the shared
electron pair is shifted in the molecules given
below.

111
Answer:

112
Exercise 2

Predicting the polarity of molecules.

State which of them are polar and which are
nonpolar.
a) H2O
b) NH3
c) CCl4
d) CHCl3

113
Answer:

polar molecules:
H2O, NH3, CHCl3
non-polar molecule:
CCl4

114
LECTURE 7

115
 Learning Outcomes

At the end of the lesson the students

should be able to:

1. Draw and describe the formation of

sigma (σ) and pi (π) bonds from
overlapping of orbitals.

2. Draw orbitals overlap and label sigma

(σ) and pi (π) of a molecule.

116
 Valence bond theory
Valence bond theory is based on the
following four postulates:

Postulate 1:
A bond is formed when atomic valence
orbitals overlap with each other.

117
Postulate 2:
Overlapping orbitals contain a pair of
electrons.

Postulate 3:
Electron density concentrates between
bonded atoms.

118
Postulate 4:
The strength of the bond depends on the
degree of overlapping.

119
 Covalent bond is formed when atomic
orbitals overlap.

 Only 2 electrons with their spins paired

may be shared in one set of overlapping
orbitals.

 2 types of bond:
• sigma bond (σ)
• pi bond (π)
120
The simplest molecule we can discuss in
terms of valence bond theory is a
hydrogen gas, H2

121
- Sigma bond occurs when there is one
bonding interaction that results from the
overlapping of two orbitals.

- A bond can result from overlapping end

to end of atomic orbitals on neighbouring
atoms.

122
(i) Result from the overlapping of two s orbitals.

Example: H2
H : _
1s

123
(ii) Result from the overlapping of s and p
orbitals.
Example: HF

124
 H : _
1s
F : _ ___
2s 2p
valence electrons

• One of the 2p orbital of F atom is occupied

by a single electron.
• H electron and the F electron pair up and
be shared between the two nuclei.
125
126
iii) Result from overlapping of two p orbitals.

Example: Cl2

Cl : _ _ ___ _ ___
1s 2s 2p 3s 3p

valence electrons

- One of the 3p orbitals is

occupied by a single e

127
Cl Cl Cl - Cl
+ 
3p 3p

128
Example 2: F2

129
 Two lobes of p orbitals overlap side-to-side
gives pi bond (sideways overlapping of two p
orbitals).

 It occurs in molecules with double or triple

bonds


130
Example: N2

N : _ _ ___
1s 2s 2p
valence electrons
pz pz
π
py
π
px px
σ

py
N  N
131
Example 2:
Nitrogen monoxide ion, NO+
The Lewis structure is :N ≡ O:+
There is a σ bond and two π bonds.

7N : _ _ ___
1s 2s 2p
valence electrons
O + : _ _ ___
8
1s 2s 2p
132
valence electrons
 pz pz
π
py
π
px px
σ

py
N  O

133
Exercise 1:

Give the number of σ and π bonds in:

a) N2 molecule
b) O2 molecule
c) F2 molecule

134
Answers:

a) 1 sigma bond, 2 pi bonds

b) 1 sigma bond, 1 pi bond
c) 1 sigma bond

135
 Conclusion

The formation of a sigma bond:

1. Formed by overlapping of s orbitals

2. Formed by overlapping of s and p orbitals.
3. Formed by head-to-head overlapping of p orbitals.

The formation of a pi bond:

1. Formed by side-to-side overlapping of p orbitals.

136
 Lecture 8 and 9
Learning Outcomes

At the end of the lesson the students should

be able to:

• Draw and explain hybrid orbital of a

central atom : sp, sp2, sp3, sp3d, and sp3d2.
• Use appropriate examples.

137
 Terms:
• Hybridization – the process of mixing
two or more orbitals to form a set of
new orbitals of identical shape and
energy.

• Hybrid orbitals – atomic orbitals

obained when two or more nonequivalent
orbitals of the same atom combine.

138
 There are 5 types of hybrid orbital:
1. sp hybridization – are formed from one s orbital and
one p orbital (linear shape).

2. sp2 hybridization – are formed from one s orbital and

two p orbitals (trigonal planar shape).

3. sp3 hybridization – are formed from one s orbital and

three p orbitals (tetrahedral shape).

4. sp3d hybridization – are formed from one s orbital,

three p orbitals and one d orbital (trigonal bipyramidal).

5. sp3d2 hybridization – are formed from one s orbital,

three p orbitals and two139d orbitals (octahedral shape).
 sp3 hybridization
• The sp3 hybrid orbitals - one s orbital and
three p orbitals .

• These four hybrid orbitals are directed

towards the four corners of a regular
tetrahedral shape

• all the angles are 109.50

140
+

141
142
143
 Hybridization of carbon atom in
methane ( CH4)

• The carbon atom has two unpaired electrons

(one in each of the two 2p orbitals).

144
• The orbital diagram for valence
electron in carbon atom is

Ground state C:
2s 2p

145
• It can form only two  bonds with
hydrogen in its ground state.

• Four C –H bonds in methane, one

electron from the 2s orbital has to be
excited to unoccupied 2p orbital.

Excited state C:
2s 2p

146
• In the exited state there are four unpaired
electrons in carbon atom. The 2s orbital
and 2p orbitals mix to form sp3 hybrid
orbitals.

Hybrid state C:
sp3

147
• The four sp3 hybrid orbitals of carbon
overlap with s orbital of hydrogen to
form  bonds in methane molecule.

148
 Hybridization of C atom in CH4

Ground State :
2s 2p

Excited State:
(Promotion of e) 2s 2p

sp3–hybridized state :
sp3
149
150
 Hybridization of nitrogen atom in
ammonia ( NH3 ).

• The orbital diagram for valence

electrons in nitrogen atom is

Ground state N:
2s 2p

151
• The nitrogen atom has three unpaired
electrons. The electron will not be
promoted from 2s orbital to 2p orbital.

However 2s and 2p orbitals hybridize to

form sp3 orbitals.

Hybrid state N:
sp3

152
• Overlapping of sp3 orbitals with s orbital
of hydrogen atoms to form sigma bonds.

• Three of the four hybridize orbitals form

covalent N-H bonds

• The fourth hybrid orbital accommodates

the lone pair electrons in nitrogen

153
 Hybridization of N atom in NH3

Ground State :
2s 2p

sp3–hybridized state :
sp3

154
 

155
 Hybridization of oxygen atom in
water ( H2O)

• The H2O molecule has a V-shaped

geometry based on VSEPR .

• The orbital diagram for the valence

electrons in oxygen atom is :

Ground state O:
2s 2p

156
• The 2s and 2p orbitals hybridized to
form sp3 hybrid orbitals.

Hybrid state O:
sp3

157
 Hybridization of O atom in H2O

Ground State :
2s 2p

sp3–hybridized state :
sp3

158
Formation of water molecule

(i) (ii)

159
(iii) (iv)

160
(v) (vi)

161
 sp2 hybridization
• Mixing the s orbital with the two p
orbitals to form three sp2 hybrid
orbitals.

• These three sp2 orbital lie in the same

plane and the angle between any two of
them is 120o.

162
Formation of sp2 Hybrid Orbitals

163
164
 Boron triflouride ( BF3 )
molecule

• Orbital diagram for the valence electron

in boron is

Ground state B:
2s 2p

165
• Boron atom has one unpaired electron
and can form only one bond with other
orbital.
• This will form a very unstable BF
molecule.
• The electron in 2s orbital is promoted
to an unoccupied 2p orbital.

Excited state B:
2s 2p

166
• The mixing the 2s orbital with the two
2p orbitals form three sp2 hybrid
orbitals.

Hybrid state B:
sp2

167
• Overlap of boron sp2 hybrid orbitals and
2p orbital flourin atom to form sigma ( )
bond in each of the BF bond.

• The BF3 molecule is planar with all the

FBF angle equal to 120o .

168
 Hybridization of B atom in BF3

Ground State :
2s 2p

Excited State:
(Promotion of e) 2s 2p

sp2 –hybridized state :

sp2

169
Example: sp2 hybridization
Boron Triflouride Molecule

170
 Hybridization of carbon atom in
ethene molecule
• In ethene molecule contains a carbon-
carbon double bond and has planar
geometry.

171
• The ground-state electron configuration
of C atom is

Ground state C:
2s 2p

172
• Promoting a 2s electron into a 2p
orbital

Excited state C:
2s 2p

173
• Mixing the 2s orbital and two 2p orbitals
generates three sp2 hybrid orbital. One of
2p orbital remains unchanged.

Hybrid state C:
sp2 2p

174
Pi bond () – electron density above and below plane of
nuclei of the bonding atoms
Sigma bond () – electron density between the 2 atoms
175
176
 sp hybridization

• Mixing the s orbital and p orbital will

form two sp hybrid orbitals .

• The shape of sp hybrid orbital will form

a linear and the angle is 180o

177
Formation of sp Hybrid Orbitals

178
180o

179
 Beryllium chloride ( BeCl2)

• The beryllium chloride (BeCl2) molecule is

predicted to be linear by VSEPR .

• The orbital diagram for the valence electrons

in Be is:

Ground state Be:

2s 2p

180
• In ground state, Be atom does not form
covalent bond with Cl atom because
electrons are paired in the 2s orbital in Be
atom.

• Electron from 2s orbital is promoted to a 2p

orbital,

Excited state Be:

2s 2p

181
• Mixing 2s orbital and 2p orbital to form two
equivalent sp orbitals.

Hybrid state Be:

sp

182
• These two hybrid orbitals lie on the same
line, angle between them is 180o .

• Each of BeCl bond is then formed by the

overlapping of a sp hybrid orbitals atom Be
and p orbital atom Cl resulting BeCl2
molecule with a linear geometry.

183
 Formation of acetylene molecule
(C2H2)

• The acetylene molecule contains a carbon-

carbon triple bond. The molecule is linear.

  
H C C H


184
• The orbital diagram for the ground state of
carbon is:

Ground state C:
2s 2p

185
• Promoting a 2s orbital electron into a 2p
orbital result in the following excited state

Excited state C:
2s 2p

186
• Mixing 2s orbital with one 2p orbital
generates two sp hybrid orbitals and that the
two 2p orbitals remains unchanged.

Hybrid state C:
sp 2p

187
188
189
 


s s
sp  sp

 

C C
190
   
H C C H


191
Exercise
Determine the hybridization state of the central
atom in HgCl2. Describe the hybridization
process and determine the molecular geometry.

Solution:

- Electron conf. of Hg : [Xe] 6s2 4f14 5d10

- Hg is sp-hybridized because it has the

geometry of the two sp hybrid orbitals: linear.

192
In ground state, e are paired in the 6s orbital in Hg
atom.
Ground State :
6s 6p

Electron from 6s orbital is promoted to

unoccupied 6p orbital.

Excited state :
6s 6p

193
In the excited state, there are 2 unpaired e. The 6s
orbital and 6p orbital mix to form sp hybrid orbital.

sp hybridized state :
sp unoccupied

The two sp hybrid orbitals of Hg overlap with p

orbitals of Cl to form  bonds in HgCl2.

194
 Hybridization of s, p and d
orbitals
• For the third period & beyond elements,
molecular geometry cannot always be
accounted by assuming only s & p orbitals
hybridize.

• The formation of molecules with trigonal

bipyramidal & octahedral geometries must
include d orbitals in the hybridization concept.

195
a) sp3d hybridization

• Mixing the one s orbital, three p orbitals

and one d orbital generates five sp3d
hybrid orbitals

• the molecular geometry is trigonal

bipyramidal

196
sp3d hybrid orbitals

197
 Formation of phosphorus
pentahydride
• The phosphorus pentahydride molecule is
predicted to be trigonal bipyramidal
geometry base on VSEPR.

• The orbital diagram for the ground state

valence electrons in P is:

Ground state P:
3s 3p 3d
198
• Promoting a 3s electron into a 3d orbital
result in the following exited state:

Excited state P:
3s 3p 3d

199
• Mixing the one 3s , three 3p and one 3d
orbitals generates five sp3d hybrid
orbitals.:

Hybrid state P:
sp3d

200
 VIDEO 1

Hybridization of P atom in PCl5

Ground State :
3s 3p

Excited State :
3s 3p 3d

sp3d–hybridized state :
sp3d
201
202
Phosphorus Pentahydride

203
b) sp3d2 hybridization

• Mixing the one s, three p and two d

orbitals generates six sp3d2 hybrid
orbitals.

204
205
 Formation of sulphur
hexaflouride molecule
• The sulphur hexaflouride (SF6) molecule
has octahedral geometry base on VSEPR.

• The ground state electron configuration of

S is:

Ground state S:
3s 3p 3d

206
• Promoting a 3s and 3p electrons into a 3d
orbital result in the following excited state

Excited state S:
3s 3p 3d

207
• Mixing the 3s, three 3p and two 3d orbitals
generate six sp3d2 hybrid orbitals.

Hybrid state S:
sp3d2

208
 Hybridization of S atom in SF6

Ground State :
3s 3p

Excited State:
3s 3p 3d

sp3d2–hybridized
state : sp3d2
209
 A=S
B=F

210
211
 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 (or sigma bond).
# of Lone Pairs
+
# of Bonded Hybridization Examples
Atoms
2 sp BeCl2

3 sp2 BF3

4 sp3 CH4, NH3, H2O

5 sp3d PCl5

6 3d2
sp212 SF6
 The benzene molecule
• Benzene is a planar hexagonal molecule
with carbon atoms situated at the six
corners and angles are all at 120o.

• Each carbon atom is sp2 hybridized, it

forms three sigma bonds with two
adjacent carbon atom and hydrogen atom.

213
• Electron residing in any of these orbitals
are free to move around the benzene ring.

• Each carbon-to-carbon linkage in

benzene contains a sigma bond and a
‘partial’ pi bond.

214
Exercise:
Benzene molecule

215
 Exercise
1. Describe the bonding of the formaldehyde
molecule with the given Lewis structure:

H ..
C O
..
H
Assume that the O atom is sp2 hybridized

216
2. Determine the hybridization state of the
central (underlined) atom in each of the
following molecules:
a) HgCl2
b) AlI3
c) PF3

Describe the hybridization process and

determine the molecular geometry in each
case.

217
 LECTURE 10

4.4
Intermolecular forces

218
 Learning Outcomes:

At the end of the lesson the students should be

able to:
(a) Describe the intermolecular forces.
i. Van der waals forces ;
- dipole-dipole interactions or permanent
dipole.
- London forces or dispersion forces.
ii. Hydrogen bonding
(b) Explain factors that influence the strength of :
i. van der waals forces.
ii. Hydrogen bond 219
• Intermolecular forces are attractive forces
between molecules.
• Generally much weaker than covalent
bonds.
• The strength of intermolecular forces
determine the physical properties of the
substances

220
221
• Attractive forces between neutral
molecules are

1. Van der Waals forces

2. Hydrogen Bond

222
 Van der Waals forces
• 2 types of Van der Waals forces
a. dipole-dipole forces
(permanent dipole forces)
b. London dispersion forces

• The intermolecular forces increase in

strength according to the following;

London < dipole-dipole < H-bonding

dispersion
223
 (a) Dipole-Dipole Forces
• A dipole-dipole forces exist between
neutral polar molecules.

224
Orientation of Polar Molecules in a Solid

225
• The strength of dipole-dipole forces
depends on the dipole moment of the
molecule.

• A more polar molecule, have stronger

dipole-dipole forces.

• Example:
the dipole-dipole forces in H-Cl are
stronger than in H-Br
226
 Substance Molecular Dipole Boiling
Mass moment,u Point (K)
(amu) (D)
Propane 44 0.1 231

Dimethyl ether 46 1.3 248

Methyl chloride 50 2.0 249

Acetaldehyde 44 2.7 294

Acetonitrile 41 3.9 355

Relationship between boiling point and dipole moments.

227
 (b) London Dispersion Forces
• Exist in all atoms and molecules.
• Nonpolar molecules do not seem to have any
basis for attractive interactions
• At any instant one side of the molecule has
higher electron density while the other side has
lower electron density.
• At this instant, the atoms or molecules become
a small instantaneous dipole. Then, induce a
dipole on the neighboring atom and molecule.

228
• Due to electrons repulsion, a temporary
dipole on one atom can induce a similar dipole
on a neighboring atom which can cause the
neighboring atoms to be attracted to one
another.

• This interaction is called the London

dispersion forces (or just dispersion forces)
and only significant when the atoms are close
together.

229
Polarizability is the ease with which the
electron distribution in the atom or
molecule can be distorted.

Polarizability increases with:

 greater number of electrons
 more diffuse electron cloud

Dispersion
forces usually
increase with
molar mass.

230
What type(s) of intermolecular forces exist between
each of the following molecules?
• HBr
HBr is a polar molecule: dipole-dipole forces.
There are also dispersion forces between HBr
molecules.

• SO2
SO2 is a polar molecule: dipole-dipole forces.
There are also dispersion forces between SO2
molecules.
• CH4
CH4 is nonpolar: dispersion forces. 231
Factors which influence van der
Waals forces

i. Molecular size
ii. Molecular shape
iii. Molecular Polarity

232
 i. Molecular Size
 Down a group, number of electrons increases,
atomic radius increases.

The more electrons, the more distance over

which they can move, the bigger the possible
temporary dipoles and therefore the bigger the
dispersion forces.

Therefore, the bigger molecules are "stickier".

233
 The boiling points of the noble gases are:

• The boiling points

Noble gas Boiling
increase down the group: points
- no. of electrons increases helium -269°C
- atomic radius increases neon -246°C
- more distance over which
electron can moves argon -186°C
increases krypton -152°C
- stronger dispersion
forces (van der Waals xenon -108°C
forces)
radon -62°C
234
Xenon :
• has larger molecular size
• greater dispersion forces
• hence xenon has the higher boiling point.
235
 ii. Molecular shape
• Long and linear molecules can develop
bigger temporary dipoles due to larger
surface area which electron can move than
short and branched ones containing the
same numbers of electrons.

• Long and linear molecules can also lie

closer together - these attractions are at
their most effective if the molecules are
really close.
236
Butane has a higher boiling point because
• It has larger surface area
• Stronger dispersion forces (van der Waals
forces) 237
 iii. Molecular Polarity
• The boiling points of ethane CH3CH3,
and fluoromethane, CH3F, are:

238
• Both molecules have identical numbers
of electrons, and almost similar
molecular mass.

• The higher boiling point of

fluoromethane is due to the large
permanent dipole on the molecule
because of the high electronegativity of
fluorine.

239
trichloromethane, CHCl3 tetrachloromethane, CCl4

(b.p = 61.2C, m  0) (b.p = 76.8C, m = 0)

240
• CCl4 has higher boiling point because it
is a bigger molecule with more
electrons.

• The increase in the dispersion forces

dominates the dipole-dipole
interactions.

241
Factors influencing hydrogen bond
1.The electronegativity of atom that bonded to hydrogen atom.

The greater the electronegativity of the atom, the stronger

the hydrogen bond. If we increase the polarization between
the atoms involved in the hydrogen bond, the hydrogen
bond should become much stronger. Therefore, hydrogen
bonds in alcohol are stronger than in amine because oxygen
atom is more electronegative than nitrogen.

2.Number of hydrogen bond present in the compound

Increasing number of hydrogen bond will increase the

strength of hydrogen bond

3.Position of hydrogen bond

Hydrogen bond in straight chain is much stronger than

hydrogen bond in branched chain. Linear networks of
hydrogen bonds increase the dipole moment and lead to
stronger hydrogen bonds. The dipoles in hydrogen bonds 242
are induced dipoles
 LECTURE 11

HYDROGEN BONDING

243
 HYDROGEN BONDING
At the end of the lesson, student should be able to:
c) Explain the effects of hydrogen bonding on :
i. boiling point
ii. solubility
iii. density of water compared to ice.

244
Hydrogen bonding ?
Attractive forces between the positively
charged H atom of a molecule and the
negatively charged electronegative atom of
another molecule.
Example: N-H, O-H, or F-H bond

245
δ+ δ– δ+ δ– δ+ δ–
H–F H–F H–F

hydrogen bonding

246
hydrogen bonding

247
 Effects of Hydrogen Bond
on Physical Properties

i) The boiling points

ii) The solubility of simple covalent
molecules such as NH3, CH3OH in water
iii) The density of water and ice

248
i) Effects of Hydrogen Bonding on boiling
point

Figure: The boiling point of the hydrides of

element in group 14 to 17.
249
 From the figure:

1. The boiling points of hydrides of

group 14 elements (CH4,SiH4, GeH4
and SnH4) displays normal behavior.

CH4 < SiH4 < GeH4 < SnH4

250
 The type of intermolecular forces exist
between the molecules are only van der
Waals

 Hydrogen bonding is not present.

 The boiling point increases regularly when

the relative molecular mass increases.
because the van der Waals forces increase
as the molecular size increases.

251
2. For hydrides of group 15, 16 & 17elements
(except NH3, H2O & HF) hydrogen bondings are
not present.

 The increase in the boiling points for the

hydrides of each periodic group is due to the
increase in van der Waals forces as the
molecular size increases.

252
3. The strength of H-bonding is proportional to the
polarity of the bond.
Thus, H-F > H2O > NH3

However, boiling point increases in such order

H2O > HF > NH3

 Even though fluorine is more electronegative than

oxygen, H2O has higher boiling point than HF
because there are 4 H-bonding per H2O molecule
compared to only 2 per HF molecule.

 HF has higher boiling point than NH3 because of

stronger H-bonding of HF.
253
ii) Effects of H-Bonding on the solubility of
simple covalent compounds

- Water is a good solvent for liquids and gases

consisting of small polar molecules, that can
form hydrogen bonds with water molecules.

- For example, ammonia is soluble in water

because ammonia molecules can form
hydrogen bonding with water molecules.

254
 H H H

H─N─H------:O─
.. .. H ----- :N─H

Hydrogen bonding
255
Most organic compounds are insoluble in
water.

Organic compounds that are soluble in water

include:
- amines, for example ethylamine C2H5NH2.
- alcohols, for example ethanol, C2H5OH.
- carboxylic acid, such as ethanoic acid,
CH3CH2OH.

Amines are soluble in water because the -

NH2 group in amines can form H-bonding
with the water molecules.
256
 H H H
CH3–N-H------:O-H-----:N-CH
.. 3
..
H

Hydrogen bonding
257
Alcohol and carboxylic acids are soluble in water
because the -OH groups in the compounds can
form H-bonding with the water molecules.

However, not all organic compounds that contain

-NH2 group or –OH groups are soluble in water.

As the relative molecular mass increases, the

non-polar hydrocarbon portion becomes
larger.

258
Since hydrocarbons are insoluble in
water, the solubility decreases as the
relative molecular mass of the organic
compound increases

259
 H

R-OH------:O-H
..

hydrogen bonding

260
iii) Effects of Hydrogen Bonding on the
density of water and ice

H2O is unusual in its ability to form an

extensive hydrogen bonding network.

When cooled to a solid the water

molecules arrange themselves to form
tetrahedral arrangement in such a way to
maximise the amount of hydrogen
bonding between them.

261
The leaves a relatively large amount of space
between them and gives rise to an “open”
structure.

This arrangement of molecules has greater

volume (is less dense) than liquid water, thus
water expands when frozen.

The three-dimensional structure of the

covalent bonds and the hydrogen bonding in
ice is shown in the figure.

262
Figure: Hydrogen bonding (dotted lines)
between water molecules in ice.
263
 This “open” structure of the ice accounts
for the fact that is less dense than water at
0oC.

When ice melts, some of the hydrogen bonds

are broken.

This allows the water molecules to be more

compactly arranged, resulting in a 9%
decrease in volume.

Water has a higher density than ice.

264
 Water is a Unique Substance
Maximum Density
40C
Density of Water

Ice is less dense than water

265
 Lecture 12

4.5 Metallic bonding

At the of the lesson, student should be able to:
(a) Explain the formation of metallic bond using electron
sea model.
(b) Relate metallic bond to the properties of metal;
i. malleability
ii. ductility
iii. electrical conductivity
iv. thermal conductivity
(c) Explain the factors that affect the strength of metallic
bond.
(d) Relate the strength of metallic bond to boiling point.
266
 Metallic Bond
• A metallic bond can be defined as the
electrostatic force between the
positively charged metallic ions and the
‘sea’ of electrons .

267
 Electron sea model

Reminder :
The number of electron in the
model must equal to the
valence electrons released by
the metal atoms.
e- i.e: 8 Mg ≡ 16 e-
8 Al ≡ 24 e-

Metal cation

e- Valence electron from metal

268
 Electron Sea Model

• Electrostatic attraction between cation and sea of electrons

• A metal which has more valence electron will have more
electrons to contribute to the sea
• Cation becomes more positive, hence stronger attraction
between electrons and cations. Therefore, stronger metallic
bond.

269
In a metallic bond, metals atoms can be
imagined as an array of positive ions
immersed in a sea of delocalized
valence electrons.

These delocalized electrons are not

bound to individual atoms and they can
therefore serve to bind large numbers
of metal atoms together.

270
 Metals
• Metals are shiny solids are room temperature
(except mercury), with characteristic high
melting points and densities.
• Properties of metals:
– Able to be deformed without breaking.
Malleability is the ability of a metal to be
hammered into shapes.
– Ductility is the ability of a metal to be drawn
into wire.
– Because the valence electrons can move
freely (or mobility of the delocalized
electrons), metals are good heat conductors
and electrical conductors.
271
 The change of melting point and boiling
points

• A melting point of a metal indicates the

strength of its metallic bonding in its
structure.

The strength of α no. of valence e per atom

metallic bonding cationic size

272
So, the bonding will be weaker in sodium ( 1
valence e) compared to magnesium (2 valence
e) and aluminium (3 valence e).

273
 Table : The melting points and the boiling
points for elements in group 1,2,13 and the
block.
Element Na Mg Al Li Be B

Melting point (0C) 98 650 660 180 1280 2300

Boiling point (0C) 892 1107 2450 1330 2480 3930

No of valence 1 2 3 1 2 3
electron
274