CHAPTER 4

CHEMICAL BONDING
4.1 The Lewis Structure
4.2 Molecular Shape and Polarity
4.3 Orbital Overlap and
Hybridisation
4.4 Intermolecular Forces
4.5 Metallic Bond
1
2
INTRODUCTION

Chemical bonding refers to the

theories, ideas and models
chemist use to explain
how atoms are hold together
to form
molecule and compound.
3
3 models of chemical bonding

4
 LEWIS SYMBOL FOR AN ATOM

Show the symbol of an

Shows only number of element & one
valence ē dot/cross for each
valence ē

Examples:
Sodium atom Sulphur atom
1s2 2s2 2p6 3s1 1s2 2s2 2p6 3s2 3p4

Na ●

5
LEWIS SYMBOL FOR VARIOUS ELEMENTS

6
 OCTET RULE/ OCTET CONFIGURATION
OCTET RULE State:
Atoms tend to give, receive or share
electrons in order to attain the stable
electronic configuration of a noble gas
(an octet of electron) : duplet or octet.

Gaining / Ways to achieve a noble gas Sharing

accepting electronic configuration electrons
electrons

F + F F F

Li + F Li+ F -
Losing /
1s22s1 1s22s22p5 1s2 1s22s22p6
[He] [Ne] donating
the valence
electrons
7
FORMATION OF BONDS USING LEWIS
SYMBOL FOR:
i) Ionic or electrovalent bond
ii) Covalent bond
iii) Dative or coordinate bond

8
 IONIC/ELECTROVALENT BOND
Definition The electrostatic force of attraction between the
positive and negative ions in an ionic compound.
Formation Metal elements - donate ē  cation
Non-metal elements - receive ē  anion
Cation Valence electron in neutral atom is removed to
achieve noble gas configuration.

Anion The valence shell is completely filled with

valence ē (octet).
Example: i)

Show the transfer ii)

of electrons by
using arrows in
examples ii) & iii). iii)
 COVALENT BOND
Definition Atoms share electrons so that the stable
electronic configuration of the noble gas
can be obtained.
Formation Involves only the non-metal atoms.

Example: Lewis structure of F2

7e- 7e- 8e- 8e-

COORDINATE BOND/DATIVE BOND
Example 1:
Formation of ammonium ion, NH4+
Starting with ammonia :

The non-bonding pair of N is then shared with H+ ion

thus forming a dative bond :
Acceptor

Donor 11
 COORDINATE BOND/DATIVE BOND
Example 2: Ammonia-boron trifluoride compounds

Acceptor

Donor

Example 3: Al2Cl6
Acceptor

+ →
Donor AlCl3 AlCl3
12
COORDINATE BOND/DATIVE BOND
Example 3: Hydronium ion, H3O+

Acceptor

Donor

13
 COVALENT SPECIES WITH SINGLE, DOUBLE OR TRIPLE BOND

Examples:
Single bond single covalent bonds

or

Double bond – two atoms share two pairs of electrons.

or

Triple bond – two atoms share three pairs of electrons.

or
14
 LENGTH OF COVALENT BONDS
Bond
Bond Length
Type
(pm)
C-C 154
CC 133
CC 120
C-N 143
CN 138
CN 116
Triple bond < Double Bond < Single Bond
15
WRITING THE LEWIS STRUCTURE OF COVALENT COMPOUNDS & POLYATOMIC ION

• Determine the central atom (the least electronegative

atom).
1.
• Hydrogen is never a central atom.

• Count the total number of valence ē from all the atoms

in the molecule or ion.
• The number of valence ē is deduced from the group in
2. the PT to which the element belong.
• For ions, add 1 for each negative charge and subtract 1
for each positive charge.

3. • Draw the skeletal structure of the compound by joining

the atoms together.

4.
• Draw a single covalent bond between the central atom
and each of the surrounding (terminal) atom. 16
WRITING THE LEWIS STRUCTURE OF COVALENT COMPOUNDS & POLYATOMIC ION

• Calculate the number of non-bonding electrons.

• Since 1 covalent bond is formed by using 2 electrons.
5. Thus, Non-bonding ē = Valence ē - bonding ē

• Assign the remaining electrons to the terminal atom so

that each terminal atom has 8 electrons.
6. • Take note that if hydrogen is the terminal atom, it can
only have 2 electrons.

• Place the balance of the electrons to the central atom.

• If the central atom is from the Period 3 elements, it may
7. have more than 8 electrons.

• If the octet rule is not satisfied for the central atom, try
adding double or triple bonds between the terminal and
8. the central atom.
17
 DRAWING LEWIS STRUCTURE
Example 1: NF3
Step 1 – N is less electronegative than F → N is the central atom.
Step 2 – Count valence electrons N : 5
3 F : 3(7)
Total : 26
Step 3 – Draw single bonds between N and F atoms and
calculate the non-bonding e-.
Non bonding e- = 26 – 3 (2) = 20

Step 4 – Complete the octets of the terminal atom, remaining

electron > central atom

F N F

F
Example 2: HCN




If the central atom still has less than an octet, try to
form double or triple bonds by using the lone pairs
from the surrounding atoms.

i. Multiple bond formation is limited to four atoms :

C, N, O and S.
ii. Elements that can form double bond :
C, N, O and S.
iii. Elements that can form triple bond :
C and N. 19
FORMAL CHARGE AND MOST PLAUSIBLE LEWIS STRUCTURE

• It is often that we can write more than one Lewis

structures for a molecule.
• Example :

• The concept of FORMAL CHARGE is one way to

determine the most stable Lewis structure.
• Formal charge on an atom in a Lewis structure is the
charge it would have if the bonding electrons were
shared equally.
20
FORMAL CHARGE AND MOST PLAUSIBLE LEWIS STRUCTURE
• The FC can be calculated by using :

Formal charge = No. of valence ē – [(No. of lone pair ē) +

½ (No. of bonding ē)]

• Formal charge is used to determine the most stable or the

most plausible Lewis structure.
• The most plausible Lewis structure is one which:
(a) The atoms bear the smallest formal charges.
(b) The -ve FC appears on most electronegative atom.
(c) The +ve FC appears on the least electronegative atom.

• The sum of the FC on the atoms must equal zero for a

neutral molecule or must equal to the ionic charge of the
polyatomic ion. 21
Example 1:
(-1)
(0) The more stable Lewis
(0) (0) structure: Structure II
(-1) (0) (0) because negative formal
(0) charge resides at the more
(0) (0)
(0) (0) electronegative atom (O
atom).
Structure I Structure II

Example 2:
(+1) The more stable Lewis
(0)
structure: Structure I
because all of the atoms
(0) (0) (0) bear the smallest formal
(0) (-1)
(0) charges.

Structure I Structure II
22
 Exception To The Octet Rule
There are covalent molecules that fail to obey the
octet rule.

Incomplete Octet

Exception to the
octet rule Expanded Octet

Odd-Electron Molecule

23
 INCOMPLETE OCTET

A central atom has less than 8 electron in its

valence shell.

Example: Beryllium, boron and aluminum do not

achieve octet configuration even after sharing
electron with other atoms.

Example: BeCl2 BF3 AlCl3

.....
Cl Be
...
..
Cl

Be surrounded by only four

electrons and not eight.
24
 EXPANDED OCTET

A central atom has more than 8 electron in its

valence shell.

When expanding the octet, the central atom uses

the empty d orbital available at its valence level
(non-metal elements in Period 3 and above).

....
The electronic configuration for atom of S : ..... ....
F
F
F

1s2 2s2 2p6 3s2 3p4 3d F

..
.... . ...
S ..
F
Empty d orbitals ..
F

The central atom S can contain the 12 valence ē due to the

presence of the empty d orbitals. 25
ODD-ELECTRON MOLECULE

Odd-electron molecules have a central atom

from an odd-numbered group, such as
nitrogen, N (G15) and chlorine, Cl (G17)

Example: NO
The number of e- at N is five (odd number).
..
. .
N O
..
26
Concept of Resonance/Resonance Structures
Two or more Lewis structures for a single molecule
that cannot be represented accurately by only one
Lewis structure (due to delocalisation of ē).

These structures are known as resonance

structures.

The double headed arrow (↔) indicates that the

structures shown are resonance structures.
Example: NO3-

The Lewis structure is somewhere in between these 3 structures.

27
Exercise 1:
Draw all Lewis structure of NCO- and determine the best
structure.
Solution 1: - -

O C N O C N

Structure (A) Structure (B)

Formal charges : Formal charges :
C = 4 - [ 0 + ½ (8)] = 0 C = 4 - [0 + ½(8)] = 0
N = 5 - [4 + ½(4)] = -1 N = 5 - [2 + ½(6)] = 0
O = 6 - [4 + ½(4)] = 0 O = 6 - [6 + ½(2)] = -1

The most plausible structure is structure (B). O atom is more

electronegative than N atom, hence should take up FC of -1. 28
Exercise 2:
Draw all possible Lewis structures for the H3PO4 and BFCl2
molecule and determine the more stable structure.
(0)
(-1)

(0) (0) (0) (0)

(0) (+1) (0) (0) (0) (0)

(0) (0)
(0)
MORE STABLE
(0)
• Note that H3PO4 molecule contains P which is a period-3
element and can have an expanded valence shell.

• The most stable Lewis structure is structure II because all of

the atoms bear the smallest formal charges, FC = 0.
30
4.2 MOLECULAR SHAPE AND POLARITY

.... ...
What is the actual shape of this compound?

...
F Lewis structure
F P
..
.. . . .....
F
F
Number of ē surrounding
..
F
the central atom
VSEPR Theory
Assumption :
Study of molecular ē pair/bonding pair in the
geometry valence shell repel one another

Study of ē pair
Gives the position of all atoms
geometry 31
 VSEPR THEORY
MOLECULAR SHAPE/GEOMETRY
- Is the 3D arrangement of atoms in a molecule.
- It affects the physical and chemical properties of a
molecule.
- It is predicted by using Valence Shell Electron Pair
Repulsion(VSEPR) theory.

VSEPR THEORY
The valence electron pairs surrounding a central
atom repel one another. Thus, the bonding pair
and lone pair electron arranged themselves to be
as far apart as possible.
32
 VSEPR THEORY

In VSEPR theory;

 Double bonds and triple bonds are treated

like single bonds.

 If a molecule has two or more resonance

structures, we can apply VSEPR Theory to
any one of the resonance structures.

33
 BASIC MOLECULAR SHAPE

Linear

BASIC
Octahedral MOLECULAR Trigonal Planar
SHAPES

Trigonal bipyramidal Tetrahedral

34
 BASIC MOLECULAR SHAPE : Linear
For molecules without the lone pairs.

Class : AB2

B A B
Bond angle = 180°
Atoms are arranged in a straight line.
• Eg: BeH2, HgCl2

2 atoms bonded to central atom. 35

BASIC MOLECULAR SHAPE : Trigonal Planar
For molecules without the lone pairs ē.

Class : AB3

Bond angle = 120°

Central atom are bonded to 3 terminal atoms.
Eg: BH3

36
 BASIC MOLECULAR SHAPE : Tetrahedral
For molecules without the lone pairs.

Class : AB4

Bond angle = 109.5°

Central atom are bonded to 4 terminal atoms.
Eg: CH4

37
BASIC MOLECULAR SHAPE : Trigonal bipyramidal
For molecules without the lone pairs.
Class : AB5

Bond angle = 120°, 90o

Central atom are bonded to 5 terminal atoms.
Eg: PCl5

38
 BASIC MOLECULAR SHAPE : Octahedral
For molecules without the lone pairs.
Class : AB6

Bond angle = 90o

Central atom are bonded to 6
terminal atoms.
Eg: SF6
39
MOLECULAR SHAPE FOR MOLECULES WITH LONE PAIRS ē

For molecules with the lone pairs;

• Geometry of molecule is more complicated if the
central atom has both lone pairs and bonding
pairs.
• 3 types of repulsive force :
 between bonding pairs (BP – BP)
 between lone pairs (LP – LP)
 between a bonding pair & lone pair (BP – LP)
• The order of repulsion strength
LP – LP > LP – BP > BP- BP
40
MOLECULAR SHAPE FOR MOLECULES WITH LONE PAIRS ē

41
MOLECULAR SHAPE FOR MOLECULES WITH LONE PAIRS ē
MOLECULAR SHAPE FOR MOLECULES WITH LONE PAIRS ē

43
STEPS IN PREDICTING MOLECULAR SHAPE OF A MOLECULE

Draw a Lewis structure

Count the total number of electron pairs

(bonding pairs + lone pairs) at a central atom

A double / triple bond is counted as one bonding pair when

predicting geometry

Establish the electron – pair geometry

around the central atom

Use VSEPR to predict a molecular shape/geometry.

44
Before proceeding, let’s clarify the difference between
two related terms :

ELECTRON PAIR GEOMETRY

It describes how GROUPS OF VALENCE
ELECTRONS are arranged about the central atom.

MOLECULAR GEOMETRY
It describes how BONDED ATOMS are arranged
about the same central atom.

45
EXAMPLE 1: PCl3

P = 5 e-
3 x Cl = 21 e-
Total = 26 e-

One lone pair Class

P has 4 e- pairs
Three bonding pairs AX3E


Electron-pair geometry : Molecular geometry :

tetrahedral Trigonal pyramidal 46
EXAMPLE 2: H2S

2xH = 2é
S = 6é
H–S–H
Total = 8 é

2 lone pairs Class

S has 4 é pairs
2 bonding pairs AX2E2

Electron-pair geometry : Molecular geometry :

tetrahedral V-shaped 47
Exercise:
Draw the Lewis structure and predict the molecular
geometry of the following molecules or ions :
(a) SnCl2 d) CCl4
(b) CO2 e) SO3
(c) PCl3 f) ICl5

48
BOND POLARITY
- Covalent bonds with unequal electron sharing are
called polar covalent bonds.

- The atom with the higher electronegativity will have

a greater share of the bonding electrons.

Electron distribution

Electronegativity:
F>H
This asymmetry results in regions of slight negative
and positive charge in different regions of the
molecule. 49
BOND POLARITY

- Polarity of covalent bond can be measured by its

bond dipole.
- Bond dipole is shown by using a cross-based arrow
( ).
- This arrow indicates the direction of electron
displacement, from less electronegative to more
electronegative element.
- The bond dipole is a vector quantity, it has both
magnitude and direction.
50
BOND POLARITY
Resultant The sum of the vector for bond
=
dipole moment, µ dipole of each atom

If the resultant   0 Molecules are polar

If the resultant  = 0 Molecules are non-polar

2 vectors of the same direction,

the resultant   0
2 vectors of the opposite
direction, they cancel one another
 the resultant  = 0
51
BOND POLARITY

Draw the molecular geometry.

Identify polar bonds in the molecule. Indicate each

bond dipole using a vector quantity “ ”

Determine sum of vectors of bond dipole

If  = 0  nonpolar molecule.
If  ≠ 0  polar molecule.

52
BOND POLARITY
Non-polar molecules:
In symmetrical molecules containing polar bonds, if
bond dipoles cancel each other, then the molecules
do not possess a dipole moment (  = 0 ).
F
BeCl2

Cl Be Cl B
Linear F F
BF3
Trigonal planar

53
Example: SO3
3 x O = 18 é
S = 6é Lewis structure:
Total = 24 é
- 6é
Molecular Shape: Trigonal planar
18 é
- 18 é

The S O dipoles are in

opposite directions & cancel one
another.
No dipole moment ( = 0)
 non-polar molecule. 54
BOND POLARITY
Polar molecules:
Molecules with lone pairs are usually polar.
Because of the molecular geometry, the bond dipoles
do not cancel each other, but combine to give a
resultant dipole moment for the molecule(  0).

H2O SO2 S
O O
 = 1.60 D
 = 1.87 D
Bent Bent
55
Exercise:
Explain why the NH3 molecule is polar whereas the NH4+ ion is
non-polar.
H
Solution :

N
N H
H H
H
H
H

NH4+ NH3
Molecular geometry : Molecular geometry :
Tetrahedral Trigonal pyramidal
Bond dipole cancel each Bond dipole does not cancel
other. each other.
 =0  0
 Non polar molecule  polar molecule 5656
57
4.3 ORBITAL OVERLAP & HYBRIDIZATION
VALENCE BOND THEORY
When atoms share a pair of electrons to form a bond,
the overlapping of valence orbitals occurs.

58
 VALENCE BOND THEORY
Sigma bond (σ)
Types of covalent bond
Pi bond (π)

59
 SIGMA BOND (σ)
A covalent bond produced by the end to end
overlapping of atomic orbitals on neighbouring atoms.
Overlapping of two s orbitals
Types of
sigma bond Overlapping of two p orbitals
Overlapping of s and p orbitals

60
Sigma bond (σ): Overlapping of two s orbitals
Example: H2
H : 
1s

1s 1s H2

61
Sigma bond (σ): Overlapping of one s and one p orbitals
Example: HF
H : 
1s

F :    
2s 2p
(Valence electrons configuration)
- One of the 2p orbital is singly occupied.
- The 1s orbital of hydrogen overlaps with the 2p
orbital of flourine.

62
Sigma bond (σ): Overlapping of two p orbitals
Example: F2

F:     
1s 2s 2p
F:     
1s 2s 2p




63
 PI BOND ()
 A covalent bond produced when two lobes of p
orbitals overlap side-to-side.
 It occurs in molecules with double or triple bonds.

64
EXAMPLE: N2
N :     
1s 2s 2p
N :     
1s 2s 2p
pz π pz
py

px px
σ

There are 1 σ bond and 2

py
π π bonds in one molecule
N  Nσ of N2 65
π
 Types of normal covalent bonds

Single bond Double bond Triple bond

1  bond 1  bond 1  bond

1  bond 2  bond
66
 LIMITATION OF VALENCE BOND THEORY
- The theory assumes a simple overlap of adjacent
atomic orbitals in the formation of a covalent
bond.
- The theory predicts correctly the structures of
some simple diatomic molecules like H2 , F2 and
HCl.
- But it fails when applied to polyatomic molecules
or ions where sometimes the no. of bonds formed
exceeds the no. of unpaired electrons.

67
LIMITATION OF VALENCE BOND THEORY
Example: Carbon atom



6 C : 1s 2 2s2 2p2   
1s 2s
2p
It shows that C has only 2 unpaired ē.
This indicates that C can form only 2 covalent bonds.
However, carbon can form 4 bonds in all of its
compounds such as CH4 , CH3Cl....
To explain this abnormalities, the hybridisation
theory was introduced.
68
4.3 ORBITAL OVERLAP & HYBRIDISATION
HYBRIDISATION THEORY
The process of mixing together two or more atomic
orbitals that have similar energy
(same quantum number) to form a new set of hybrid
orbitals.
HYBRID ORBITAL

The new atomic orbitals produced by hybridisation.

69
 TYPE OF HYBRIDISATION

sp

Hybrid
sp3d2 sp2
Orbital

sp3d sp3

70
 HYBRIDISATION: sp
sp hybridisation The mixing of one s and one p orbital to
produce two equivalent sp hybrid orbitals
arranged in a linear geometry.

NOTE: There are two

unhybridised p orbitals
which are perpendicular
to the hybrid orbitals.
71
 HYBRIDISATION: sp2
sp2 hybridisation The mixing of one s and two p orbitals to
produce three equivalent sp2 hybrid orbitals
arranged in a trigonal planar geometry.

Trigonal planar72
 HYBRIDISATION: sp3

sp3 hybridisation The mixing of one s and three p orbitals to

produce four equivalent sp3 hybrid orbitals
arranged in a tetrahedral geometry.

73
 HYBRIDISATION: sp3d
sp3d hybridisation The mixing of one s, three p and one d
orbitals to produce five equivalent sp3d
hybrid orbitals arranged in the trigonal
bipyramidal geometry.

Example: PCl5

Trigonal bipyramidal

74
 HYBRIDISATION: sp3d2
The mixing of one s, three p and two d
sp3d2 hybridisation orbitals to produce six equivalent sp3d2
hybrid orbitals arranged in the
octahedral geometry.

Example: SF6

Octahedral
75
 DRAWING AN ORBITAL OVERLAPPING
Step by step …
1. Draw the Lewis Structure.
2. Determine the electron-pair geometry.
3. Predict the molecular geometry.
4. Write the electron configuration of the central atom
(ground state of valence e).
5. Promote the electron to possible hybridisation state
(excited state). In some cases excitation of electrons is
not necessary.
6. Hybridise the orbitals accordingly (hybridised state).
7. State a brief explanation.
76
 EXAMPLE 1: CH4
C = 4é Lewis Structure
4xH = 4é

Total = 8é

C (ground state):
2s 2p
C (excited state):
2s 2p
C (hybridised state):

4 sp3 hybrid orbitals 77

 Orbital-Overlap Diagram for CH4

Four sp3 hybrid orbitals 

are formed: tetrahedral  
shape. 
78
 EXAMPLE 2: C2H4
H H
Total electron-pair at C = 3
C C Type of hybridisation : sp2
H H
C (ground state):
2s 2p
C (excited state):
2s 2p

C (hybridised state):

1 unhybridised
sp2 2p orbital 79
Orbital-Overlap Diagram for C2H4


  H H
 
 C C

C  C
 H
 H


80
 C (hybridised state):

sp2 orbitals 2p (unhybridised)

- 3 sp2 hybrid orbitals of C (each contains an unpaired

electron)
- Overlap with sp2 orbital of adjacent C and s orbital of
H atom to form 3  bonds.
- The unhybridised 2p orbital of C which contains an
unpaired electron overlap side-by-side with similar
orbital of the adjacent C to form a  bond.

81
 EXAMPLE 3: NH3
Lewis Structure Total electron-pair at
N=4
Type of hybridization:
sp3
N at ground state :
2s 2p

N at excited state :
 N 
2s 2p   

At hybridisation
state :
sp3 hybrid
orbital
• sp3 orbitals overlap with s orbital of three
hydrogen atoms to form three sigma bonds.

• Therefore, three out of four sp3 hybridised

orbitals form covalent N-H bonds.

• The fourth hybrid orbital accommodates the lone

pair ē at the nitrogen.

83
84
4.4 INTERMOLECULAR FORCES
INTERMOLECULAR FORCES
Forces of attraction between molecules

Intermolecular
Forces

85
 4.4 INTERMOLECULAR FORCES

Types of Intermolecular
Forces

van der Waals Hydrogen

bonding

Dipole-dipole London/dispersion
forces forces (induced dipole-
dipole forces)

• Relative strength of intermolecular forces:

London dispersion < dipole-dipole < H-bonding
86
4.4 INTERMOLECULAR FORCES
The strength of IMF are responsible for the physical
properties of simple molecular compounds.

87
INTERMOLECULAR FORCES: Dipole-dipole Forces
Polar covalent molecules are sometimes
described as “dipoles” molecules as it has 2 poles.

1 end (pole) of the molecule has a +ve charge and

the other end (pole) has a –ve charge.

The molecules will orientate themselves so that

the opposite charges attract each other effectively.

The polar molecules must be closed to each other

for the dipole-dipole forces to be significant.

Dipole-dipole forces increase with an increase in

polarity of the molecule.
88
INTERMOLECULAR FORCES: Dipole-dipole Forces
Example: HCl molecules

Dipole-dipole Dipole-dipole
forces forces

89
INTERMOLECULAR FORCES: Dipole-dipole Forces

Orientation of Polar Molecules in a Solid

90
INTERMOLECULAR FORCES: Dipole-dipole Forces

Table 1 Relationship between boiling point and

dipole moments :

91
INTERMOLECULAR FORCES: London/Dispersion Forces

Results from instantaneous non-permanent dipoles created

by random electron motion.

The distribution of electrons at a given instant in time, may

not be equal around an individual atom. This gives rise to a
temporary dipole.

These temporary dipoles attract or repel the electron clouds

of nearby non-polar molecules.

Due to electron repulsion ,the electrons of the neighboring

atom would move away from the negative region of the
dipole – giving rise to an induced dipole.

Consequently, a temporary dipole on one atom can induce a

similar dipole on a neighboring atom.
92
This will cause the neighboring atoms to be attracted to one
another.

Note : London dispersion forces also exists between polar

molecules.

 Polar molecules have dipole-dipole as well as temporary

dipole (London forces) attraction.

London forces are directly proportional to molecular size.

93
INTERMOLECULAR FORCES: London/Dispersion Forces

Model to explain London Forces:

Helium atoms (2 electrons)

94
INTERMOLECULAR FORCES: London/Dispersion Forces
- The exact magnitude of London forces depends on
the polarisability of the atom.

- Polarisability is the ease with which the ē distribution

in the atom or molecule can be distorted by a nearby
electric field.

- Polarisability increases with :

i. Greater number of ē
ii. More diffuse ē cloud

- London forces usually increase with molar mass

because the larger the molecule, the larger the
orbitals and the larger the momentarily distortion.
Therefore, London forces increase. 95
Exercise:
State the type(s) of intermolecular forces exist
between each of the following molecules?

HBr HBr is a polar molecule.

- Dipole-dipole forces.
- London forces between HBr molecules.

SO2 SO2 is a polar molecule.

- Dipole-dipole forces.
- London forces

CH4 CH4 is non-polar.

- London forces.
96
Factors that influence van der Waals forces

Molecular
Molecular size
shape

Molecular
Polarity

97
 i) Molecular Size

Down the group, the number of inner electron increases

and also the radius.

The greater the no of e-, the greater the distance over

which they can move, the higher the possible of
temporary dipoles and therefore the stronger the
London forces.

Polarisability is the ease with which a particle’s

electron cloud can be distorted.

The greater the polarisability of a molecule, the easier it

is to induce a momentary dipole, thus the stronger the
London forces.
98
Larger molecules tend to have greater
polarisability because electrons are further away
from the nucleus.

Thus, London forces tend to increase with

increasing molecular size.

The stronger the London forces, the higher the

boiling point and the melting point of the
molecules.

99
 Example:

Molecular P4 S8 Cl2
formula
Melting 317 392 172
point/K
Boiling 553 718 238
point/K

• Sulphur molecule is the biggest and most

polarisable.

• Therefore, sulphur has a melting point which

is higher than that of phosphorus or chlorine.
100
 ii) Molecular Shape
- The shapes of the molecules influence the magnitude of
London forces.
- The strength of van der Waals increases with the total
surface area of the molecule.
Example:

CH3-CH2-CH2-CH3 -0.5 0C

CH3-CH-CH3
-11.7 0C
CH3
- Butane has a higher boiling point because the London forces
are greater.
- Surface area that is in contact with other butane molecules
is greater for the long cylindrical shaped butane molecules.
101
 ii) Molecular Polarity
• Both molecules have
identical numbers of ē, and
comparable molecular
mass. That means that the
London forces in both
molecules should be much
the same.

• van der Waals (dipole-dipole forces) between the polar

fluoromethane molecule is stronger than the non-polar
ethane molecule (London forces).
• The higher the polarity of a molecule, the higher the van
der Waals forces, therefore the higher the boiling point.

102
 INTERMOLECULAR FORCES: Hydrogen Bond
Is the force exerted between H atom which attached to N, O
or F in one molecule and N, O or F of a neighboring
molecule.

Is stronger intermolecular force than either London forces or

dipole-dipole forces.

Hydrogen nucleus is extremely small and positively charged

while fluorine, oxygen and nitrogen are being very
electronegative.

Therefore, electron on the hydrogen atom is strongly

attracted to the fluorine, oxygen or nitrogen atom.

The electrostatic attraction between these molecules will be

greater than for the polar molecules. 103
HYDROGEN BOND BETWEEN MOLECULES

Example 1 : Hydrogen bonding Example 2 : Hydrogen bonding

between water molecules between CH3OH molecules

Example 3 : Hydrogen bonding Example 4 : Hydrogen bonding

between NH3 molecules between HF molecules

104
 EFFECT OF HYDROGEN BOND
i) The boiling points.
ii) The solubility of simple covalent molecules
such as NH3, CH3OH in water.
iii) The density of water and ice.

105
Effects of hydrogen bonding: boiling point

 Boiling points of a series of

compounds generally increase
as the molecules get larger.
 This is due to the increase in
London forces.
However, for hydrides of Group
17 elements, HF is an
exception because of the
stronger force of attraction
between HF molecules
resulting from hydrogen bonds
acting between the HF
molecules. Thus, it has highest
boiling point.

Halides HF HCl HBr HI

Molecular
20 37 81 128
mass
106
• Boiling point of H2O is higher than NH3
because the hydrogen bonds between
water molecules are stronger due to
the higher electronegativity of the
oxygen atom compared to nitrogen
atom in NH3.
• Boiling point of H2O is higher than HF.
• Although F is more electronegative
than O and the hydrogen bond
between HF molecules are stronger
than the hydrogen bonds in H2O
molecules, each HF molecule can
form fewer number of hydrogen bond
compared to H2O molecules.
Effects of hydrogen bonding: solubility

Water is a good solvent due to its polarity.

When an ionic or polar compound enters water, it is

surrounded by water molecules

The partially negative dipoles of the water are attracted

to positively charged components of the solute, and
vice versa for the positive dipoles.

The relatively small size of water molecules typically

allows many water molecules to surround one molecule
of solute.
In general, ionic and polar substances such as acids,
alcohols, and salts are easily soluble in water, and non-
polar substances such as fats and oils are not.

The solubility of a substance is greatly dependent on its

ability to form hydrogen bonds with water molecules.

Organic molecules with – OH, - NH2 and – COOH

groups are soluble in water because these groups are
able to form hydrogen bonds with water molecules.

109
Example 1: Ethanol in water

Example 2: Methylamine in water

●●

●●

Example 3: Ammonia in water

110
• However, solubility of substances decreases with
increase in size of the molecules.
i.e. solubility is inversely proportional to the molecular
size of the molecule (solubility decreases as molecular
size increases).
• This is due to increase in hydrophobic area of the
substances.
Effects of hydrogen bonding: density of water compared to 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 maximize the amount of hydrogen bonding
between them.

They leave a relatively large amount of space between

them and gives rise to an “open” structure.

This arrangement of molecules has greater volume (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 following
figure.

Hydrogen bonding (dotted lines) between water molecules

in ice. 113
This “open” structure of the ice accounts for the fact that
ice 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.

Ice is less dense
than water

115
116
4.5 METALLIC BOND
Defined as the electrostatic force between the
positively charged metallic ions and the ‘sea’ of its
delocalised valence electrons.

The Electron Sea Model

Delocalised
Positive valence
ions electrons

Metallic bond 117

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

 These delocalised valence electrons are not bound

to individual ions and they can therefore serve to
bind large numbers of metal ions together.
118
PROPERTIES OF METAL
i) Malleability and Ductility

In metallic bonding, the delocalised

valence ē do not belong to any
particular metal ion.

If sufficient force is applied to the metal,

one layer of atoms can slide over one
another without disrupting the metallic
bonding.

This means that metallic bond is flexible

and strong.

Therefore, metal can be hammered into

sheets (malleable) or drawn into wires
119
(ductile) without breaking.
PROPERTIES OF METAL
ii) Thermal and Electrical Conductivity

The delocalised valence ē in metals are mobile and

free to move away from a negative electrode to a
positive electrode when a metal is subjected to an
electrical potential.

Hence, metals have high electrical conductivity.

The mobile delocalised valence ē can also conduct

heat by carrying kinetic energy from a hot part of the
metal lattice to a cold one; high thermal conductivity.
120
Factors that Affect the Strength of Metallic Bonds
The strength of metallic bonds depends on the number of
valence electrons.

Number of valence
Strength of
metallic bond α electron per atom
Atomic radius

Thus, metallic bonding is weaker in sodium (1 valence e-)

compared to magnesium (2 valence e-) and aluminium
(3 valence e- ).

121
Effect of Strength of Metallic Bonding on Melting and

Boiling Point of Metals.

The stronger the metallic bonds in the metal lattice, the

higher the melting and boiling point of a metal.

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
Number of valence
1 2 3 1 2 3
e-

Period 3 Period 2
Analyse the trend and explain. 122
Trend Across Period 2 & 3
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
Number of valence
1 2 3 1 2 3
e-

MP and BP increase from Na to Al due to the increasing

strength of metallic bonds.

Same trend is shown in the P2 elements, Li  Be  B.

Al has the highest number of valence electron, hence

strongest metallic bond, more heat is needed to overcome the
strong bond  highest MP and BP. 123
Trend Down Group 1

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
Number of valence
1 2 3 1 2 3
e-

Elements in P2 have higher BP and MP compared to P3

because elements in P2 have smaller atomic radius, thus
stronger metallic bonding.
More heat is needed to overcome the strong bond  higher
MP and BP.
When going down the group, size increases, thus metallic
bond becomes weaker.
That is why the MP and BP of Na is lower than Li. 124
Trend Down Group 17

Element Boling point (oC) Melting point (oC)

F2 -188 -233
Cl2 -35 -103
Br2 59 -7.2
I2 184.4 113
Going down Group 17, the boiling point and
melting point increases.

Going down a group, size of molecules increase

which lead to a stronger van der Waals forces and
results in high MP and BP.
125