CHM 122 GENERAL INORGANIC CHEMISTRY 2UNITS

MODULE I:
CHEMICAL BONDING.
OBJECTIVES
a) To study the formation of the major types of chemical bonds usually
encountered in compounds.
b) To study the general characteristic properties of the compounds formed by the
different chemical bonding.
The types of chemical bonding to be considered are
i) Ionic or electrovalent bonding
ii) Covalent bonding
iii) Coordinating covalent (dative) bonding
iv) Metallic bonding
v) Hydrogen bonding
c) In this module you will also learn about the following concept or terms:
(i) Valence electrons (ii) Ionization energy (iii) Electron affinity (iv) Octet rule and
exceptions to the Octet rule (v) Lewis formulas or structures
(vi) Non bonding electrons, bonding pairs of electrons and lone pairs of electrons
(vii) Polar compounds (viii)Intermolecular forces of attraction etc

INTRODUCTION
i) Valence (or Outermost Shell) Electrons
Valence electrons are those involved in forming compounds. They are the
outermost shell electrons of atoms. For example, nitrogen has the electronic
configuration 1s2 2s2 3p3. The outermost shell electrons are those in the 2s and 2p
orbitals.
Atom
and
Electronic
Configuration
N[1s2 2s2 2p3]
O[1s2 2s2 2p4]
CI[1s2 2s2 2p63s23p5]
Na[1s2 2s2 2p6 3s1]
Mg[1s22s22p63s2]
AL[1s2 2s2 2p6 3s2 3p1]

Valence Electrons
2s2 2p3 = 5
2s2 2p4 = 6
3s2 3p5 = 7
3s1
=1
2
3s
=2
2
1
3s 3p = 3

ii) Ionization Energy (IE) or Ionization Potential (IP) is the energy required to
remove one mole of electrons from one mole of gaseous atoms or ions e.g.
Process
Energy
KJ mol-1
-1
ev mol
2
2
6
1
+
2
2
6
a)Na[1s 2s 2p 3s ](g)
Na [1s 2s 2p ] + e
5.10
495
+
b) Al (g)
Al (g) + e
5.95
577
Al+ (g)
Al2+(g)

Al2+(g) + e
Al3+(g) + e

18.82
28.44

1816
2745

This example illustrates that as the charge on the atom increases IE increases
General Comments on IE
In general metals have relatively low IE compared to non-metals
In a period IE increases as the nuclear charge, z increases.
In a Group IE decreases as z increases
e.g. Li
Li+ + e, IE = 5200 KJ mol-1
Na
Na+ + e, IE = 495 KJ mol-1
K
K+ + e, IE = 418 KJ mol-1
Rb
Rb+ + e, IE = 403 KJ mol-1
iii) Electron Affinity (EA) is the energy change accompanying the addition of one
mole of electrons to one mole of gaseous atoms or ions
e.g. F (g) + e
F(g)-, EA = -364 KJmol-1
Cl (g) + e
Cl-(g), EA = -342 KJmol-1
I(g) + e
I(g) -, EA = -295 KJmol-1
O(g) + e
O-(g), EA = -141 KJmol-1
2

O-(g) + e
S(g) + e
S (g) + e

O2-(g), EA = +791 KJmol-1

S-(g), EA = -200 KJmol-1
S2-(g), EA = + 649 KJmol-1

General Comments on EA
In most cases, energy is liberated when the first electron is added because it is
attracted to the atoms nuclear charge, hence EA, is usually negative.
EA2 is always positive because energy must be absorbed to overcome
electrostatic repulsive ion.
In general non metals have relatively high EA values than metals
As a general trend EA increases as z increases in a Period.
In a Group EA decreases as z increases. This is an indication of increasing
metallic properties.
iv) Electronegativity (EN) is the relative ability of a bonded atom to attract the
shared electrons. Alternatively, EN is a measure of the relative tendency of an atom
to attract electrons to itself when chemically combined with another atom.
Elements that tend to attract rather than lose electrons are said to electronegative.
Elements with high EN values (nonmetals) often gain electrons to form anions
while elements with low EN values (metals) often lose electrons to form cations
e.g. O + e
OF+e
FCl + e
CINa
Na+ + e
Ca
Ca2+ + 2e
EN of the elements are expressed on a somewhat arbitrary scale, called Pauling
Scale.

Table 1: Electronegativity Values of the main group elements

Group
1
(IA)

Group
2
(IIA)

Group
13
(IIIA)

H
2.2
Li
1.0
Na
0.9
K
0.8
Rb
0.8

Be
1.6
Mg
1.3
Ca
1.0
Sr
0.9

B
2.0
AI(III)
1.6
(d-block Ga(III)
elements) 1.8
In (III)
1.8

Cs
0.8

Ba
0.9

TI(I)
1.6
TI(III)
2.0

Group
14
(IVA)

C
2.6
Si
1.9
Ge(IV)
2.0
Sn(II)
1.8
Sn(IV)
2.0
Pb(II)
1.9
Pb(IV)
2.3

Group
15
(VA)

Group
16
(VA)

Group
17
(VIIA)

N
3.0
P
2.2
As(III)
2.2
Sb
2.1

O
3.4
S
2.6
Se
2.6
Te
2.1

F
4.0
Cl
3.2
Br
3.0
I
2.7

Bi
2.0

Po
2.0

At

EN increases as z increases across a Period

EN decreases as z increases down a Group
EN values can be used to predict the bond type in a particular compound as
indicated in Table 2 below.
Table 2. Relationship between bond type and electronegativity difference (EN) of
the two bonded atoms.
Bond
EN
Types of Bond
Cl Cl
3.2 - 3.2 = 0
Covalent
Cl C
3.2 2.6 = 0.6
Polar Covalent
Cl H
3.2 2.2 = 1.0
Polar Covalent
F Na
4.0 -0.9 = 3.1
Ionic

Ionic Bonding:
Na (1S 2 2S2 2P6 3S1 )

Na+ (1S 2 2S2 2P6 ) + e

Cation

Cl[Ne]3S2 3P5 + e

Cl-[Ne]3S2 3P6
Anion
The ions thus formed are held together by coulombic or
electrostatic forces e.g.
Na+ + ClNaCl
The bond formed is called electrovalent or ionic bond.
Further examples:
a) MgCl2
Mg [Ne] 3S2
Cl[Ne] 3S2 3P5 + e
Mg2+ + 2Cl-

Mg2+ [Ne] + 2e
Cl- [Ne] 3S2 3P6
MgCl2

b) CaO
Ca[Ar] 4S2
O [He] 2S2 2P4 + 2e
Ca2+ + O2-

Ca2+ [Ar] + 2e
O2- [Ne]
CaO

Factors influencing the formation of ions

i) Ease of formation of cations- i.e. lower IE
ii) Ease of formation of anions- i.e. the more negative the EA
is, the more stable is the anion formed. e.g.
F
F- ; Cl
Cl- ; Br
Br- ; I
I-333
-364
-342
-295KJ mol-1
O - ; O-

O
-141

O2- ; S
+791

S- ;
-200

SS2-,
+600 KJ mol-1
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iii) Lattice energy: The more exothermic the lattice energy,

the more stable is the ionic compound formed. e.g.
Na+ (g) + F- (g)
NaF(s),
HLE = -915 KJ
Na+ (g) + Cl- (g)
NaCI(s),
HLE = -781 KJ
Mg2+(g) + O2- (g)
MgO(s),
HLE = -3933 KJ
By definition, the lattice energy is the energy change when
one mole of a crystal is formed from its component ions in
the gaseous state.
General Characteristic Properties of Ionic Compounds
i) They exist not in molecular but in ionic forms e.g. NaCl
exists in the solid state as Na+CIii) As a result of (i), ionic compounds conduct electricity
when in molten state or in solution.
iii) They have relatively high melting and boiling points e.g.
melting points (C) of NaCl is 1413, CaF2 ~ 2500.
iv) They dissolve readily in solvents with high dielectric
constants (polar solvents e.g. water) but generally
insoluble in non polar solvents such as benzene,
hexane, carbon tetrachloride, chloroform etc.
Covalent Bonding:
Covalent bonding involves the sharing of one or more pairs
of electrons between two atoms of either the same element or
two different elements e.g.

a) Formation of hydrogen molecule, H2

Using a dot/cross representation:

H
x
+ xH
H H or H

H2

Covalent
bond

The bond formed is called covalent bond or electron pair

bond.
b) Formation of chlorine molecule, CI2

Cl

xx

Cl

xx

xx

Cl
Cl

Cl2

x
x

xx

Cl Cl

x
x

c) Formation of hydrogen chloride, HCI

Cl

H
Cl

H

H Cl

Cl

The electron pairs between the two atoms are called bonding
pairs of electrons. The remaining electron pairs on each atom
are called lone pairs of electrons or non-bonding electrons.
Octet Rule
In covalent bonding, each atom in the bond often attains the
electronic configuration of the nearest noble gas i.e. the atom
part from H tends to achieve an octet of electrons in its
valence shell.
Further examples of the formation of covalent compounds
i) Water,H2O

2Hx + O

H2O

ii) Ammonia, NH3

3H

N
x

N
H

NH3

iii)

Methane, CH4
H

4H

C
x

C H
H

CH4

The structures with the covalent bonds indicated are called

Lewis structures.
Remarks:
i)

Homonuclear diatomic molecules such as H2, CI2, O2

etc have even distribution of bonding electron
density equal share of the bonding pairs of
electrons.

ii)

Heteronuclear diatomic molecules such as HCI, HF

etc have an uneven distribution of bonding electron
density because of the difference in the
electronegativities of the elements.

Cl

Partial charges

The existence of partial charges imparts a dipole moment

to the molecules i.e. thus leading to bond polarity
= charges x d (distance between and charges)
General Characteristic Properties of Covalent Compounds
i)
Covalent compounds exist in molecular forms
(i.e discrete molecules or a big giant molecule such as
diamond).
ii)

The forces between the molecules are weak. As a

result, they generally have low melting and boiling
points except giant molecules.

iii) At room temperature, they are usually gases (CH4,

CO2, SO3, e.t.c), liquids (H2O, C2H5OH, C6H6) or low
melting solids (urea, glucose, phenol)
iv) They are usually insoluble in polar solvents but are
soluble in non-polar solvents.
v)

Covalent compounds do not conduct electricity in

the solid or molten state or in solution. They are nonelectrolytes.

Failure of Octet Rule

The atoms in some molecules cannot obey the octet rule
because there are too few or too many electrons. This
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generally occurs when an atom forms more than 4 bonds e.g.

PCl5 (5bonds), SF6(6bonds).

Cl

Cl
P

Cl

Cl

Cl

F
F

8e-s around each Cl, 10e-s around P

8e-s around each F, 12e-s around S

In a few cases, an atom has less than an octet e.g.

Cl

Be

Cl

Cl

4e-s around Be

Cl

Cl

6e-s around B

Writing of Lewis Structures

The following guidelines will be found useful
Decide which atoms are bonded

Count all valence electrons

Place any remaining e on central

atoms in pairs

If central atom has no octet,

form double or triple bonds
if necessary.

Examples
1. write the Lewis structure for SO3

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Solution
O
i)

Skeletal structure: O

O
ii) Valence electrons: 6 x 3 + 6 = 24
O
iii) Placing 2 electrons in each bond

S
O

iv) Remaining electrons: 24 6 = 18e

v) Complete octet of the oxygen atom

O
O

O
Central atom has no octet. A double bond will enable it to
have octet.
Lewis structure

O
O

O
O

2) Write the Lewis structure for C O

Solution.
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i) Skeletal structure: C O
ii) Valence electrons: 4 + 6 = 10e
iii) Form electron pair bond: C: O
iv) Remaining electrons: 10 2 = 8e.
v) Form octet around oxygen atom

C O

For C and O atom to have octet, triple bond has to be

formed.

C O

Study Question
Write the Lewis structure for SO42Formal Charge is defined as the residual charge on an atom
in the Lewis structure and is obtained by using the following
equation;
Formal charge = Group Number Number of unshared
electrons Number of bonds
(a)
OR
= Valence electrons Number of
1
unshared electrons - 2 Number of
bonding electrons
(b)
Example 1. The Lewis structure of HCN is

H C
I

or

H N
II

Determine the formal charge of each structure and hence the

more plausible structure.
Solution
Using the equation:
Formal charge = Group No No of unshared
12

electrons No of bonds.
Structure I
H: 1 0 1 = 0
C: 4 0 4 = 0
N: 5 - 2 3 = 0

Formal charges on the atoms

Structure II
H: 1 0 1 = 0
C: 4 2 3 = -1
Formal charges on the atoms
N: 5 0 4 = +1
Based on the formal charges on the atoms, structure I in
which the formal charges are zero is more plausible
structure.
Example 2.
The Lewis structure of thionyl chloride could be written as;

Cl

Cl

or

Cl

Cl

II

Determine the formal charge on each atom and hence the

more probable structure.
Solution
Using equation (a), the calculated formal charges are:
Structure I
CI: 7 6 1 = 0
S: 6 2 3 = 1
O: 6 - 6 - 1 = -1

Formal charges on the atoms

Structure II
CI:

761=0
13

S: 6 6 1 = -1
Formal charges on the atoms
O: 6 - 2 - 3 = 1
Oxygen is a more electronegative atom than S. Therefore,
structure I is more probable than structure II.
Study Questions
i) Write the Lewis structure of each of the following species:
a) HCOF b) CIF3
2) Determine all the possible structures for a) HCOF.
Using the formal charges on the atoms technique, determine
the most probable structure.
RESONANCE:
There are some cases in which the Lewis structure of a
specie does not account for the properties (e.g. bond length
and bond energy) of the ion or molecule it represents. For
example. Consider the formate ion, HCO 2 .
Its Lewis structure is:

O
H

C
O

The actual structure of the molecule or ion that we cannot

draw satisfactorily is considered as an average of a number
of Lewis structures that we can draw. For HCO 2 , we can
write

H C O

H C O

I
II
The actual structure of the ion is said to be a resonance
hybrid of the two contributing structures I and II.
14

The concept of resonance does not suggest that the structure

of HCO 2 fluctuates between I and II or the ion exists in two
different forms. There is only one form of the ion that can be
observed experimentally.
A resonance hybrid may be the characteristics of its
parents but it never has the exact structure of any one of
them.

Further Example:Draw the resonance structures of:

i) SO3,
ii) NO3
Solution:
i) SO3: The resonance structures are

O
O

S
O

S
O

S
O

iv) NO
3

Lewis Structure:
15

Resonance Structures:

Coordinate Covalent (Dative) Bonding:

This is a special case of covalent bonding. Here, the electrons
shared are all donated by only one of the atoms involved in
the bond formation. Usually the donor atom is an atom
having an unshared pair of electrons in the valence shell
after the formation of the covalent bonds e.g. O, N, CI.
An acceptor atom is an atom which is electron deficient i.e.
lacks sufficient valence electrons to attain the octet
configuration e.g. B, AI, H+, Mn+ ( where M = a metal and n+,
the oxidation number e.g. Mg2+,Cu2+, fe2+)
Formation of the Bond
Example 1

+
H

H2O

H O

H
(H3O+, Hydronium ion)
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Denotes the dative bond.

The oxygen atom donates one of its lone pairs of electrons
which is shared between it and H+ ion.
Example 2

F
F B

BF3 + NH3

H
N
H

Denotes the dative bond.

Example 3

Cl

Cl

AlCl3 + NH3

Al
Cl

H
N
H

Example 4
H
H O

Cu2+ + 4H2O

H
O H

2+
Cu

O
O
H
H
H
H

[Cu(H2O)4]2+

17

H H

H H

H
H

[Mg(H2O)6]2+

+ 6H2O

Mg

2+

H O
H
Mg2+
H O

NH3

NH3
H3N
Co2+
H3N
NH3
NH3

Co2+ + 6NH3

[Co(NH3)6 ]2+

Metallic Bonding is pictured as a series of (+) ions

surrounded by a sea of mobile valence electrons (-) i.e

+
Metal ions

Valence

electrons

In solid metals, the atoms are packed closely together in

regular array: Closed packed or body centered cubic
systems. The structures are held together by metallic
bonding.

18

Properties of metallic compounds

1. Metals are solids except Hg
2. They are hard (Pt, Fe) or soft (Li, Na, K)
3. They have luster appearance
4. They are good conductors of heat and electricity.

Hydrogen Bonding:
1. Introduction
Covalent bonding between two different electronegative
atoms always leads to bond polarity. For instance, a
molecule that has a highly electronegative atom connected to
a hydrogen atom is strongly polar e.g. HF, NH3, H2O.

HF :

H2O:

NH3 :

H
19

The hydrogen atom, because of its partial positive charge, is

attracted to a lone pair of electrons on the atom of another
molecule. The new bond formed is called a Hydrogen Bond
i.e
i) HF + HF

HF

ii) H2O + H2O

iii) NH3 + NH3

HF
H

H N
H

N
H

Covalent bond
Hydrogen bond
Hydrogen bond is essentially an electrostatic bond, but
certainly not as strong as ionic bond.
The bond strength (or energy) is weaker than that of
covalent bond, but stronger than that of van der waals bonds
as indicated in the table below:
Nature of Bond
Ionic bonds
Covalent bonds
Hydrogen bonds
Van der waal bonds

Typical Bond strength

(KJ/ mol)
>1000
100 900
20 50
<20
20

The higher the electronegativity of the heteroatom X, the

stronger the hydrogen bond. Thus N H

N < O-H.O

< F-H.F
(weakest)

(strongest)

This parallels the increasing electronegativity of X (N, O, F)

atom bonded to hydrogen; N < O < F

21