Electronic theory of Valency and

Bonding

Ukwueze, N.N.(Mrs.)
 OUTLINE
• Introduction
• Definition of valency and valence electron
for some elements
• Types of bonding/factors responsible for
bonding between atoms
• Electrovalent
• Ordinary covalent
• Coordinate covalent
• H-bonding
• Van der Waals
• Dispersion forces
• Dipole interaction
 Outline continue
• Lewis structures of bonded atoms/
electron distribution
• Solved examples and end of lecture
questions
Valency:
• This is a periodic function of element in the
periodic table. It is the function of maximum
number of outermost or beta (β) electron
available for bonding. In other words,
elements with the same valency fall in the
same group. E.g. All elements in group 1 have
+1 valency. An element attains its oxidation
state when it gains or losses its valency. The
oxidation state of a neutral element is zero.
But for metals they are greater than zero and
less than zero in non-metals.
• E.g. Na , gives out 1electron while Cl gains 1e
+ - -

• Na → Na + e , Cl + e → Cl
+ - - -
• The oxidation number of hydrogen in non-
ionic compounds is +1, but in metallic
hydrides it becomes -1 i.e. H in NaH = – 1
and H in H2O = +1
• The type of valency in an atom determines
the type of bonding that will exist.
Valence electron:
• This is the total number of electron in the
outermost configuration of an atom. It
determines the group number in which the
element belongs to. The group number can
be determined following any of this
procedure;
• If the number of valence electron is less
than 3, then the group number is equal to
the number of valence electron in the
atom
• If the number of valence electron is
greater than or equal to 3 and d-orbital is
absent in the valence configuration, then
the group number is equal to the number
of valence electron plus 10
• Finally, if the number of valence electron
is greater than or equal to 3 and d-ordital
is present, then the group number is also
equal to the number of valence electron
in the atom.
 CHEMICAL BONDING
• The forces of attractions holding atoms
together in their numerous compounds
are called chemical bond. The bonds
are electrons interacting by overlap of
their orbitals or by complete transfer to
form more stable configuration.
• It is a force of attraction that holds
atoms together in their combined state.
• For chemical reaction between two
elements to take place, this union
attachment can be achieved by bond
formation between them. Such bond that
links atoms together is chemical bond
and by a process called chemical
bonding. E.g. some element like Na(s)
can only attain octet state after bonding.
Note: when a chemical reaction involves
loss or gain of electrons, ionic or
electrovalent bond is formed, but
covalent bonds are formed when a
reaction involves electron sharing.
TYPES OF BONDING
• Ionic/electrovalent
• Covalent
– Ordinary
– Co-ordinate/Dative
 Types of bonding continues
• Metallic bond
• Intermolecular forces
–Hydrogen bonds
•Intermolecular H-bond
•Intramolecular H-bond
–Van der Waals
•Dipole – dipole interaction
•Dispersion forces/London forces
•Dipole – induced dipole
 Ionic or Electrovalent Bond
• This is the electrostatic force of
attraction between oppositely charged
ions. They are formed when an atom of
element loses an electron(s) and another
atom then accept the electron(s), the
resulting charged species unite to form
a strong bond called electrovalent bond.
• Kossel formulated the theory of ionic
bond in 1916
• When elements in group 1,2 and 13 react
with those in groups 15,16,and 17 in the
periodic table ionic bond is formed.
Example of electrovalent bond are bond
formed between Mg + O in MgO. NaCl,
CaF2, CaCl2 are also examples.
• Na = 2, 8, 1 has a valency of +1 by
11
losing 1 electron to form Na+ with Neon
noble gas configuration as 2, 8. Then 17Cl
=2, 8, 7 has a valency of -1 by gaining 1
electron to form Cl- with Argon noble
configuration as 2, 8, 8.
• The Na Cl are then held together by
+ -

electrostatic force of attraction between

oppositely charged ion known as ionic or
electrovalent bond. Group II (Be, Mg, Ca, Sr,
Ba) and group 13 (Al, Ga, In, Tl) has positive
valency of +2 and +3 respectively by losing
2 and 3 electrons each.
• Examples of group I cations in ionic
compounds: Na F , Na Br , K I , (Na ) O ,
+ - + - + - +
2
2-

• Examples of group II cations in ionic

compounds: Ca (F ) , Ba (Cl ) , Ca O
2+ -
2
2+ -
2
2+ 2-

• Examples of group 13 cations in ionic

compounds: Al (Cl ) , (Al ) (O ) etc.
3+ -
3
3+
2
2-
3
• Using electronic configuration we can
represent a typical ionic combination as
follows;
• (LiF). Li (1s2 2s1) + F (1s2 2s2 2p5) → Li+
(1s2) + F (1s2 2s2 2p6)
• Ionic bond is found in compounds which
are formed by the reaction of very
electropositive elements, such as the
alkali and alkaline earth metals and
very electronegative elements such as
the halogens. It involves complete
transfer of electron from the
electropositive to electronegative atom.
• Ionic compound is formed during the
formation of electrovalent bond and is
favored by;
• Low ionization energy of the metal
• High electron affinity of the non-metal
• High lattice energy of the resulting
compound (the product).
• Examples of ionic compounds are salts,
alkalis and bases. It is not true that
elements react in order to gain noble gas
electronic configuration, rather they react
because the compounds formed are more
energetically stable than their elements
 Properties of Ionic Compounds
 They have high melting and boiling point due to
strong electrostatic force of attraction between the
ions.
 They are crystalline, strong, hard and found in the
solid state at room temperature. They do not
vaporize easily.
 Because they dissociate to form ions, in water, they
are good conductor of electricity. Hence, they
conduct electricity in solutions, molten or fused
state because of mobile ions.
 Soluble in polar solvent due to the ion-dipole
attraction. They dissociate to form ion in water,
thus they do not contain molecules. When ionic
compound is placed in water, the force between the
ions in the crystal weakens.
 Covalent Bonds:
• This is the overlap of atomic orbital to
form molecular orbital. It involves the
sharing of valence electrons of the
nonmetallic atoms of an element. A
chemical bond formed through sharing
of valence electrons is called covalent
bond. Examples of compounds formed
through covalent bond are H2, F2, CCl4,
CO2, CO, HF, H2O and HCl.
Here, two atoms share jointly one, two or
three (or more) pair(s) of electrons giving
rise to ‒, =, and ≡ bonds respectively. The
atoms of most molecules are firmly held
by covalent bond. A typical covalent bond
might be homopolar (the bond formed in
diatomic molecules having only one type
of atoms as in H2, F2, O2, N2, and Cl2) or
heteropolar (which is formed when the
atoms involved in the bond formation are
different. The electron density reside
closer to the atom with greater electron
affinity e.g. HCl, HF. Thus the bond is
polarized
 Homopolar covalent bond
• H + H → H : H i.e. H – H (H ) single
2

homopolar covalent bond(1 shared pair of

electron)
• Cl + Cl → Cl : Cl i.e. Cl – Cl (1 shared pair
of electron and 6 unshared pairs of
electrons)
• O + O → O = O (2 shared pairs of electrons
and 4 unshared pairs of electron)
• N + N → N ≡ N (3 shared pairs of electrons
and 2 unshared pairs of electrons
 heteropolar covalent bond
• H + Cl → H – Cl (one shared pair of electrons and 3
unshared pairs of electrons)
• The type of bond formed depends on temperature,
pressure and medium. For example, HCl at STP is
(g)

near covalent bond but on heating, electrons return to

H then the bond factually become covalent. In aqueous
solution, HCl becomes acid forming H (H O).
+
2

• Transfer of electron can only lead to electrovalent

bond but the sharing of electrons leads to the covalent
or coordinate covalent bond. In the above examples
involving Cl , only a single electron is required by such
2

atom to complete its valence shell (octet structure). The

covalent molecules formed from atoms requiring more
than one electron to complete the valence shell e.g in
case of tetrachloromethane CCl are also part of our
4

discuss. Other examples of covalent bond are CH , NH ,

4 3

CO , H O, CO, C H etc.
2 2 2 2
Properties of Covalent Compound

• Covalent compounds consist of molecules which

do not form ion in solution.
• They do not conduct electricity and so they are
non-electrolyte because they do not form ions in
solution. However, they conduct electricity in
solution only if they react with solvent molecule
to form ions. E.g. HCl → H + Cl . Graphite as
+ -

well conducts electricity due to its structure

• They occur mainly in organic compounds so they
are soluble in organic solvent like benzene which
dissolve camphor or carbon disulphide which
dissolve sulphur
Properties of Covalent Compound
continues
• They have low melting and boiling points as
little energy are needed to break the weak
intermolecular forces. This is why they are
gases or volatile liquid or solid.
• Some covalent compounds such as diamond,
graphite and silicon (iv) oxide have high
melting and boiling point. This is because
they form great/giant crystalline structure.
• They are soluble in non-polar solvent like
CCl , but sugar, methyl alcohol, glycerol etc
4

dissolves in H O and other polar solvents

2

because of H – bonding
Coordinate Covalent Bond(Dative bond)

• Electron deficient species H , BCl , AlCl , etc

+
3 3

react with electron rich species like :NH ; 3

where the 2 electron pair been shared is

donated by one of the participating atom
giving rise to dative bond or co-ordinate
covalent bond. One atom contributes in the 2
valence electrons to be shared in contrast to
the previous cases where there is equal
electron contribution. In this case, one atom
will have non-bonding electron or lone pair of
electron. E.g NH Cl, Al Cl , CO, NH BCl etc
4 2 3 3 3
 Hydrogen Bonding

• Hydrogen bond is strong intermolecular force

of attraction between hydrogen atom attached
to an electronegative atom (by covalent bond)
and the lone pair of another electronegative
atom. Water with molecular weight of 18 has
boiling point of 100 C and high surface tension
o

which could not be accounted for by bond

types like ionic, covalent, dative etc. hydrogen
bond which is formed between a hydrogen
atom and a highly electronegative atom such
as F, O and N accounted for this. The hydrogen
atom itself must be bonded to an atom with a
high electronegativity. H O, NH and HF form H
2 3

– bonding as shown below

 HCN also exhibits hydrogen bond.

H CN H CN H CN
 H H H

H N H N H N

H H H

H F
H F H F
. .

All these are examples of intermolecular

H-bond .
 Hydrogen bonding continues
• When 2 molecules of HF put close to one another,
the hydrogen of one molecule will be attracted to
the F atom of the other. This happens because of
the δ + of the H and δ- of the F atom.
• The attraction that holds the hydrogen atom
and F – atom of the other molecule is called
hydrogen bond. The more electronegative the
atom is the stronger the H bond. Hydrogen bond
-

that occurs between 2 different molecules is

called intermolecular hydrogen bonds. While
hydrogen bond that are form within the same
molecule are called intra-molecular bond. These
are shown below
Due to proximity of the O-H to oxygen of NO2, intramolecular
H-bond occurred
 Consequences /effects of H – Bond
• It increases viscosity and di-electric constant
of the liquid.
• It increases melting point and boiling point
and heat of vaporization and fusion higher
than expected. (as could be seen in the table 1
below)
• It increase hardness and rigidity of the
crystalline solid
• It increases stability of molecules
• Ethanol mixes with water because of H –
bonding.
• Molecular association e.g. dimerization and
polymerization
 O H O

C H3 C C - C H3

O
O H
Ethanoic acid dimer
D im e riza tio n
 Table 1: molecular weight and boiling temperatures of hydrides of group
15, 16 &17elements
Hydrides of group
15 NH3 PH3 AsH3 SbH3

Molecular Mass 17 34 78 125

(gmol-1)

Boiling point(oC) -38 -84 -68 -20

Hydrides of group
16 H2O H2S H2Se H2Te

Molecular 18 34 81 130
Mass(gmol-1)

Boiling point(oC) 100 -60 -40 2

Hydrides of group
17 HF HCl HBr HI

Molecular 10 36.5 81 128

Mass(gmol-1)

Boiling point(oC) 19 -85 -67 -35

 Van der Waal forces

• The Van der Waals forces named after Dutch

Scientist Johannes Didenik Van der Waals is
the sum of the attractive or repulsive forces
between molecules other than those due to
covalent bond, H – bond or electrostatic
interaction of ions with one another or with
neutral molecules. They are generally
intermolecular forces of attraction. The
forces that hold helium atoms or covalent
substances like iodine together in a liquid or
solid are called inter molecular force of
attraction also known as Van der Waal forces.
They occur as a result of:
• Forces between two permanent dipoles (dipole-
dipole interaction also known as Keesom force)
that result from the separation of negative and
positive charges producing a dipole. E.g in HCl
• Forces between a permanent dipole and a
corresponding induced dipole (temporal dipole
interaction also known as Debye force).
• Forces between two instantaneously induced
dipoles (London or dispersion force). These 2
dipoles will briefly attract each other. “The
force of attractive between 2 temporal dipoles
is known as London forces or dispersion forces”
. “Therefore intermolecular forces between
non-polar molecules are referred to as London
or dispersion forces”. E.g in Cl
2
• Van der Waals forces are relatively weak
compared to covalent bonds but plays a
fundamental role in life. It is a weak attractive
force between atoms of non-polar molecules
caused by a temporary change in dipole
moment arising from a brief shift of orbital
electrons to one side of one atom or molecule
creating a similar shift in adjacent atoms or
molecules. They arise from the random motion
of electrons in an atom or molecule. It provides
low binding energy leading to molecular
crystals having low melting point and boiling
point. This is responsible for Helium being
liquid and iodine solid at room temperature.
 Dispersion forces

• London forces or dispersion force is one

type of intermolecular force named after a
German physicist Fritz London who first
calculated it. It is the force of attraction
between two temporary dipoles. i.e.
temporary → temporary induced dipole
attraction of one another. The overall
strength of London forces depends on
molecular shapes and size. E.g. Non-polar:
[dry ice (CO ), O , naphthalene and Argon etc.
2 2

]
Lewis Structure of Bonded Atoms/ Electron
Distribution

• The Lewis structure of a covalent

compound or polyatomic ion shows how
the valence electrons are arranged
among the atoms in the molecule to show
the connectivity of the atoms. It makes use
of symbols . or * known as Lewis symbols
placed around the letter symbol of the
element. Each dot (.) or * represents one
electron.
• A covalent bond is a chemical bond
formed by the sharing of a pair of
electron between 2 atoms.
 Methane (CH4); has a Lewis
structure represented
below Covalent bond represents 2 electron
H
H
. x
. H C H
H x. C x H
x.
H H

We have A: B denoted as A-B (single bond) where 1

pair of electron is shared .
We have A꞉꞉ B denoted as A= B (double bond)
where 2 pairs of electrons are shared.
We have A:::B denoted as A≡ B(triple bond) where
3 pairs of electrons are shared.
An unshared electron pair on an atom (A:)
is called a lone pair. Lone pairs do not
contribute directly to the bonding but
they influence the shape of the
molecules and play an important role in
its properties. The octet rule (which
states that each atom shares electrons
with neighbouring atoms to achieve a
total of 8 valence electrons (an ‘octet’)
provides a simple way of constructing a
Lewis structure – a diagram that shows
the pattern of bonds and lone pairs in a
molecule
 Steps in Determining Lewis Structure
• Determine the number of electrons that are to be
included in the structure by adding up the number of
valence electrons of the atoms in the molecules e.g
CO2. Each negative charge on an ion corresponding to
an additional electron and each positive charge
corresponds to one electron less.
• Write the chemical symbols of the atoms in
arrangement that shows which atoms are bonded
together. O-C-O. Usually, the less electronegative
element is usually the central atom of a molecule but
there are many well known exceptions (H2O and NH3
among them)
• Distribute the electrons in pair so that there is one pair
of atoms bonded together and then supply electron
pairs (to form lone pairs or multiple bonds) until each
atom has an octet.
 .. ..
: O :C : O :
.. ..

.. ..
O C O
.. ..
Example: Write a Lewis Structure for BF4- ion
-
F

F B F

F
Here a total of 31 valence electrons exists i.
e B=3, F=7; 3+ (4×7) =31
The single negative charge of the ion reflects
the presence of an additional electron. Thus a
total of 32 electrons must be accounted for (16
electron pairs)
Draw the Lewis structure of the
following
a) H2 b) N2 c)CO d)O3
e)SO2 f)NH3 g)PF3 h)SO3 i)PO4
j)SO4 k)ClO4 l)NO2 n)BF3
Solution
 Resonance
• The Lewis structure of O3, suggest
incorrectly that one O-O bond is different
from the other, where as in fact they are
identical in length (128pm) intermediate
between those of typical single O-O and
O=O double bonds (148pm and 121pm
respectively). This deficiency of the Lewis
description is overcome by the concept of
the molecule is taken to be a superposition,
or average of all the feasible Lewis
structures by a double-headed arrow as in
• Resonance is pictured as a blending of
structures,
• Resonance has 2 main effects
• a) Averages the bond characteristics
over the molecule
• b) The ẻnergy of resonance hybrid
structure is lower than that of any
single contributing structure.
FACTORS THAT DETERMINE THE POLARISABILITY
OF AN ANION
The polarisability or deformability of anions depends
on two main factors namely
•Radius of gyration
•Charge of the anion
Radius of gyration
The polarisability increase as radius of anion increases.
For example under the same condition of temperature
and pressure, the polarisability of halide anion increases
as follows
F-˂Cl-˂Br-˂I-
Charge of the anion
Polarisability increases as the anionic charge increase
Cl + Cl --------- Cl : Cl
This one is the one shared pair and three unshared pairs.
Oxygen atoms lack two electrons to be equal the octet
shell of neon.
:O: + :O: ----------------- : O: : O:
[: O = O:] O2
Therefore two atom of oxygen would give
out each two electrons to the common bonding
pool to form two bonds.
E.g F- ˂ O2-˂ N3- ˂ C4-
Therefore you expect the polarizability to
increase in that order.
Factors that determine the polarizing power of
a cation
• Intensity of positive charge.
• Electronic configuration of cations.
 Molecular parameters

• Bond order- this is defined as the one-half

number of the electrons between the nucleus e.g.
F →F-F
2

O →O = O
2

C H → CH = CH
2 4 2 2

N→N≡N
2

• Bond length- this is measured in Armstrong Å ,

cm, nm. 1nm = 10 m, = 10 cm, 1Å = 10 cm. bond
-9 -7 -8

length is defined as the equilibrium distance

between nuclei of two bounded atoms.
• Bond energy- this is the dissociation energy (A-
B) of the bond between part A and B of the
molecules in the enthalpy change for the
reaction e.g
A–B→A +B (g) (g)

H → 2H
2(g) (g

H-H = ΔH = 104cal.mol
These bond energies are equal to the heat of
formation (ΔH˚) of diatomic molecules from the
atoms
2F -------------------F + 153kg/mol 2(g)

2Cl ---------------Cl + 243kg/mol

(g) 2(g)

2Br ----------------Br + 193kg/mol

(g) 2(g)

2I ----------------I + 151kg/mol
(g) 2(g)
The bond energy of HF is equal to H(g) + F(g) ------
-- HF + 563kj.mol
or 2H + 2F ---------2HF + 1126kj/mol
(g) (g)

HYBRIDIZATION
• Hybridization is defined as the mixing of
different atomic orbitals during covalent bonding
to give equivalent hybrid orbitals. When an atom
is excited through absorption of energy, unpairing
of its electrons may occur. For instance,
beryllium in its ground state has an electron
configuration of 1s 2s . When excited, the
2 2

configuration transforms into 1s 2s 2p , like the 2 1 1

boron atomic element that has the electronic

configuration of 1s , 2s , 2p in its ground state and
2 2 1

1s , 2s , 2p in excited state. The ground state

2 2 2

configuration for carbon is 1s , 2s , 2p , 2p , 2p

2 2 1
x
1
y
0
Z.

When excited it becomes 1s , 2s , 2p , 2p , 2p

2 1 1
x
1
y
1
Z
 Formal Charge

• Formal charge is an accounting procedure.

It allows chemists to determine the
location of charge in a molecule as well
as compare how good a Lewis structure
might be. The formula for calculating
formal charge is shown below:

Formal charge = No of valence electrons –

(No of non-bonding electrons + ½ No of
bonding electrons)
• Consider the molecule H2CO2. There are
two possible Lewis structures for this
molecule. Each has the same number of
bonds. We can determine which is better
by determining which has the least
formal charge. It takes energy to get a
separation of charge in the molecule (as
indicated by the formal charge) so the
structure with the least formal charge
should be lower in energy and thereby
be the better Lewis structure.
• The two possible Lewis
structures are shown below.
They are connected by a
double headed arrow and
placed in brackets. The non-
zero formal charge on any
atoms in the molecule has been
written near the atom.
The two structures differ only in the
arrangement of the valence electrons in the
molecule. No atoms have been moved. These
resonance structures . The better
are called
Lewis structure or resonance structure is that
which has the least amount of formal charge.
Try out other examples for mastering
 QUESTIONS
1a. Define valency b. Boron trihydride BH3
is regarded as electron deficient specie
why?
2a. Discuss the origin of Van der Waal
forces.
b. State the factors that affect the strength
of Van der Waal forces.
3a. What is responsible for the
abnormalous boiling points of water,
hydrogen fluoride and ammonia?
 Questions continues
• b. Explain the following observations
• i. Ethanoic acid molar mass found from
measurements in the vapour phase and solutions in
organic solvents was twice the value calculated
from chemical formular.
• ii. Benzoic acid has an apparent relative molecular
mass of 224 in hexane, but of only 122 when in
aqueous solution.
• iii. Cyclohexane is insoluble in water whereas
glucose is miscible with water in all proportion.
• iv. n-pentane and 2,2-dimethylpropane with the
same molecular weight has different boiling point.
 Questions continues
4a.Draw the cross and dot diagram of the
following
• hydroxonium ion H3O+
• Ammonia NH3
• Methylamine CH3NH2
• 1,2 –diaminoethane
– How many lone pair do the molecules in a.
above possess?
 Questions continues
5a. What is the type of bond formed when
• Boron trihydride react with ammonia?
• Water reacts with hydrogen ion i.e proton?
• Sodium reacts with Oxygen?
• Chlorine reacts with hydrogen?
bi. What is ionic bond?
ii. Mention at least three properties of ionic
compound.
iii. List three factors that favour the
formation of ionic bond.
 Questions continues
6ai. What is a covalent bond?
ii. When is a covalent bond said to be homopolar and
heteropolar?
bi. What is hydrogen bond?
ii. Briefly describe any four effects of H-bonding in
nature.
iii. Mention the two types of H-bonding with example.
7a.How many bond pair and lone pair electrons are
there in the following?
• CCl , H S, NF , NO, AlCl , CH OH, CH NH , CO , HCl,
4 2 3 3 3 3 2 2

H O, NH
2 3