CHEMICAL BONDING

Dr. ASHOK KUMAR SINGH

DEPARTMENT OF CHEMISTRY
LUCKNOW UNIVERSITY
LUCKNOW-226997
 COVALENT BOND

First covalent bond (a σ bond) is formed

when two atoms share electrons in
between them from their electron clouds.
They can only share these electrons by
approaching each other, and they can only
approach each other in a straight line
because there are only two atoms.
Another perspective is that the first
covalent bond formed (a σ bond) between
free atoms requires head-on overlap of
atomic orbitals. This view does in fact
require the atoms to approach each other
in a straight line, or else the overlap won't
be head-on
Either way, forming the first covalent
bond requires two free atoms to
approach each other in a straight line,
which is therefore directional.
This is directional in the sense that the overlap requires the
orbitals to remain aligned in the same manner (which they will)
as the atoms approach each other, and that shall be
accomplished as long as they approach each other in a straight
line.
 VALENCE BOND THEORY

V.B.T was proposed by Heitler and

London to explain the shapes of covalent
molecules, their bond angles and bond
lengths. It was extended by pauling and
slater to explain the directional nature of
covalent bonds.
• Valence bond theory predicts covalent
bond formation between atoms when they
have half-filled valence atomic orbitals,
each containing a single unpaired electron.
These atomic orbitals overlap, so
electrons have the highest probability of
being within the bond region. Both atoms
then share the single unpaired electrons
to form weakly coupled orbitals.
• The two atomic orbitals do not need to be
the same as each other. For example,
sigma and pi bonds may overlap. Sigma
bonds form when the two shared
electrons have orbitals that overlap head-
to-head. In contrast, pi bonds form when
the orbitals overlap but are parallel to each
other.
• The two atomic orbitals do not need to be
the same as each other. For example,
sigma and pi bonds may overlap. Sigma
bonds form when the two shared
electrons have orbitals that overlap head-
to-head. In contrast, pi bonds form when
the orbitals overlap but are parallel to each
other.
• Sigma bonds form between electrons of
two s-orbitals because the orbital shape is
spherical. Single bonds contain one sigma
bond. Double bonds contain a sigma bond
and a pi bond. Triple bonds contain a
sigma bond and two pi bonds. When
chemical bonds form between atoms, the
atomic orbitals may be hybrids of sigma
and pi bonds.
 The theory helps explain bond formation
in cases where a Lewis structure can't
describe real behavior. In this case,
several valence bond structures may be
used to describe a single Lewis stricture.
• Valence bond theory draws from Lewis
structures. G.N. Lewis proposed these
structures in 1916, based on the idea that
two shared bonding electrons formed
chemical bonds. Quantum mechanics was
applied to describe bonding properties in
the Heitler-London theory of 1927. This
theory described chemical bond formation
between hydrogen atoms in the H2
molecule using Schrödinger's wave
equation to merge the wavefunctions of the
two hydrogen atoms.
• In 1928, Linus Pauling combined Lewis's pair
bonding idea with the Heitler-London theory
to propose valence bond theory. Valence
bond theory was developed to describe
resonance and orbital hybridization. In 1931,
Pauling published a paper on valence bond
theory entitled, "On the Nature of the
Chemical Bond." The first computer programs
used to describe chemical bonding used
molecular orbital theory, but since the 1980s,
principles of valence bond theory have
become programmable. Today, the modern
versions of these theories are competitive
with each other in terms of accurately
describing real behavior.
• Valence bond theory can often explain
how covalent bonds form.
The diatomic fluorine molecule, F2, is an
example. Fluorine atoms form single
covalent bonds with each other. The F-F
bond results from overlapping pz orbitals,
which each contain a single unpaired
electron. A similar situation occurs in
hydrogen, H2, but the bond lengths and
strength are different between H2 and
F2 molecules.
• A covalent bond forms between hydrogen
and fluorine in hydrofluoric acid, HF. This
bond forms from the overlap of the
hydrogen 1s orbital and the fluorine
2pz orbital, which each have an unpaired
electron. In HF, both the hydrogen and
fluorine atoms share these electrons in a
covalent bond.
• Covalent bond is formed by the
overlapping of two orbitals having
unpaired electrons. The two orbitals
involving in overlapping must belong to
two different atoms and the electrons
present in them must have opposite spins.
• The greater the extent of overlapping, the
stronger is the bond formed.The
overlapping of atomic orbitals follows the
order. p-p >s-p > s-s
• The bond is formed in the direction of
overlapping of orbitals.
 A covalent bond formed due to Axial or Linear
overlapping of atomic orbitals results in the
formation of sigma bond(s ). its electron
cloud is concentrated symmetrically around
the inter nuclear axis.
• A covalent bond formed by the side wise
overlap (or) Lateral overlapping of atomic
orbitals is known as a pi bond( p ) .Its
electron cloud is present on either side of the
inter nuclear axis . ‘s ’ bond is formed only
after the formation of ‘p ’ bond.
• Any type of orbitals can involve in s ‘’
bond formation.Only ‘p’ or‘d’ - orbitals can
involve in p ‘’ bond formation.
• Single bond is always ‘s ’ bond. Double
bond contains one ‘s ’ bond and one ‘ p ’
bond. Triple bond contains one ‘s ’ bond
and two p ‘’ bonds.
• ‘’ s bond is stronger than ‘ p ’ bonddue to
greater extent of overlapping.
• Strength of the bonds follows the order σ p- p >
σ >σ >p
s- p s -s

• Strength of the bonds follows the order

triple bond > double bond > single bond.
• i) H2 contains one ‘s ’ formed by 1s - 1s axial
overlapping
– Cl2 contains one ‘s ’ formed by 2pz - 2pz axial
overlapping
– O2 contains one ‘s ’ & 1 p bond i.e. ‘s ’is Formed
by Py - Py axial overlapping and p bond is
formed by side wise overlapping
According to this theory, the bond
formed between the central metal
atom and the ligand is due to the
overlap of filled ligand orbitals
containing a lone pair of electron
with the vacant hybrid orbitals of the
central metal atom.
 Main assumptions of VBT
1. The ligand → metal bond in a coordination
complex is covalent in nature. It is formed by
sharing of electrons (provided by the ligands)
between the central metal atom and the ligand.

2. Each ligand should have at least one filled

orbital containing a lone pair of electrons.

3.  In order to accommodate the electron pairs

donated by the ligands, the central metal ion
present in a complex provides required number
(coordination number) of vacant orbitals.
4. These vacant orbitals of central metal atom
undergo hybridisation, the process of mixing
of atomic orbitals of comparable energy to
form equal number of new orbitals called
hybridised orbitals with same energy.
5. The vacant hybridised orbitals of the central
metal ion, linearly overlap with filled orbitals
of the ligands to form coordinate covalent
sigma bonds between the metal and the
ligand.
6.  The hybridised orbitals are directional and
their orientation in space gives a definite
geometry to the complex ion.
7.  In the octahedral complexes, if the (n-1) d
orbitals are involved in hybridisation, then
they are called inner orbital complexes or low
spin complexes or spin paired complexes. If
the nd orbitals are involved in hybridisation,
then such complexes are called outer orbital
or high spin or spin free complexes. Here n
represents the principle quantum number of
the outermost shell.
8.  The complexes containing a central metal
atom with unpaired electron(s) are
paramagnetic. If all the electrons are paired,
then the complexes will be diamagnetic.
9. Ligands such as CO, CN-, en, and
NH3 present in the complexes cause
pairing of electrons present in the central
metal atom. Such ligands are called
strong field ligands.
10. Greater the overlapping between the
ligand orbitals and the hybridised metal
orbital, greater is the bond strength.
 Limitations of VBT
Even though VBT explains many of the
observed properties of complexes, it still
has following limitations
1.  It does not explain the colour of the
complex

2.  It considers only the spin only magnetic

moments and does not consider the other
components of magnetic moments.
3. It does not provide a quantitative
explanation as to why certain complexes
are inner orbital complexes and the others
are outer orbital complexes for the same
metal. For example, [Fe(CN)6]4- is
diamagnetic (low spin) whereas [FeF6]4- is
paramagnetic (high spin).
VSEPR Theory, Valence Bond theory,
characteristic of covalent compounds
1. VSEPR theory was proposed by Gillespie
and Nyholm to explain the shapes of
molecules and ions.
2. The orbital which contains the bonded pair
of electrons is known as the localised
orbital.
3. The orbital which contains the non bonded
pair of electrons is known as the
delocalised orbital and that electron pair is
called delocalised electron pair (or) lone
pair.
• Lone pair occupies more space than bond
pair around the nucleus of central atom.
• The shape of a simple molecule depends
on the number of electron pairs present in
valence shell of central atom.
• The lone pairs of electrons and bonded
pairs of electrons on central atom are
oriented in such a way they feel minimum
repulsion and maximum stability.
• The repulsion between electron pairs is in
the order.
• The number of electron pairs in single bond
(or) double bond (or) triple bond (or) dative
bond is counted as only one pair because all
the electron pairs in the same bond are
oriented in the same direction.
• The molecules without lone pairs have a
regular geometry. The presence of lone pairs
give an irregular geometry due to unequal
repulsive forces.
• The number of lone pairs of electrons (l.p)
and bond pairs of electrons (b.p) on central
atom determines the shape of molecule or
ion.
• It follows that repulsion between two lone pairs is
greater than repulsion between a lone pair and a bond
pair, which in tum is greater than the repulsion
between two bond pairs.
lp-lp repulsion > lp-bp repulsion > bp-bp
repulsion
• Thus the presence of lone pair on the central atom
causes slight distortion of the bond angles from the
ideal shape. If the angle between a lone pair, the
central atom and a bond pair is increased, it follows
that the actual bond angles between the atoms must
be decreased.
• The magnitude of repulsions between bonding pairs of
electrons depends on the electronegativity difference
between the central atom and the other atoms.
• Double bonds cause more repulsion than single bonds,
and triple bonds cause more repulsion than a double
bond.
• Regular Geometries
• Some Bond Angle Trends

NH3>PH3>AsH3>SbH3
107.3°> 93.6°>91.8°>91.3°

H2O>H2S>H2Se>H2Te
10.4.5°>92.5°>90.0°>89.0°
As we move down the group, radius of
elements increases and
electronegativity decreases so bond
angle decreases.
 NF3< NCl3< NBr3< NI3
Because of greater electonegativity
there is a shift of electrons towards
the atom reducing the bond pair -
bond pair repulsion and in turn
reducing the bond angle so the
decreasing order of electronegativity
BF3 = BCl3 = BBr3 = BI3 is F> Cl> Br> I

Why bond angles are equal here?

Because they contain only bond pairs, no lone pairs and
in accordance with VSEPR theory compounds in which
central atom contains only bond pairs will have regular
geometry.
• Covalent Character of Ionic Bond
 • Fajan’s Rule
Fajan gave some postulates or condition to explain how
does covalent character gradually increase in ionic bond or
ionic compounds. 
• The cation with smaller size have higher polarizing power,
that is, they cause polarization of electron charge cloud
of an anion to a greater extent. Hence, with
decreasing cationic size, the covalent character of the
concerned compounds for a particular anion increases.
The cationic size M of group-II alkaline metal elements
2+

gradually increases from top to bottom along the group so

covalent character decreases from top to bottom.
• The anions with large size have high polarizability. That
is, their electron charge cloud can be deformed by cation
easily. Hence, with increasing anionic size , the covalent
character of the related compound increases.
The size of halide ions gradually increase from top to
bottom, so the covalent character of halogen compounds
for a particular cation increases from top to bottom.
 • For effective polarization, there should be a high charge on the
cation or the anion both. The electrostatic forces which cause
polarisation, would increase in the charge on the ions.
• Cations with pseudo inert gas configuration nsnpnd or with inert
2 6 1 0

pair configuration nd (n+1)s have high polarising power while

1 0 2

cation with noble gas configuration nsnp have low polarising

2 6

power. That is due to greater effective nuclear charge  in the

former cases and smaller effective nuclear charge in the later
cases.
Effect of Polarization
• Bromides and iodides have higher lattice energies (and hence
higher stabilities) than expected from theoretical calculations.
This extra stability is due to polarization of the anions resulting in
the formation of polar covalent bond which is more stable than a
pure ionic bond.
• The solubility of ionic compounds in polar solvents decreases
with increase in the degree of polarisation i.e. with increase in the
degree of covalent bonding.
• The hardness of ionic compounds decreases with increases in
the degree of polarisation i.e. with increase in the covalent
character.
• On the left, the cation charge increases (size
decreases) and on the right, the anion size
increases,
both variations leading to an increase in the
covalency.
Thus covalency increases in the order:
+ - 2+ -
[Na  Cl , NaCl] < [Mg  2(Cl) , MgCl2] <
[Al3+ 3(Cl)-, AlCl3] and
[Al3+ 3(F)-, AlF3] < [Al3+ 3(Cl)-, AlCl3] <
[Al3+ 3(Br)-, AlBr3]
• Some Examples
• Why does AgI is more covalent than AgCl?
Why does MgCl2 is more covalent than NaCl ?
• When an cation approaches an anion closely,
the net positive charge on the cation tends to
attract the electron cloud of the anion
towards itself due to the electrostatic force of
attraction existing between them. At the same
time the cation also tends to repel the
positively charged nucleus of the atom. The
combined effect of these two forces is that
the electron cloud of the anion no longer
remains symmetrical but is bulged or
elongated towards the cations.This is called
distortion ,deformation or polarisation of the
anion.
 By the cation and the anion is said to be
polarisation of the anion by the cation and
the anion is said to be polarsed. The ability
of a cation to polarise a nearby anion is
called its polarisation abillity of a cation to
polarise a nearby anion is called
polarisation abillity or polarisation power.
• To understand the Fajans’ rule, Let us first
understand a few terms:
• Polarising power
• It is the extent to which a cation can
polarise an anion. It is proportional to
charge density. Charge density is the ratio
of charge to volume. Polarising power α
Charge density. More the charge density,
greater is the polarising power for that
cation.
 Polarising power
It is the extent to which a cation can
polarise an anion. It is proportional to
charge density. Charge density is the ratio
of charge to volume. Polarising power α
Charge density. More the charge density,
greater is the polarising power for that
cation.
• Polarisability
• It is the extent to which an ion can be
polarised. It can also be called as the ease
with which an ion can be polarised.
Polarisation is the distortion of a
spherically symmetric electron cloud to an
unsymmetric cloud.
 Postulates of Fajans’ Rule
• The rule can be stated on the basis of 3
factors, which are:
• Size of the ion: Smaller the size of cation,
the larger the size of the anion, greater is
the covalent character of the ionic bond.
• The charge of Cation: Greater the charge of
cation, greater is the covalent character of
the ionic bond.
 Electronic configuration
For cations with same charge and size,
the one, with (n-1)dn nso which is found in
transition elements have greater covalent
character than the cation with
ns2 np6 electronic configuration, which is
commonly found in alkali or alkaline earth
metals.
• Explanation of Fazans’ Rule
• Rule 1:
• The first rule speaks about the polarising
power of the cation. If the cation is smaller,
then we can say that the volume of the ion
is less. If the volume is less, we can
conclude that the charge density of the ion
would be high.
• Since the charge density is high, the
polarising power of the ion would be high.
This makes the compound to be more
covalent.
• Rule 2:
• The second rule speaks about the
polarizability of the anion. Larger the anion,
less is the effective nuclear charge that
holds the valence electron of the ion in
place. Since the last electron is loosely
bound in large anions, it can easily be
polarised by a cation, thereby making the
compound more covalent.
• Rule 3
• The third rule is a special case. Let us use an
example to explain this point.
• Example: If we want to find the more covalent
compound among HgCl2 and Calcium
Chloride we cannot use size as a factor to
conclude. This is because both Hg2+ and
Ca2+ are of almost equal size. To explain this,
we employ the third rule.
• The electronic configuration of Hg2+ is 6s0 5d10.
This configuration is called pseudo-octet
because d-orbital is fully filled, but the
element does not have 8 electrons or an
octet.
• We know that d orbitals are not good at
shielding, so we can say that the anion (Cl–)
would be more polarised because the d
orbital is poor at shielding making HgCl2 more
covalent than CaCl2 because Ca2+ ion has a
noble gas configuration.
• Now to answer the question that we asked first,
amongst the alkali chlorides, which one is the
most covalent?
• Since the anion is the same, we have to
compare the cations. According to Fajans’ rules,
smaller the cation, more is the covalency.
Therefore, LiCl is the most covalent.
• Consider Aluminum Iodide (AlI3)
• This is an ionic bond which was formed
by transfer of electrons.
• The iodine being bigger has a lesser effective
nuclear charge. Thus, the bonding electrons
are attracted lesser towards the Iodine nucleus.
• On the contrary, the aluminium having three
positive charges attracts the shared pair of
electrons towards itself.
• This leads to insufficient charge separation for
it to be ionic and so it results in the
development of covalent character in AlI3.
• Consider Aluminium Fluoride (AlF3)
• This is an ionic bond which was also
formed by transfer of electron. But here
the fluorine being smaller attracts the
shared pair of an electron more towards
itself and so there is sufficient charge
separation to make it ionic.
• HYBRIDISATION
• The intermixing of atomic orbitals of
almost same energy and their
redistribution into an equal number of
identical orbitals is known as hybridisation.
• Covalent bond is formed by the
overlapping of two orbitals having
unpaired electrons. The two orbitals
involving in overlapping must belong to
two different atoms and the electrons
present in them must have opposite spins.
• The greater the extent of overlapping, the
stronger is the bond formed.The
overlapping of atomic orbitals follows the
order. p-p >s-p > s-s.
• The bond is formed in the direction of
overlapping of orbitals.
• A covalent bond formed due to Axial or
Linear overlapping of atomic orbitals
results in the formation of sigma bond(s ).
its electron cloud is concentrated
symmetrically around the inter nuclear axis
• A covalent bond formed by the side wise
overlap (or) Lateral overlapping of atomic
orbitals is known as a pi bond( p ) .Its
electron cloud is present on either side of
the inter nuclear axis . ‘s ’ bond is formed
only after the formation of ‘p ’ bond.
• Any type of orbitals can involve in s ‘’
bond formation.Only ‘p’ or‘d’ - orbitals can
involve in p ‘’ bond formation.
• Single bond is always ‘sigma ’ bond. Double
bond contains one ‘sigma ’ bond and one ‘
pi ’ bond. Triple bond contains one ‘sigma ’
bond and two pi ‘’ bonds.
• sigma bond is stronger than ‘ π’ bond due
to greater extent of overlapping.
• Percentage ionic character of a Polar Covalent Bond
The percent ionic character of a polar covalent bond
depends upon two factors:
• The electronegativity difference of the bonded atoms
• Dipole moment of the compound formed
Electronegativity difference and Percent Ionic Character
• A pure covalent bond is formed between atoms A and
B if both the atoms are same.
• If A and B have different electronegativities, the
resulting bond would be polar covalent since the
bonding electron pair is pulled more towards the
more electronegative atom bringing some excess
negative charge on the later. As a result some excess
positive charge will be developed on less
electronegative atom.
A–B
-δ δ+
Several empirical equations have been proposed
The Pauling Equation
Percent ionic character = 1-e - 1/4(χ
A
χ )
B

Where χ and χ are the electronegativities of A and B.

A B

He established the following empirical relationship

between χ - χ and the percent ionic character.
A B

χA- χB 0.6 1.0 1.4 2.0 2.4 3.0

Percent ionic 9 22 39 63 76 89
character

The Hannay-Smith Equation

Percent ionic character = 16(χ - χ ) + 3.5(χ - χ )
A B A B
2
Dipole Moment and Percent Ionic Character
• Consider the bond H-X where X is a halogen.
• If the bond is purely covalent, its dipole moment
would be negligible.
• If the bond is ionic, like H X it implies that transfer of
+ -

an electron has operated from H to X and the bond

would have an appreciable dipole moment which is
determined by the product of the electronic charges
and the inter-nuclear distance between H and X.
• For a polar covalent bond which intermediate
between a pure covalent and pure ionic bond, the
dipole moment would be given by the product of the
charge (δ) separated due to polarisation and the
internuclear distance.
•
• It may be mentioned, however, that dipole
moment calculated from the ionic character
of the compound alone contributes only partly
towards the total molecular dipole moment.
Other factors
• difference in the sizes of two atoms
• Hybridization of orbitals involved
• Direction of lone pairs with respect to the
nucleus
Also contribute towards the total molecular
dipole moment.
Hence, the percent ionic character calculated on
the basis of dipole moment is only approximate.
• Dipole Moment and Structure of Molecules
• Hybridization
• Hybridization is defined as the concept of mixing
two atomic orbitals with the same energy levels to
give a degenerated new type of orbitals.
• This intermixing is based on quantum mechanics.
• The atomic orbitals of the same energy level can
only take part in hybridization and both full filled
and half-filled orbitals can also take part in this
process, provided they have equal energy.
• Redistribution of the energy of orbitals of
individual atoms to give orbitals of equivalent
energy happens when two atomic orbitals
combine to form hybrid orbital in a molecule. This
process is called hybridization. The new orbitals
thus formed are known as hybrid orbitals.
• Steps Involved in Hybridization
• Formation of Excited State

• Mixing and Recasting of Atomic Orbitals

• Proper Orientation of Hybrid Orbitals in

Space
Essential Conditions for Hybridization
• The participating orbitals must have nearly
the same energy.
• The hybridization of 2s and 2p orbitals is
possible but hybridization of 2s and 3p
orbitals is not possible.
π-bonding is not considered in hybridization
as it is always formed after the formation of
σ-bond and also does not decides the final
geometry of any molecule.
Characteristics and Rules of Hybridization
• Atomic orbitals undergoing hybridization should belong to
the same atom or ion.
• The participating orbitals must have nearly the same
energy.
• The total number of hybrid orbital formed is equal to the
number of atomic orbitals participating in hybridization.
• All orbitals are identical with respect to energy and
direction.
• The hybrid orbital differ from one another in orientation.
• The shape of hybrid orbital is different from that of the
original orbitals.
• Each hybrid orbital can occupy maximum of two electrons.
• They are concentrated in one particular direction to
achieve better overlap.
• The hybrid orbitals have maximum symmetry and definite
orientation in space to minimize the mutual force of
repulsion
Actual shape of sp hybridized orbital
 sp3d
hybridization

Involves dx2-y2 example SbF5

 O=C=O
π-bonding is not considered in hybridization
Relative Energies of Molecular Orbitals
• Bonding Molecular Orbitals (BMO) – Energy
of Bonding Molecular Orbitals is less than
that of Anti Bonding Molecular Orbitals. This
is because of the increase in the attraction of
both the nuclei for both the electron (of the
combining atom).
• Anti-Bonding Molecular Orbitals (ABMO) –
Energy of Anti Bonding Molecular Orbitals is
higher than Bonding Molecular Orbitals. This
is because the electron tries to move away
from the nuclei and are in a repulsive state.
Gerade (g) and Ungerade (u) Terminologies
 g

σBMO is gerade and σABMO is gerade

πBMO is ungerade and πABMO is gerade
• In F2 there are 14 electrons to be
accommodated and, according to the
aufbau principle, this gives a ground state
electronic configuration of:

• In O2 there are 12 electrons to be

accommodated and, according to the
aufbau principle, this gives a ground state
electronic configuration of:
What happens if the s–p separation is small?
• A comparison of theoretical with
experimental data for F2 and O2 indicates
that the approximations we have made
above are appropriate.
• However, this is not the case if the s–p
energy difference is relatively small. In
going from Li to F, the effective nuclear
charge experienced by an electron in a 2s
or 2p atomic orbital increases and the
orbital energy decreases.
The trend is non-linear and the s–p separation increases
significantly from B to F.
The relatively small s–p separation observed for B and C
means that the approximation made when constructing the
orbital interaction diagram in Figure is no longer valid when
we construct similar diagrams for the formation of B2 and C2.
• Here, orbital mixing may occur between
orbitals of similar symmetry and energy,
with the result that the ordering of the MOs
in B2, C2 and N2 differs from that in F2 and
O2.
The Fig. compares the energy levels of the MOs and the
ground state electronic configurations of the diatomics X2 for
X = B, C, N, O and F. Notice the so-called σ-π crossover that
occurs between N2 and O2.
• Concise Inorganic Chemistry By J. D. Lee
• Principles of Inorganic Chemistry, Puri,
Sharma and Kalia