STUDY CENTRE

CHAPTER - 04
CHEMICAL BONDING AND MOLECULAR
STRUCTURE

Chemical bond
A chemical bond is an attraction that holds the constituent particles together in a chemical species.
KOSSEL-LEWIS ELECTRONIC THEORY OF CHEMICAL BONDING
I. Lewis approach
Lewis pictured the atom in terms of
1. A positively charged “Kernel” [Nucleous + inner electrons] and
The outer shell that could accomodate a maximum of eight electrons.
2. When all the eight corners of the cube are occupied then an atom is said to have stable electronic
configuraiton.

 Cheaply noble gases which have 8 outer most electrons already have stable configuration while all
other.
Lewis symbols
G.N. Lewis introduced a simple notation to represent valence electrons in an atom. These notations
are called Lewis symbols or electron dot symbols. According to Lewis notatinos, the valence electrons
are represented by dots around the symbol of the element.

Eg:- Li ; Be ; B; C; N; O ; F ; Ne

Significance of Lewis dot symbols

The number of dots around the symbol represents the number of valence electrons. This number of
valence electron helps to calculate the common or group valence of the element. The group valence
of the elements is generally either equal to the number of dots in Lewis symbols or 8 minus
the number of dots or valence electrons.
2. Kossel approach

 Kossel, in relation to chemical bonding, drew attention to the following facts.

 In the periodic table, the highly electronegative halogen and the highly electropositive alkali metals
are separated by the noble gases.

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 The formation of a negative ion from a halogen atom and a positive ion from an alkali metal atom
is associated with the gain and loss of an electron by the respective atoms.

 The negative and positive ions thus formed attain stable noble gas electronic configurations.

 The noble gases have a particularly stable outer electronic configuration of eight.

 Negative and positive ions are stabilized by electrostatic attraction.

Octet Rule [Kossel and Lewis - 1916] (Electronic theory of chemical bonding)

According to octet rule, atoms of various elements take part in chemical combination in order to attain
octet of electrons in their outermost shell.

Atoms generally achieve octect of electrons in two ways.

1. By the transfer of electron from one atom to another

2. By the mutual sharing of electron betwen the atoms.

Covalent bond : (Lewis - Langmuir concept)

It is the bond formed by mutual sharing of electrons between two atoms so as the complete their
octect or duplets.

Covalency : Of an element may be defined as the number of electrons contributed by its atom while
forming covalent bond.

Types of covalent bond

1. Single bond : When two atoms share one electron pair,the bond formed is called single covalent
bond.

H + F H :F: or H F

2. Double bond : When two atoms share two electron pairs, the bond formed is called double bond.

Eg: O2 molecule

O + O O : : O or O O

3. Triple bond : When two atoms share three electron pairs, the bond formed is called triple bond.

Eg: N2 molecule

N + N N N

Double and triple bonds are together called multiple bond.

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General characteristics of covalent compounds

1. Covalent compounds exist in all the three states (solid, liquid and gas)

2. Covalent compounds generally have low melting and boiling points because the molecules in covalent
compounds are usually held together by weak vander waals forces.

3. They are generally soluble in organic solvents but insoluble in water.

4. They are generally bad conductors of electricity.

Co-ordinate bond or Dative bond

The bond formed between two atoms in which contribution of an electron pair is made by one atom
out of them while the sharing is done by both (one side sharing).

Eg :

+
H

1) NH3 + H+ N
H H H

Ammonium ion

O
2) O3
O O

+
O
3) H3O+ H H
H

Formal charge

The charge possessed by an atom in a polyatomic ion or molecule considering its Lewis structure is
called formal charge of that atom.

Formal charge = Total number of valence electron in the free atom – Total number of non bonding
electron – 1/2  no.of bonding electrons.

Eg : O3 molecule

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2
O
1 3
O O

F.C. of OI = 6 – 4 – ½  4

F.C. of OII = 6 – 2 – ½  6 = +1

F.C. of OIII = 6 – 6 – ½  2 = –1

Limitations of Octet rule

1. The incomplete octet of central atom:- In some compounds, the number of electrons surrounding
the central atom is less than eight.

Eg : BeH2, BCl3, BF3 etc

2. Odd Electron molecules:- In molecules with an odd number of electrons like NO and NO2, the octet
rule is not satisfied for all the atoms.

Eg: NO - N O

N
NO2 - O
O

3. The expanded octet :- The octet rule is violated in the formation fo compounds such as PCl5, SF6
and IF7 etc. In these molecules, the central atoms have more than eight electrons in their valence
shells.

Eg : PCl5, SF6, IF7, SF4 etc.

4. Formation of compounds by xenon and krypton

5. This theory does not account for the shape of moleucles.

6. If does not explain the relative stability of the molecules.

Ionic or Electrovalent bond

An ionic bond or electrovalent bond is formed by the complete tranference of one or more valence
electrons of one atom to another. In this way both the atoms acquire electronic configuration of the
nearest noble gas.

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The atom which loses its valence electrons acquire positive charge and is known as cation or positive
ion. The atom which gains electrons acquires negative charge and is called anion or -ve ion. These
two oppositely charged ions then formed attracts each other by electrostatic force of attraction. The
bond thus formed is known as ionic bond or electrovalent bond.

Na + Cl [Na] + + [Cl]

Factors favouring formation of ionic bond

1. Low ionisation energy of the electropositive atom

2. High negative electron gain enthalpy of the electronegative atom

3. High lattice energy of the compound formed

4. Difference in electronegativity between bonded atoms should be greater than 1.7

Lattice energy

It is the energy required to completely separate one mole of the solid ionic compound into constituent
gaseous ions.

 
Eg : NaCls   Na (g )  Cl(g ) ;  latticeH  788 kJ / mol

Factors affecting lattice energy

q q 
L.E 
r
q+  charge on cation
q–  charge on anion

r  r  r  interionic distance

Partial covalent character in ionic compounds (Fajan’s rule):

When anion and cation approach each other, the valence shell of anion is pulled towards cation
nucleus and thus shape of anion is deformed. This phenomenon of deformation of anion by a cation is
known as polarisation and the ability of cation to polarize a nearby anion is called as polarizing power
of cation.

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Fajan’s pointed out that greater is the polarization of anion in a molecule, more is covalent character
in it.
More distrortion of anion, more will be polarisation, then covalent character incresaes.
Fajan’s gives some rules which govern the covalent character in the ionic compounds, which are as
follows:
i. Size of cation : Smaller is the cation more is its polarizing power and thus more will be the polarisation
of anion. Hence more will be covalent character in compound.
ii. Size of anion : Larger is the anion, greater is its polarisability and, therefore, more will be the
polarisation. Thus more will be covalent character in compound.
iii. Charge on cation : Higher is the oxidation state of cation, more will be the deformation of anion and
thus, more will be covalent character in compound.
iv. Charge on anion : Higher is the charge on anion more will be the polarisation of anion and thus more
will be covalent character in the compound.
v. Pseudo inert gas configuration of cation : Cation having pseudo inert gas configuration has more
polarizing power than the cation that has inert configuration.

Valence Bond Theory (VBT)

In valence bond theory, it is assumed that atoms with all their bonding electrons approach each other
to form a molecule. This theory was first applied by Heitier and London in 1927 to the formation of the
hydrogen molecule. It was further extended by Slater and Pauling.

According to the modern concept, the formation of bonds between atoms occur only if it is accompanied
by decrease of energy. Thus, the tendency of atoms to acquire stability by lowering their potential
energy is repsonsible for the formation of bond between them.

Let us consider two hydrogen atoms HA and HB lying far apart from each other, so that no interaction
occurs between them. It is assumed that when the two atoms are far away from each other, that is the
distance between HA and HB is infinity, the potential energy of the system is zero.

When the two atoms come closer, new attractive and repulsive forces begin to operate.

a. Attractive forces : Attractive forces operate between

i) Nucleus of one atom and its own electron ie. NA – eA and NB – eB

ii) Nucleus of one atom and electron of other atom .i.e, NA – eB and NB – eA

b. Repulsive forces : Repulsive forces operate between

i) Electron of the two atoms i.e., eA – eB

ii) nuclei of the two atoms i.e., NA – NB

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It has been found that in the beginning, the magnitude of attractive forces is greater than the repulsive
forces. As a result, the two atoms go on approaching each other and the potential energy of the
system goes on decreasing. Ultimately a stage is reached at which the total forces of attraction
balance the forces of repulsion. At this stage the system will have minimum energy and the two
hydrogen atoms are said to be bonded together resulting in the formation of H2 molecule. The distance
between the two nuclei in the molecule is called the bond length and it is found to be 74 pm (or 0.74 A0)
for H2, The potential energy changes taking place during the formation of H2 molecule is shown
graphically below.

The decrease in potential energy is accompanied by a release of energy when the H2 molecule is
formed from the two H atoms. That means heat is given out when a bond is formed. If a H2 molecule
(H–H) is to be broken, the process is endothermic or energy must be supplied.

Orbital overlap concept of covalent bond formation

In covalent bonding, there is a change in electron densities in the combining atoms. Accumulation of
electron densities between the two nuclei results in bond formation. When two atoms approach, there
is overlapping of electron waves.

The main ideas of orbital overlap concept of covalent bond formation are

i. Covalent bonds are formed by overlapping of half filled atomic orbitals present in the valence shell of
the atoms taking part in bonding.

ii. The orbitals undergoing overlapping must have electrons with opposite spins

iii. The strength of a covalent bond depends upon the extend of overlapping.

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Overlapping of atomic orbitals

When two atoms come close to each other there is overlapping of atomic orbitals. This overlap may
be positive, negative or zero depending upon the properties of overlapping of atomic orbitals. The
various arrangement of s and p orbitals resulting in positive, negative and zero overlap are depicted
in the following figure.

The criterion of overlap, as the main factor for the formation of covalent bonds applies uniformly to the
homonuclear/heteronuclear diatomic molecules and polyatomic molecules. In the case of polyatomic
molecules like CH4, NH3 and H2O, the VB theory has to account for their characteristic shapes as well.
We know that the shapes of CH4, NH3 and H2O molecules are tetrahedral, pyramidal and bent
respectivley.

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TYPES OF COVALENT BONDS

Sigma (  ) and pi (  ) bonds

a. Sigma (  ) bond : The bond formed by the axial (or head-on) overlap of atomic orbitals along the
internuclear axis is known as (  ) bond. Sigma bond may be formed by any one of the following types
of overlapping.

i. Overlapping of s-s orbitals : Hydrogen molecule (H2) formation is an example of 1s-1s overlap
between two hydrogen atoms, resulting in the formation of a covalent bond.

ii. Overlapping of s-p orbitals

The half filled s orbital of one of the two elements overlaps with the half-filled p-orbital of the other
element resulting in the formation of a chemical bond. Examples of this type of s–p overlap are the
formation of compounds HF, HCl etc. The general representation of an s–p orbital overlap can be
made as shown.

iii. Overlapping of p–p orbitals

The half filled p orbital of one of the two elements overlaps with the half filled p orbital of the other
element resulting in the formation of a chemical bond. Examples of this type are the formation of
compounds like F2, Cl2 etc.

b. Pi    bond: Covalent bond formed by the lateral or sidewise overlap of half-filled atomic orbitals is

known as pi    bond. The atomic orbitals overlap in such a way that their axes remain parallel to
each other and perpendicular to the internuclear axis.

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Differences between sigma and pi bonds

 bond  bond

It is form ed by axial overlap of s-s or s-p or

It is form ed by lateral overlap of p-p orbitals
p-p orbitals of two atom s

Extent of overlappiing is quite large and Overlapping is to a sm all extent and hence 
hence  bond is a strong bond bond is a weak bond

There can only be one  bond between There can be one or two  bonds between two
two atom s atoms

Electron cloud is cylindrically sym m etrical Elec tron cloud of  bond is uns ymm etrical
about the line joining the two nuclei about the internuclear axis.

 bond may involve the overlapping of  bond usually involves the overlapping of pure
hybrid orbitals. They determine the shape orbitals . They do not determine the shape of
of the m olecule m olecules.

Hybridisation

It is defined as the intermixing of atomic orbitals of slightly different energy and shape so as to redistribute
their energies, resulting in the formation of new set of orbitals of identical shape and similar energy.This
explains why atoms like Be, B, C show a valency of 2, 3 and 4 respectively. The energy required for
excitation is compensated by energy released during bond formation.

Characteristics of hybridisation

1. The number of hybrid orbitals formed is equal to the number of orbitals that get hybridised.

2. The hybrid orbitals are always equivalent in energy and shape.

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3. The hybrid orbitals are more effective in forming stable bonds than unhybridised atomic orbitals.
4. The hybrid orbitals are directed in space in some preferred directions so as to have minimum repulsion
between electron pairs. Therefore, the type of hybridisation indicates the geometry of the molecule.
Types of hybridisation
1. sp hybridisation : This involves one s and one p orbital of the valence shell of an atom resulting in
the formation of two new equivalent hybridised orbitals. The sp hybrid orbitals have 50% s and 50%
p character. The sp hybrid orbitals are linear and lie in the same line at an angle of 180° from each
other.
Structure of BeCl2 : In BeCl2, Cl–Be–Cl, the central Be atom uses both its valence electrons in
forming 2 bonds with the two chlorine atoms.

Each of these orbitals overlaps axially with half filled 3p orbitals of chlorine to form two Be–Cl bonds.
Few other compounds which exhibit sp hybridization are BeF2, CO2, CH3CN, HCN etc.
2. sp2 hybridisation : This involves the mixing up of one s and two p orbitals of the valence shell of an
atom to form three new equivalent orbitals. The three new equivalent sp2 orbitals are formed with
33% s character and 67% p character. The three equivalent orbitals have a symmetrical distribution
and are directed towards the corners of a trigonal planar structure at an angle of 120° from one
another.
Strucutre of BCl3 : In BCl3, the ground state electronic configuraiton of the central boron atom is 1s2
2s2 2p1. In the excited state, one of the 2s electrons is promoted to vacant 2p orbital, as a result boron
has three unpaired electrons. These three orbitals hybridise to form three sp2 hybrid orbitals. The
hybrid orbitals formed are oriented in a trigonal planar arrangement and overlap with the 3p orbitals of
chlorine to form three B–Cl bonds.

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3. sp3 hybridisation : This involves the mixing up of one s and three p orbitals of the valence shell of an
atom to form four new equivalent orbitals. Each sp3 hybrid orbital has 25% s-character and 75% p-
character. The four sp3 hybrid orbitals are directed towards the four corners of a tetrahedron to minimise
repulsion. The angle between the sp3 hybrid orbitals is 109°28/ or approximately 109.5°.

Structure of methane (CH4)

Carbon atom in the ground state

Carbon atom in the excited state

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Carbon atom after sp3 hybridisation

In methane, the four sp3 hybridised orbitals of carbon are directed towards the four corners of a
regular tetrahedron with the carbon atom located at the centre and four hydrogen atoms at the corners.
Each of the four sp3 hybrid orbitals on carbon is singly filled. In the formation of methane, each of
these hybrid orbitals overlap with the half filled 1s orbital of hydrogen. This results in four C–H bonds
and these single bonds are known as sigma    bonds. The axes of the sp3 orbitals are directed
towards the four corners of a regular tetrahedron, with the carbon at the centre with H–C–H bond
angle 109°28/
Energy is required for the promotion of a 2s electron to 2p orbital and for the hybridisation of the
orbitals to give equivalent orbitals, but this is compensated by the release of energy in the formation
of covalent bonds involving the sp3 hybrid orbitals.
4. sp3d hybridisation : When one s orbital, three p orbitals and one d orbital are involved in the
hybridisaiton, it is called sp3d hybridisation. For example, phosphorus in PCl5 is sp3d hybridised.
Structure of PCl5 : The structure of PCl5 shows that the central atom P uses all its five electrons from
its valence shell (3s2 3p3) in forming the 5 bonds with five chlorine atoms.

P atom in the ground state :

P atom in the excited state:

The result is that there are five non-equivalent sp3d hybrid orbitals with 2 axial orientations and 3
equatorial (lateral) orientations. sp3d hybrid orbitals are singly occupied with electrons. They form five
 bonds with five p orbitals of five chlorine atoms.
PCl5 has a trigonal bipyramidal shape. Of the five bonds, three equatorial bonds are equal in length
and two axial bonds are longer than the equatorial bonds. This is because axial bond pairs suffer
more repulsive interaction from the equatorial bond pairs. Axial bonds are less stronger than equatorial
bonds.

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5. sp3d2 hybridisation: It involves the mixing up of one s orbital three p orbitals and two d orbitals to give
six hybridised orbitals. Sulphur hexafluoride (SF6) is an example of a molecule where sulphur shows
sp3d2 hybridisation.
Structure of SF6 : In SF6, all the six valence electrons of sulphur are used up. There are six sp3d2
equivalent orbitals formed after hybridisation with no lone pair of electrons. Each of the six hybridised
sp3d2 orbitals are singly filled before bonding.
Each one of these sp3d2 hybridised orbitals overlaps with p orbitals of six fluorine atoms to form SF6.
The molecule has an octahedral shape.

As the s-character in a hybrid orbital increases its electronegativity increases, since the s-electrons
are more close to the nucleus.

Structure of acetylene (H–C  C–H)

Both the carbons in acetylene are sp hybridised.

Carbon atom in the excited state

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Carbon atom after hybridisation

One sp hybrid orbital of one carbon atom overlaps axially with sp hybrid orbital of the other to form
C–C sigma bond. The other sp hybrid orbital of each carbon overlaps axially with 1s orbitals of
hydrogen atoms to form C–H sigma bonds. Each of the two unhybrisides orbitals (2py and 2pz) of one
carbon atom overlaps sidewise with similar orbitals of the other carbon atom to form two  bonds.
Acetylene molecule is linear with bond angle of 180°.

Structure of ethyelen (CH2 = CH2) : Both the carbons in ethylene are sp2 hybridised.

Carbon atom in the excited state :

Carbon atom after hybridisation :

The three sp2 hybrid orbitals of carbon are oriented in a plane and are inclined at an angle of 120°.
One sp2 hybrid orbital of one carbon atom overlaps axially with sp2 hybrid orbitals of the other carbon
to form C–C sigma bond. The remaining two sp2 hybrid orbitals of each carbon atom overlap axially
with one s orbital of each carbon atom overlap axially with one s orbital of hydrogen to form C–H
sigma bonds. The unhybridised two p orbitals (2pz) of each carbon atom is oriented at right angles to
the sp2 hybridised orbitals. These unhybridised 2pz orbitals of the two carbon atoms overlap sidewise
to form a  bond. The  bond consist of two equal electron clouds distributed above and below the
plane of other atom.

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Structure of ammonia molecule (NH 3): The electronic configuration of nitrogen atom is
1s1 2s2 2p1x 2p1y 2p1z . In the formation of NH3 molecule, nitrogen undergoes sp3 hybridisation in
which one 2s and three 2p orbitals hybridise to form four sp3 hybrid orbitals.

One of these hybrid orbitals contains a lone pair of electrons while the other three contain one unpaired
electron each. The four sp3 hybrid orbitals will be directed towards the corners of a tetrahedron. The
three hybrid orbitals containing unpaired electrons overlap axially with half filled 1s orbitals of hydrogen
to form three N–H sigma bonds. The lone pair of electrons do not participate in bond formation. Thus
in ammonia, nitrogen is surrounded by three bond pairs and one lone pair of electrons. The lone pair
of electrons repel the bond pairs strongly. As a result, the three N–H bonds mvoe slightly closer. Thus
the bond angle in ammonia decreases from 109.5° to 107°.
Since one of the tetrahedral positions is occupied by a lone pair, the shape of ammonia molecule is
said to be pyramidal.

2
Structure of water molecule (H2O) : The electronic configuration of oxygen is 1s 2s2 2p2x 2p1y 2p1z .
It contains two unpaired electrons. In the formation of H2O molecule, oxgen undergoes sp3 hybridisation
in which 2s and three 2p orbitals hybridise to form four sp3 hybrid orbitals.

Two of these hybrid orbitals contain lone pairs while the other two contain one unpaired electron
each. These hybrid orbitals containing unpaired electrons overlap axially with half filled 1s orbitals of
hydrogen to form two O–H sigma bonds. Thus in water, oxygen is surrounded by two lone pairs and
two bond pairs of electrons. Since the lone pairs repel the bond pairs very strongly, the two O–H
bonds move closer. Thus the bond angle in water is reduced to 104.5°.
Since two of the tetrahedral positions are occupied by lone pairs, water is said to be V-shaped (Bent)

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VALENCE SHELL ELECTRON PAIR REPULSION (VSEPR) THEORY :

Lewis concept is unable to explain the shapes of molecules. This theory provides a simple procedure
to predict the shapes of covalent molecules. Sidgwick and Powell in 1940, proposed a simple theory
based on the repulsive interactions of the electron pairs in the valence shell of the atoms. It was
further developed and redefined by Nyholm and Gillespie (1957).

The main postulaes of VSEPR theory are as follows:

i. The shape of a molecule depends upon the number of valence shell electron pairs (bonded or
nonbonded) around the central atom.

ii. Pairs of electrons in the valence shell repel one another since their electron clouds are negatively
charged.

iii. These pairs of electrons tend to occupy such positions in space that minimise repulsion and thus
maximise distance between them.

iv. The valence shell is taken as a sphere with the electron pairs localising on the spherical surface at
maximum distance from one another.

v. A multiple bond is treated as it it is a single electron pair and the two or three electron pairs of a
multiple bond are treated as a single super pair.

vi. Where two or more resonance structures can represent a molecule, the VSEPR model is applicable
to any such structure.

The repulsive interaction of electron pairs decreases in the order:

lone pair  p  – lon pair  p  > long pair  p  – bond pair (bp) > bond pair (bp) > bond pair (bp)

Nyholm and Gillespie (1957) refined the VSEPR model by explaining the important difference between
the lone pairs and bonding pairs of electrons. While the lone pairs are localised on the central atom,
each bonded pair is shared between two atoms. As a result, the lone pair electrons in a molecule
occupy more space as compared to the bonding pairs of electrons. This resultant in greater repulsion
between lone pairs of electrons as compared to the lone pair - bond pair and bond pair - bond pair
repulsion. These repulsion effects result in deviations from idealised shapes and alterations in bond
angles in molecules.

For the prediction of geometrical shapes of molecules with the help of VSEPR theory it is convenient
to divide molecules into two categories as (i) molecules in which the central atom has no lone pair and
(ii) molecules in which the central atom / ion has one or more lone pairs.

Shape (molecular geometry) of some simple molecules/ions with central atom/ion having no
lone pairs of electrons (E).

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Shape (molecular geometry) of some simple molecules/ions with central atom/ions having one or
more lone pairs of electrons (E).

Dipole moment
The degree of polar character in a polar covalent bond is given in terms of dipole moment. This is
expressed as the product of the magnitude of the electric charge (Q) and the distance (r) between the
positive and negative ends of the molecule.

Dipole moment is represented as  ;  = Q  r

Where  - dipole moment, r - distance between two atoms

SI unit of dipole moment is coulomb meter (Cm). Dipole moment is usually expressed in Debye units
(D)

1D = 3.33564  10 30 Cm  1  1018 esu cm

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BOND PARAMETERS:
1. Bond length : The average distance between the centres of the nuclei of the two bonded atoms is
called bond length.

 For ionic compounds, the sum of ionic radius of cation and anion is called B.L.
 For covalent compounds sum of covalent radius is called B.L.
2. Bond Energy : The amount of energy required to break one mole of bonds of a particular type. So as
to separate them into gaseous atoms is called bond energy (B.E.)
3. Bond order : It is the number of covalent bonds between two atoms in a molecule. It is lobe noted
that isoelectronic ions and molecules will have the same bond order.
Eg : NO+, CO and N2 have the same bond order of 3.
4. Bond angle : It is the angle between the orbitals containing bonding electron pairs around the central
atom in a molecule.
Molecular orbital theory
Molecular orbital theory was developed by Hund and Mulliken in 1932. The main ideas of this theory
may be summed up as follows:-
i. In molecules, electrons are present in new orbitals called molecular orbitals.
ii. Molecular orbitals are formed by the combination of atomic orbitals of nearly same energies and
proper symmetry.
iii. Molecular orbitals are associated with the nuclei of all the bonded atoms in a molecule. ie., a molecular
orbitals is polycentric. (But an electron in an atomic orbital is under the influence of the nucleus of only
one atom. ie,atomic orbitals are monocentric).
iv. The number of molecular orbitals formed is equal to the number of combining atomic orbitals. Among
the new molecular orbitals formed, half are of lower energy than the combining atomic orbitals (called
bonding molecular orbitals) and the other half are of higher energy than the combining atomic orbitals
(called antibonding molecular orbitals)
v. Like atomic orbitals, molecular orbitals are also filled in accordance with Pauli’s exclusion principle,
Hund’s rule and Aufbau principle.
Linear Combinatin of Atomic Orbitals (LCAO)

According to wave mechanics, atomic orbital is expressed by wave function  . Molecular orbitals are
formed by linear combination of atomic orbitals which takes place by addition and subtraction of wave
functions of individual atomic orbitals.
The method can be illustrated by considering the formation of hydrogen moleucle from two hdyrogen
atoms A and B. Le the wave functions of the electrons in the atomic orbitals of the two atoms be
A and B respectively. According to LCAO method, the wave functions of the two molecular orbitals
formed are obtained by linear combination of A and B as shown below

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The two molecular orbitals  and * formed can be represented as

 BMO  A  B

 AMO  A  B

The molecular orbital formed by the addition of atomic orbitals is called the bonding molecular orbital
while the molecular orbital formed by subtraction of atomic orbitals is called antibonding molecular
orbital.
In bonding MO, the electron charge density between the two nuclei is high and therefore the repulsion
between the nuclei is very low. Bonding molecular orbital, therefore, gets stabilised and bond formation
is favoured.
In an antibonding MO, the electron charge density between the two nuclei is low and therefore the
repulsion between the nuclei is high and hence the anti bonding molecular orbital is destabilized.
Bond formation is not favoured in teh anti bonding molecular orbital.
Combination of s-s atomic orbitals

Energy level diagram for 1s bonding and  *1s antibonding molecular orbitals formed by the linear
combination of 1s atomic orbitals of the two hydrogen atoms in a hydrogen molecule is shown below.

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Difference between bonding and antibonding molecular orbitals

Conditions for combination of atomic orbitals

1. The combining atomic orbitals must have the same or nearly the same energy.
2. The atomic orbitals must have the same symmetry about the molecular axis. Thus a 2pz orbital can
combine with 2pz of another atom but not with the 2px or 2py of the second atom.
3. The atomic orbitals must overlap to maximum extend.
Types of molecular orbitals
There are different types of molecular orbitals called  orbital,  orbital etc.

If two atomic orbitals overlap along the internuclear axis, the molecular orbital formed is called a
sigma    molecular orbital. Sigma molecular orbitals are symmetrical around the internuclear axis.
For example, the molecular orbitals formed by the combination of two 1s orbitals are sigma molecular
orbitals. Similarly 2s orbitals and 2pz orbitals also combine to form  molecular orbitals.

If two atomic orbitals overlap sidewise, the molecular orbitals formed is called pi    molecular orbital.

Pi    molecular orbitals are not symmetrical around the internuclear axis. For example, the molecular
orbitals formed by two 2px orbitals are  molecular orbitals. Similarly, 2py orbitals also combine to
form  molecular orbitals.
Molecular orbitals formed from p orbitals
By convention atoms form bonds along the z axis, 2pz orbitals lie along the molecular axis. Therefore
they overlap axially by addition and substraction to form two  molecular orbitals namely bonding
and antibonding sigma molecular orbitals.

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2px and 2py overlap laterally to produce MO’s which are called  MO’s. Bonding and antibonding
2p x and * 2p x molecular orbitals are formed respectively. In  -MO’s the electron density is above
and below the internuclear axis. There is zero electorn density (nodal plane) on the line joining the
two nuclei.

*
Similarly py orbitals also overlap laterally to form 2py and  2py molecular orbitals. 2p x and

2p y orbitals are degenerate (same energy orbitals) and * 2py and * 2px orbitals are also
degenerate.
Energy level diagram for molecular orbitals

We have seen that 1s atomic orbitals of two form two molecular orbitals designated as 1s and *1s .
Similarly 2s orbitals give rise to 2s and * 2s . Molecular orbitals produced from 2p orbitals are

2pz , * 2pz , 2px , 2py , * 2px and * 2py . The energy levels of these orbitals have been
determined from spectroscopic data.

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Bond order : Bond order is defined as one half of the difference between the number of electrons in
the bonding molecular orbitals (Nb) and that in the antibonding molecular orbitals (Na)

1
Bond order =  Nb  Na 
2
If the number of electrons in the bonding and antibonding orbitals is the same, the bond order is zero
and hence no bond formation occurs. Bond orders 1, 2 and 3 represent single, double and triple
bonds respectivley. The bond length decrease as bond order increase.
Magnetic properties from MOT
If all the molecular orbitals contain paired electrons, the molecule will be diamagnetic i.e., weakly
repelled by external magnetic field and if one or more molecular orbitals contain unpaired electrons
the molecule in paramagnetic.
BONDING IN SIMPLE HOMONUCLEAR DIATOMIC MOLECULES
1. Hydrogen molecule, H2
Number of electrons in H2 is 1 + 1 = 2

The electronic configuration in H2 = 1s 2

Bond order = 12  Nb  Na   12  2  0   1

There is a single bond, H–H

Molecule is stable and diamagnetic

2. Hydrogen molecule cation, H2

No. of electrons = 1

Electronic configuration = 1s1

Bond order = 12 1  0   12

H2 is less stable because bond order is less than one. H2 is paramagnetic.

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3. Hydrogen moleucle anion, H2

No. of electrons = 3

Electronic configuration = 1s 2 *1s1

Bond order = 12  2  1  12

Molecule is less stable and paramagnetic.

4. Boron molecule, B2

No. of electrons = 10

2 * 2 1 1
Electronic configuration : KK 2s  2s 2p x 2p y

Bond order = 1 2  6  4   1

Molecule has two unpaired electrons.  paramagnetic

5. Carbon molecule, C2

No.of electrons = 12

2 * 2 2 2
Electronic configuration: KK 2s  2s 2px 2p y

Bond order = 12  8  4   2

Molecule is stable and diamagnetic

6. Nitrogen molecule, N2

No.of electrons = 14

2 * 2 2 2 2
Electronic configuration : KK 2s  2s 2px  2p y 2pz

Bond order = 1 2 10  4   3

There is a triple bond. Bond energy is high (946 kJ mol–1). Bodn length is small. (110 pm). It is
diamagnetic.

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7. Oxygen molecule, O2
Number of electrons = 16

2 * 2 2 2 2 * 1 * 1
Electronic configuration : KK 2s  2s 2pz 2px  2py  2px   2py

Bond order = 12 10  6   2

There is a double bond in oxygen molecule. It has a short strong bond. It is to be specially noted that
the molecule contains two unpaired electrons and therefore paramagnetic. According to VBT, O2
molecule has only paired electrons and should be diamagnetic. Actually O2 is paramagnetic. This was
one of the earliest triumphs of MOT over VBT. Bond length = 121 pm.
Bond energy = 493 kJ mol–1.

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8.

Super oxide ion O2  
O2 ion is formed by the combination of an oxygen atom with an oxygen ion O–. There are 13 electrons
in the molecular orbital of O2 , exclusive of the K shell.

2 * 2 2 2 2 * 2 * 1
O2 = KK 2s  2s 2pz 2px  2py  2px   2py

1 1
Bond order = 10  7   1
2 2

There is one unpaired electron and O2 is paramagnetic.

Properties of O2, N2 and their ions related with bond order

9. Fluorine molecule, F2
No.of electrons = 18
2 * 2 2 2 2 * 2 * 2
Electronic configuration = KK  2s  2s pz 2p x  2p y  2p x   2p y

Bond order = 1 2 10  8   1

10. Neon molecule, Ne2

No.of electrons = 20

Electronic configuration =

Bond order = 1 2 10  10   0

Since bond order is zero, molecule cannot exist. Ne exists as monoatomic molecule.

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RESONANCE STRUCTURES
When a molecule can be represented by more than one Lewis formula, none of which is able to
describe the molecule accurately, then the actual structure is a resonance hybrid of the various Lewis
formulae (canonical forms). For example, ozone can be represented by two Lewis structures:

In structures I and II, the O = O bond length (121 pm) should be smaller than O – O (148 pm) bond
length. But experiments have shown that both bonds are of equal length, 126 pm, which is intermediate
between that of single and double bonds.
The actual structure of ozone is intermediate between structures I and II and is called a resonance
hybrid. Structures I and II are called resonating structures, contributing structures or canonical forms.
The resonance between canonical forms can be represented by a double headed arrow (  ). Although
it is not possible to draw the Lewis structure for the resonance hybrid, some idea can be drawn from
the structure shown below, in which each oxygen-oxygen bond is intermediate between single and
double bonds. The actual structure does not oscillate between the resonating forms and has its identity.
Rules for writing resonating structures
1. The contributing structures should have same arrangement of atoms. They should differ only in
electronic arrangements.
2. The contributing structures should have same number of paired and unpaired electrons.
3. The contributing structures should have nearly same energy.
4. Contributing structures should be so written that negative charge (if appears) is on electronegative
element and positive charge is on electropositive element.
5. In contributing structures, like charges should not reside on adjacent atoms.
RESONATING STRUCTURES OF SOME SPECIES
i) Carbon dioxide molecule (CO2)

O=C=O O C O O C O

ii) Carbonate ion (CO32–)

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iii) Benzene molecule (C6H6)

CHARACTERISTICS OF RESONANCE
1. Resonating structures are hypothetical and do not have real existence.
2. The actual molecule has a single structure which is a resonance hybrid of various cannonical forms
and as such it cannot be depicted by a single Lewis structure.
3. Bond lengths in hybrid structures are intermediate between the bond lengths in various resonating
forms, e.g. C–C bond length in benzene molecule is 139 pm which is intermediate between C–C (154
pm) and C = C (134 pm).
4. Resonance hybrid is more stable, i.e., having lower energy than any of the resonating forms.
5. Cannonical structures of similar energy contribute equally to the resonance hybrid. However, the
structure with higher energy is less stable and makes lesser contribution to the resonance hybrid.
6. The difference in energy between the resonance hybrid and the most stable resonating form is called
resonance energy.
7. Larger the value of resonance energy, greater will be the stability of the resonance hybrid.
8. Bond order of a particular bond in a molecule can be calculated from the resonating structure using
the following formula:

Total number of bonds between two atoms in all resonating forms

Bond order =
Total number of resonating forms
For calculating C–O bond order in CO32– ion., let us consider bonds of C atom with a particular O atom
in all the three resonating structures.

These is 1 bond in srtructure I, 1 bond in structure II and 2 bonds (double bond) in structure III. Thus
11 2
C – O bond order   1.33.
3
HYDROGEN BONDING
Nitrogen, oxygen and fluorine are the highly electronegative elements. When they are attached to a
hydrogen atom to form covalent bond, the electrons of the covalent bond are shifted towards the
more electronegative atom. This partially positively charged hydrogen atom forms a bond with the
other more electronegative atom. This bond is known as hydrogen bond and is weaker than the
covalent bond. For example, in HF molecule, the hydrogen bond exists between hydrogen atom of
one molecule and fluorine atom of another molecule as depicted below:

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  H  F     H  H    H  F  . Here, hydrogen bond acts as a bridge between two

   

atoms which holds one atom by covalent bond and the other by hydrogen bond. Hydrogen bond is
represented by a dotted line (---) while a solid line represents the covalent bond. Thus, hydrogen
bond can be defined as the attractive force which binds hydrogen atom of one molecule with the
electronegative atom (F, O or N) of another molecule.
Cause of formation of Hydrogen bond
When hydrogen is bonded to strongly electronegative element ‘X’, the electron pair shared between
the two atoms moves far away from hydrogen atom. As a result the hydrogen atom becomes highly
electropositive with respect to the other atom ‘X’. Since there is displacement of electrons towards X,

 
 
the hydrogen acquires fractional positive charge  while ‘X’ attain fractional negative charge  .  
This results in the formation of a polar molecule having electrostatic force of attraction which can be
represented as:
    
H  X     H    H  X 
The magnitude of H-bonding depends on the physical state of the compound. It is maximum in the
solid state and minimum in the gaseous state. Thus, the hydrogen bonds have strong influence on
the structure and properties of the compounds.
Types of H-Bonds : There are two types of H-bonds
i) Intermolecular hydrogen bond
ii) Intramolecular hydrogen bond
1. Intermolecular hydrogen bond : It is formed between two different molecules of the same or different
compounds. For example, H– bond in case of HF molecule, alcohol or water molecules, etc.
2. Intramolecular hydrogen bond : It is formed when hydrogen atom is in between the two highly
electronegative (F, O, N) atoms present within the same molecule. For example, in o-nitrophenol the
hydrogen is in between the two oxygen atoms.

Intramolecular hydrogen bonding in o-nitrophenol molecule.

Applications
1. To predict the boiling point of some compounds - hydrogen bonding increases the boiling point.
2. To predict the physical state of some compounds - H2O is liquid while H2S is gas.
3. To predict the existance of some compounds - KHF2 exist but KHX2 (X = Cl, Br and I) doesnot.
4. Intermolecular hydrogen bonding decreases the volatility and increases viscosity and surface tenstion.
5. Intermolecular hydrogen bonding in ice gives it an open cage like structure. As a result ice has lower
density than liquid H2O.
6. Due to hydrogen bonding ethanol has higher boiling point than diethylether.

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