CHEMICAL BONDING AND MOLECULAR STRUCTURE

CHEMICAL BOND
It is an attractive force which holds various constituents (atoms, molecules or ions) together in
different species.
Chemical bonds divided into two types:
a) Bonds which constitute molecules or formula units. These are ionic bonds, covalent bonds and
co-ordinate or dative bonds.
b) Bonds which hold various particles in solid or liquid state of the substances. These are also called
INTERMOLECULER FORCES. These are: metallic bonds, dipole-dipole forces, van der Waal forces,
hydrogen bonds.
Cause of Chemical Combination: Chemical bonding takes place due
• To acquire a state of minimum energy and maximum stability
• To convert atoms into molecule to acquire stable noble gas configuration.
LEWIS THEORY
Lewis theory gave the first explanation of a covalent bond in terms of electrons that was generally
accepted. If two electrons are shared between two atoms, this constitutes a bond and binds the
atoms together. For many light atoms, a stable arrangement is attained when the atom is
surrounded by eight electrons.
OCTET RULE- ‘Atoms combine with each other either by sharing or by the transfer of electrons to
attain stable noble gas configuration I n outer most shell.’
Lewis structures of some simple molecules.

1. H2O 2. NH3

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 3.CCl4 4. CO2

5. NF3 6. NO3-

7. CO32- 8. NH4+

9. CO 10. NO2-

11. SiCl4 12. BeF2

Limitations of Octet rule

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THE VALENCE SHELL ELECTRON
PAIR REPULSION (VSEPR) THEORY
The main postulates of VSEPR theory are:
The shape of a molecule depends upon the number of valence shell electron pairs (bonded
or nonbonded) around the central atom.
Pairs of electrons in the valence shell repel one another since their electron clouds are
negatively charged.
These pairs of electrons tend to occupy such positions in space that minimise repulsion and
thus maximise distance between them.
The valence shell is taken as a sphere with the electron pairs localising on the spherical
surface at maximum distance from one another.
A multiple bond is treated as if it is a single electron pair and the two or three electron pairs
of a multiple bond are treated as a single super pair.
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 (lp) – Lone pair (lp) > Lone pair (lp) – Bond pair (bp) > Bond pair (bp) –
Bond pair (bp)

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Geometry of molecules

1. BeCl2 - Linear

2. CO2 - Linear

3. BF3 - Triagonal planar

4. BCl3 - Triagonal planar

5. CH4 - Tetrahedral

6. PCl5 - Triagonal bipyramidal

7. SF6 - Octahedral

8. SO2 - Bent

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9. NH3- Trigonal Pyramidal

10. H2O - Bent

11. SF4 - See saw

12. ClF3 - T shape

13. BrF5- Square pyramidal

14. XeF4 - Square planar

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RESONANCE STRUCTURES
According to the concept of resonance, whenever a single Lewis structure cannot describe a
molecule accurately, a number of structures with similar energy, positions of nuclei, bonding and
non-bonding pairs of electrons are taken as the canonical structures of the hybrid which describes
the molecule accurately.
1. CO32-

NO3-

SO3

NO2-

POLARITY OF COVALENT BOND

 In a covalent molecule, the shared pairs of electrons are more closer to the electronegative
atom. As a result, a charge separation is developed in the molecule. Then the covalent
bond behaves as a polar bond. This is called polarity of covalent bond.

The polarity can be calculated in terms of Dipole moment.

Dipole moment (µ) = charge (Q) × distance of separation (r)
For example the dipole moment of HF may be represented as :

Q. Find out whether the following molecules are polar or non polar.
1. H2O – In H2O, the dipole moment is toward the oxygen atom as it is more electronegative
than the hydrogen. And the resultant dipole moment is in the direction of lone pair. Thus the total
DM is not equal to zero. Thus the molecule is polar.
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 2. BeH2 - In this the dipole moment is towards the hydrogen atom. Thus the dipoles may
cancel each other and the net dipole moment is zero. So the molecule is non polar.

3. CO2 - In this the dipole moment is towards the oxygen atom. Thus the dipoles may cancel
each other and the net dipole moment is zero. So the molecule is non polar.

4. BF3/BCl3 - In this the dipole moment is zero although the B – F bonds are oriented at an angle of
120o to one another, the three bond moments give a net sum of zero as the resultant of any two is
equal and opposite to the third.

Q. Explain why BeH2 molecule has a zero dipole moment although the Be–H bonds are polar.]

In the linear BeH2 molecule, the resultant dipole moment of two Be−H bonds cancel each other. Due to
this, the over all dipole moment of the molecule is zero.

5. Out of NH3 and NF3, which is more polar and why?

Both the molecules have pyramidal shape with a lone pair of electrons on nitrogen atom. Although
fluorine is more electronegative than nitrogen, the resultant dipole moment of NH3 is greater than
that of NF3. This is because, in case of NH3 the orbital dipole due to lone pair is in the same direction
as the resultant dipole moment of the N – H bonds, whereas in NF3 the orbital dipole is in the
direction opposite to the resultant dipole moment of the three N–F bonds.

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VALENCE BOND THEORY (VBT)
Orbital Overlap Concept
In the formation of hydrogen molecule, there is a minimum energy state when two hydrogen
atoms are so near that their atomic orbitals undergo partial interpenetration. This partial
merging of atomic orbitals is called overlapping of atomic orbitals. In general, greater the
overlap the stronger is the bond formed between two atoms.
Types of Overlapping and Nature of Covalent Bonds
The covalent bond may be classified into two types depending upon the types of
overlapping:
(i) Sigma(σ) bond, and
(ii) Pi(π) bond
(i) Sigma(σ) bond :
This type of covalent bond is formed by the end to end (hand-on) overlap of bonding orbitals
along the internuclear axis. This is called as head on overlap or axial overlap.
Types of sigma bonds
s-s overlapping : In this case, there is overlap of two half filled s-orbitals along the
internuclear axis.
s-p overlapping: This type of overlap occurs between half filled s-orbitals of one atom and
half filled p-orbitals of another atom.
p–p overlapping : This type of overlap takes place between half filled p-orbitals of the two
approaching atoms.

(ii) pi(π ) bond

In the formation of π 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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Q. Sigma bonds are stronger than pi bond. Why?
Ans: The overlapping of orbitals takes place to a larger extent in sigma bond than a pi bond.
Q. Multiple bonds are stronger than single bonds. Why?
Ans: Mutiple bonds may contain one or two pi bonds. And Pi bonds are always formed along
with a sigma bond.

Differentiate sigma and pi bond

Sigma bond Pi bond

It is single bond It is multiple bond

It is a stronger bond It is a weaker bond
It is formed due to the overlapping of It is formed due to the overlapping of
s-s, s-p or p-p orbitals. p-p orbitals.
It can exists independently It exists along with a sigma bond.
This bond is formed due to the axial This bond is formed due to the lateral
overlapping of atomic orbitals. overlapping of atomic orbitals.

HYBRIDISATION
Hybridisation can be defined as the process of intermixing of the orbitals of slightly different
energies so as to redistribute their energies, resulting in the formation of new set of orbitals
of equivalent energies and shape.

The number of hybrid orbitals is equal to the number of the atomic orbitals that get
hybridised.
The hybridised orbitals are always equivalent in energy and shape.
The hybrid orbitals are more effective in forming stable bonds than the pure atomic orbitals.
These hybrid orbitals are directed in space in some preferred direction to have minimum
repulsion between electron pairs and thus a stable arrangement.
Important conditions for hybridisation
The orbitals present in the valence shell of the atom are hybridised.
The orbitals undergoing hybridisation should have almost equal energy.

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 Promotion of electron is not essential condition prior to hybridisation.
It is not necessary that only half filled orbitals participate in hybridisation. In some cases,
even filled orbitals of valence shell take part in hybridisation.
Types of Hybridisation
• sp Hybridization: One s & one p orbital intermix to form two sp hybrid orbitals. This process
is called sp hybridization. sp-hybridised orbitals of equivalent shapes and energies and arrange
in straight line(linear shape) with angle of 180°.

sp2 Hybridisation: It is the intermixing of one s and two p orbitals to give three sp2 hybrid
orbitals is called sp2 hybridisation.

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sp3 Hybridisation:It is the intermixing of one s and 3 p orbitals to form four sp3 hybrid
orbitals is called sp3 hybridisation. Formed hybrid orbitals Oriented in tetrahedral manner with
angle between them is 109.50

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HYBRIDISATION IN CARBON COMPOUNDS
SP3 Hybridisation in C2H6 (Ethane) molecule:
In ethane molecule both the carbon atoms assume sp3 hybrid state. One of the four sp3 hybrid
orbitals of carbon atom overlaps axially with similar orbitals of other atom to form sp3 -sp3
sigma bond while the other three hybrid orbitals of each carbon atom are used in forming sp3–s
sigma bonds with hydrogen atoms.

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Formation of PCl5 (sp3d hybridisation):

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 Formation of SF6 (sp3d2 hybridisation):

MOLECULAR ORBITAL THEORY (MOT)

The electrons in a molecule are present in the various molecular orbitals as the electrons of
atoms are present in the various atomic orbitals.
The atomic orbitals of comparable energies and proper symmetry combine to form molecular
orbitals.
The number of molecular orbital formed is equal to the number of combining atomic orbitals.
When two atomic orbitals combine, two molecular orbitals are formed. One is known as
bonding molecular orbital while the other is called antibonding molecular orbital.
The bonding molecular orbital has lower energy and hence greater stability than the
corresponding antibonding molecular orbital.
Conditions for the Combination of Atomic Orbitals (LCAO)
1. The combining atomic orbitals must have the same or nearly the same energy.
2. The combining atomic orbitals must have the same symmetry about the molecular axis.
3. The combining atomic orbitals must overlap to the maximum extent.

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 Types of Molecular Orbitals
Molecular orbitals of diatomic molecules are designated as  (sigma),  (pi) etc.
In this nomenclature, the sigma () molecular orbitals are symmetrical around the bond-axis
while pi () molecular orbitals are not symmetrical.

The increasing order of energies of various molecular orbitals for O2 and F2 is

given below:

The increasing order of energies of various molecular orbitals for B2,C2 & N2 is

Electronic Configuration and Molecular Behaviour

The distribution of electrons among various molecular orbitals is called the electronic
configuration of the molecule. From the electronic configuration of the molecule, it is
possible to get important information about the molecule as discussed below
Stability of Molecules: If Nb is the number of electrons occupying bonding orbitals and Na the
number occupying the antibonding orbitals, then
i. the molecule is stable if Nb is greater than Na,
ii. the molecule is unstable if Nb is less than Na.
In (i) more bonding orbitals are occupied and so the bonding influence is stronger and a
stable molecule results. In (ii) the antibonding influence is stronger and therefore the
molecule is unstable.

BOND ORDER
Bond order (b.o.) is defined as one half the difference between the number of electrons
present in the bonding and the antibonding orbitals i.e.,
Bond order (b.o.) = ½ (Nb–Na)

Integral bond order values of 1, 2 or 3 correspond to single, double or triple bonds

respectively as studied in the classical concept.
 Bond-length
The bond order between two atoms in a molecule may be taken as an approximate measure
of the bond length. The bond length decreases as bond order increases.

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 If all the molecular orbitals in a molecule are doubly occupied, the substance is diamagnetic
(repelled by magnetic field). However if one or more molecular orbitals are singly occupied
it is paramagnetic (attracted by magnetic field), e.g., O2 molecule.
ELECTRONIC CONFIGURATION OF SOME SIMPLE MOLECULES (USING MOT)
(Refer NB)
HYDROGEN BOND
It is a force of attraction develop between Hydrogen atom and the electronegative atom
such as oxygen, fluorine or nitrogen.
TYPES OF HYDROGEN BOND
(i) Inter molecular H- bond

An intermolecular hydrogen bond is formed between two or more separate

molecules in a substance.
Eg: H2O, NH3, HF

(ii) Intramolecular H- bond

Within a single molecule, an intramolecular hydrogen bond is formed. It is

formed when two functional groups of a molecule form hydrogen bonds with
each other.

TEXTBOOK EXERCISE
4.4 4.23
4.5 4.24
4.7 4.27
4.8 4.28
4.11 4.30
4.13 4.32
4.15 4.33
4.20 4.35
4.21 4.36
4.22 4.40

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