Polarity of Bonds

Polar and Non-Polar Covalent bonds:

Non-Polar Covalent bonds: When the atoms are joined by covalent bond are the same i.e. the
shared pair of electrons is equally attracted by two atoms and thus the shared electron pair is
equidistant to both of them. As a result, no poles are developed and the bond is called as non-
polar covalent bond.
For Example,

Polar bond: When covalent bonds formed between different atoms of different
electronegativity, shared electron pair between two atoms gets displaced towards highly
electronegative atoms.
For Example, HCl molecule, since electronegativity of chlorine is high as compared to hydrogen
thus, electron pair is displaced more towards chlorine atom, thus chlorine will acquire a partial
negative charge (δ–) and hydrogen atom have a partial positive charge (δ+) with the magnitude of
charge same as on chlorination. Such covalent bond is called polar covalent bond.

Dipole moment : As a result of polarization, the molecule possesses the dipole moment which
can be defined as the product of charge and the distance between the centers of positive and
negative charge. It is usually designated by a Greek letter ‘μ’. Mathematically, it is expressed
asfollows:
Dipole moment (μ ) = charge (Q) X distance of separation (r)
Valence Bond Theory
Valence bond theory was introduced by Heitler and London (1927) and developed by Pauling
and others and based on the concept of atomic orbitals and the electronic configuration of the
atoms.
Foe example: Formation of hydrogen molecule based on valence-bond theory.
Two hydrogen atoms A and B having nuclei NA and NB and electrons are eA and eB .
As these two atoms come closer new attractive and repulsive forces begin to operate.
(i) The nucleus of one atom is attracted towards its own electron and the electron of the other and
vice versa.i.e. attraction between NA-eB and NA-eA or NB-eA and NB-eB
(ii) Repulsive forces arise between the electrons of two atoms and nuclei of two atoms.
i.e. NA-NB and eA-eB
Attractive forces tend to bring the two atoms closer whereas repulsive forces tend to push them
apart.
Orbital Overlap Concept
According to orbital overlap concept, covalent bond formed between atoms results in the overlap
of orbitals belonging to the atoms having opposite spins of electrons. Formation of hydrogen
molecule as a result of overlap of the two atomic orbitals of hydrogen atoms is shown in the
figures that follows:

Stability of a Molecular orbital depends upon the extent of the overlap of the atomic orbitals.
• Types of Orbital Overlap
Depending upon the type of overlapping, the covalent bonds are of two types, known as sigma
(σ ) and pi (π) bonds.
(i) Sigma (σ bond): Sigma bond is formed by the end to end (head-on) overlap of
bonding orbitals along the internuclear axis.
The axial overlap involving these orbitals is of three types:
• s-s overlapping: In this case, there is overlap of two half-filled s-orbitals along the
internuclear axis as shown below:

• s-p overlapping: This type of overlapping occurs between half-filled s-orbitals of

one atom and half filled p-orbitals of another atoms.

p-p overlapping: This type of overlapping takes place between half filled p-orbitals
of the two approaching atoms.
 (ii) pi (π bond): π bond is formed by the atomic orbitals when they overlap in such a
way that their axes remain parallel to each other and perpendicular to the internuclear
axis.The orbital formed is due to lateral overlapping or side wise overlapping.

Strength of Sigma and pf Bonds

Sigma bond (σ bond) is formed by the axial overlapping of the atomic orbitals while the π-bond
is formed by side wise overlapping. Since axial overlapping is greater as compared to side wise.
Thus, the sigma bond is said to be stronger bond in comparison to a π-bond.

Hybridization: It can be defined as the process of intermixing of the orbitals of slightly different
energies so as to redistribute their energies, resulting in the formations of new set of orbitals of
equivalent energies and shape.

Salient Features of hybridization :

#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.
Types of Hybridisation

(a)sp hybridisation: This type of hybridisation involves the mixing of one s and one p orbital
resulting in the formation of two equivalent sp hybrid orbitals. Each sp hybrid orbitals has 50%
s-character and 50% p-character. Such a molecule in which the central atom is sp-hybridised and
linked directly to two other central atoms possesses linear geometry with an angle of 180.
Example BeCl2 molecule

(b)sp2 hybridisation : In this hybridization there is involvement of one s and two p-orbitals in
order to form three equivalent sp2 hybridised orbitals. Each sp2 hybrid orbitals has 33.33% s-
character and 66.66 % p-character. Such a molecule in which the central atom is sp2 hybridised
and linked directly to three other central atoms possesses trigonal planar geometry 120°.
Example BCl3 molecule.

(c)sp3 hybridisation: In this type of hybridisation there is mixing of one s- orbital and three p-
orbitals of the valence shell to form four sp3 hybrid orbital of equivalent energies and shape.
There is 25% s-character and 75% p character in each Sp3 hybrid orbital. The four Sp3 hybrid
orbitals possesses tetrahedron geometry with an angle of 109.5° Example CH4 molecule
sp2 hybridisation in C2H4 molecule & sp hybridisation in C2H2 molecule

Formation of PCl5
Formation of SF6