VALENCY BOND THEORY AND

HYBRIDIZATION

ORGANIC CHEMISTRY

DR.IMMACULATE AKASO MPS

 Valence bond theory
 The valence bond theory was proposed by Heitler and London to
explain the formation of covalent bond quantitatively using quantum
mechanics.
 Later on, Linus Pauling improved this theory by introducing the concept of
hybridization.
 Valence bond (VB) theory assumes that all bonds are localized bonds
formed between two atoms by the donation of an electron from each
atom.
 Valence Bond theory describes covalent bond formation as well as the
electronic structure of molecules.
 The theory assumes that electrons occupy atomic orbital's of individual
atoms within a molecule, and that the electrons of one atom are
attracted to the nucleus of another atom.
 VALENCY BOND THEORY
Introduction:
Atoms with unpaired electrons tend to combine with other atoms which
also have unpaired electrons. In this way the unpaired electrons are paired
up, and the atoms involved all attain a stable electronic arrangement. This in
usually a full shell of electrons (i.e., a noble gas configuration). Two electrons
shared between two atoms constitute a bond.
The number of bonds formed by an atom is usually the same as the number
of unpaired electrons in the ground state, i.e., the lowest energy state.
However, in some cases the atom may form more bonds than this. This
occurs by excitation of the atom (i.e., providing it with energy) when
electrons which were paired in the ground state are unpaired and promoted
into suitable empty orbitals. This increases the number of unpaired
electrons, and hence the number of bonds which can be formed.
 Postulates of Valance Bond Theory :
 A molecule is considered to be made up of atoms.
 Electrons in atoms occupy atomic orbitals.
 Orbitals may or may not be hybridized.
 The atomic orbitals (or the hybrid orbitals) are thought to remain even
when the atom is chemically bonded in a molecule.
Example: 1. In HF, H has a singly occupied s-orbital that overlaps with a
singly filled 2p orbital on F.
2. In NH3, there are three singly occupied p-orbitals on N which overlap
with S-orbitals from three H atoms
 cont...
 A covalent bond is formed by the overlapping of two half filled
valence atomic orbital's of two different atoms.
 The electrons in the overlapping orbital's get paired and
confined between the nuclei of two atoms.
 The electron density between two bonded atoms increases due
to overlapping. This confers stability to the molecule.
 Greater the extent of overlapping, stronger is the bond
formed.
 The direction of the covalent bond is along the region of
overlapping of the atomic orbital's i.e., covalent bond is
directional.
 Limitations of valence Bond
Theory :

This theory does not explain :

 The directional nature of covalent bond.
 The formation of co-ordinate bond in which shared pair
of electrons is contributed by only one of the combining
atoms.
 The paramagnetic nature of O2 molecule.
 The structures of odd electron molecules or ions where no
pairing of electrons takes place.
 MOLECULAR ORBITAL
THEORY
Introduction: The molecular orbital theory given by Hund and
Mullikens considers that the valency electrons are associated with
all the concerned nuclii, i.e., with the molecule as a whoIe. Thus, in
other words, the atomic orbitals combine together to form
molecular orbitals in which the identity of both the atomic orbitals
is lost.
Postulates of Molecular Orbital Theory :
a) During the formation of bond, the two half-filled atomic·orbitals
with opposite spins combine to form two molecular orbitals
(M.O.).
b) One of which is bonding M.O. and other antibonding M.O. The
energy of combining atomic orbitals, however, should be of
similar magnitude
 MOLECULAR ORBITAL THEORY cont…
(b) A bonding M.O. has lower energy than the atomic orbitals from which it is
formed; while antibonding M.O. has higher energy than the atomic orbitals
from which it is formed.
(c) Two s or p-orbitals can overlap end-to-end to form one sigma bonding
molecular orbital (σ) and one sigma antibonding molecular orbital (σ *).
(d) Two p-orbitals can overlap sideways to form one pi (π)- bonding
molecular orbital and pi (π *) anti bonding orbital.
(e) The energies of σ -bonding orbitals are lower than those of π -bonding
orbitals.
(f) The orbitals of lower energy are filled first. Each orbital may hold up two
electrons, provided that they have opposite spins
g) When several orbitals have the same energy, (i.e., they are degenerate), electrons will be
arranged so as to give the maximum number of unpaired spins (Hund‘s rule).
Significance of Bond order
(a) A -ve or zero value of bond order indicates that the molecule is
unstable and does not exist. A +ve value of bond order indicates
that the molecule exists and is stable. Greater the value of bond
order, greater is stablity of the molecule.
(b) A bond order of + 1, +2, +3 indicates that the molecule is formed
by joining of two atoms by single, double or triple bond
respectively.
 Significance of Bond order
 similar 1s atomic orbitals gives rise to two molecular
orbitals, σ1s and σ *1s. σ1s is the bonding molecular
orbital, whereas σ *1s is the antibonding molecular
orbital. Similarly, the combination of two 2s atomic
 orbitals will give rise to σ2s and σ*2s molecular orbitals.
These will be of higher energy than σ1s and σ*1s
molecular orbitals as they are formed from atomic
 orbitals of higher energy.
Combination of p-orbitals : The p-orbitals can combine
either along the axis to give σ molecular orbitals or
 perpendicular to the axis to give π-molecular orbitals.
Combination of px orbitals: The overlapping of two Px
orbitals
bondingalong the
σpx and axis resultsσ*
antibonding in the formation
molecular of a The
orbitals.
orbitals with same sign producepxbonding molecular
orbitals, whereas the orbitals with unlike signs produce
 anti bonding molecular orbitals .
Combination of py or pz orbitals: The overlapping of two
py or two pz atomic orbitals takes place perpendicular to
the molecular axis and, thus, results in the formation of
bonding and antibonding π- molecu!ar orbitals.
 Valence bond theory
cont...
Overlapping as follows:
a) σ-bond ; A sigma bond b). π-bond; A pi bond (symbol: π)
(symbol: σ) is a covalent bond is a covalent bond formed via
formed via linear overlap of parallel overlap of two orbital's.
two orbital's.

π-bond
 1. Sigma bond (σ-bond )

 The covalent bond formed due to overlapping of atomic orbital

along the inter nucleus axis is called σ-bond. It is a stronger bond
and cylindrically symmetrical.
 Depending on the types of orbital's overlapping, the σ- bond is
divided into following types:
i. σs-s bond
ii. σp-p bond
iii. σs-p bond
 Sigma bonds (σ-bonds )
cont..

i. σs-s bond;

ii. σp-p bond;

iii. σs-p bond:

 A pi bond(π-bond)
The covalent bond formed by
sidewise overlapping of atomic
orbital's is called π-bond
Note: The 's' orbital's can
only form σ-bonds, whereas
the p, d & f orbital's can form
both σ and π-bonds.
 Examples
I. Hydrogen molecule:
The electronic configuration of hydrogen atom in the
ground state is 1s1 .
In the formation of hydrogen molecule, two half filled
1s orbital's of hydrogen atoms overlap along the
internuclear axis and thus by forming a σs-s bond.
 ii. Cl2 molecule:

The electronic configuration of Cl atom in the ground state is

[Ne] [Ne]3s2 3px2 3py2 3pz1.
The two half filled 3pz atomic orbital's of two chlorine atoms
overlap along the inter-nuclear axis and thus by forming a σp-p
bond.
 iii. HCl molecule
 In the ground state, the electronic configuration of hydrogen
atom is 1s1.
 And the ground state electronic configuration of Cl atom is
[Ne]3s2 3px2 3py2 3p 1.
 The half filled 1s orbital of hydrogen overlap with the half
filled 3pz atomic orbital of chlorine atom along the inter-
nuclear axis to form a σs-p bond.
 iv. O2 molecule
The electronic configuration of O in the ground state is [He] 2s2 2px2 2py1 2p
1.

The half filled 2py orbital's of two oxygen atoms overlap along the inter-
nuclear axis and form σp-p bond.
The remaining half filled 2pz orbital's overlap laterally to form a πp-p.
Thus a double bond (one σp-p and one πp-p) is formed between two
oxygen atoms.

The remaining half filled 2pz orbital's overlap laterally to

form a πp-p bond.
 v. N2 Molecule
 The ground state electronic configuration of N is [He] 2s2 2px1 2py1 2pz1.
 A σp-p bond is formed between two nitrogen atoms due to overlapping of half
filled 2px atomic orbital's along the inter-nuclear axis.
The remaining half filled 2py and 2pz orbital's form two πp-p bonds due to
lateral overlapping.
Thus a triple bond (one and two) is formed between two nitrogen atoms.
 HYBRIDIZATION.
 The intermixing of two or more pure atomic orbital's of an
atom with almost same energy to give same number
of identical and degenerate new type of orbital's is known
as hybridization.
 The new orbital's formed are also known as
hybrid orbital's.
 During hybridization, the atomic orbital's with different
characteristics are mixed with each other.
Shapes of orbitals
 Energy levels
Electrons fill orbitals according to
the Aufbau principle, in which the
lowest energy orbitals are filled
first.
Orbitals are filled as
1s22s22p63s23p64s23d104p65s24d105
p66s24f145d106p67s25f146d107p6.
 HYBRIDIZATION.
Definition: The phenomenon of mixing up of atomic orbitals of similar
energies and formation of equivalent number of entirely new orbitals of
identical shape and energy is known as "hybridization" and the new orbitals
so formed is called as "hybrid orbitals".
Important points for understanding the hybridization:
a) The number of hybrid orbitals generated is equal to the number of pure
atomic orbitals that participate in hybridization process.
b) Hybridization concept is not applicable to isolated atoms. It is used to explain
the bonding scheme in a molecule.
c) Covalent bonds in polyatomic molecules are formed by the overlap of hybrid
orbitals or of hybrid orbitals with unhybridized ones.
TYPES OF HYBRIDIZATION

 sp
 sp2
 sp3
 sp3d
 sp3d2
 sp3d3
 1) 'sp' Hybridization
 Intermixing of one 's' and one 'p' orbital's of almost equal
energy to give two identical and degenerate hybrid
orbital's is called 'sp' hybridization.
 These sp-hybrid orbital's are arranged linearly at by
making 180 ⁰ of angle.
 They possess 50% 's' and 50% 'p' character.
 Example of sp-
hybridization:
 NOTE: The combination of one s and one p- orbitals to form two
hybrid orbitals of equal energy is known as sp-hybridization.
 Example: In BeF2 Molecule the sp-hybridized orbitals of Be overlap with the
half-filled orbitals of two fluorine atoms to give a linear shape.
 2). sp2 Hybridization
 Intermixing of one 's' and two 'p' orbital's of almost equal
energy to give three identical and degenerate hybrid orbital's is
known as sp2 hybridization.
 The three sp2 hybrid orbital's are oriented in trigonal
planar symmetry at angles of 120 ⁰ to each other.
 The sp2 hybrid orbital's have 33.3% 's‘ character and 66.6% 'p'
character.
 Example of sp2-
hybridization:
 The combination of one s and two p-orbitals to form three hybrid orbitals of
equal energy is known as sp2- hybridization.
Example of BF3 Molecule : These sp2 hybridized orbitals are oriented at an
angle of 120°. When three sp2 hybridized orbitals of B overlaps with three p-
orbitals of fluorine, three σ -bonds are formed with bond angle 120°. The shape
of BF3 molecule is thus trigonal planar.
 3). sp3 Hybridization
 In sp3 hybridization, one 's' and three 'p' orbital's of almost
equal energy intermix to give four identical and
degenerate hybrid orbital's.
 These four sp3 hybrid orbital's are oriented in tetrahedral
symmetry with 109 ⁰ 28' angle with each other.
 The sp3 hybrid orbital's have 25% ‘s’ character and 75% 'p'
character.
 Example of sp3-
hybridization:
 The combination of one s and three p- orbitals to form four hybrid orbitals of
equal energy is known as sp3-hybridization.
Example of Methane (CH4) molecule: These sp3-hybridized orbitals are oriented
at an angle of 109°28'. When these four sp3 hybrid orbitals overlaps with four
1s orbitals of hydrogen, a symmetrical tetrahedral shaped CH4 molecule form.
 4). sp3d Hybridization
 In sp3d hybridization, one 's', three 'p' and one
'd' orbital's of almost equal energy intermix
to give five identical and degenerate hybrid
orbital's, which are arranged in trigonal
bipyramidal symmetry.
 Among them, three are arranged in trigonal
plane and the remaining two orbital's are
present above and below the trigonal plane at
right angles.
 The sp3d hybrid orbital's have 20% 's', 60% 'p'
and 20% 'd' characters.
 Example of sp3d-hybridization:
 The combination of one s, three p and one d-orbitals to form five hybrid
orbitals of equal energy is known as sp3d-hybridization.
Example: PCl5 molecule.
  Intermixing of one 's', three 'p' and two 'd' orbital's
5). sp3d2 of almost same energy by giving six identical and
Hybridization degenerate hybrid orbital's is called sp3d2
hybridization.
 Thus the combination of one s, three p and two d-
orbitals to form six hybrid orbitals of equal energy is
known as sp3d2-hybridization.
 These six sp3d2 orbital's are arranged in octahedral
symmetry by making 90 ⁰ angles to each other.
 This arrangement can be visualized as four
orbital's arranged in a square plane and the
remaining two are oriented above and below
this plane perpendicularly.
Examples : SF6 Molecule.
sp3d3
Hybridiza  In sp3d3 hybridization, one 's', three
tion 'p' and three 'd' orbital's of almost
same energy intermix to give seven
sp3d3 hybrid orbital's, which are
oriented in pentagonal bipyramidal
symmetry.
 Five among the sp3d3 orbital's are
arranged in a pentagonal plane by
making 72⁰ of angles. The remaining
are arranged perpendicularly above
and below this pentagonal plane.
e- Hybridization Shape
Pair
2 sp linear
3 sp2 trigonal planar
4 sp3 tetrahedral, pyramidal, or bent

5 sp3d trigonal bipyramidal, trigonal

planar, or linear
6 sp3d2 octahedral, square planar, or linear
 VALENCE SHELL ELECTRON PAIR
REPULSION (VSEPR) THEORY
 Definition: The Valence-Shell-Electrons-Pair-Repulsion Theory (VSEPR), proposes
that the stereochemistry of an atom in a molecule is determined primarily by the
repulsive interactions among all the electron pairs in its valence shell.
 Postulates of VSEPR Theory : The main postulates of this theory are :
i. The shape of the molecule is determined by repulsion between all of the
electron pairs present in the valence shell.
ii. A lone pair of electrons takes up more space round the central atom than
a bond pair, since the lone pair is attracted to one nucleus whilist the
bond pair is shared by two nuclei. It follows that repulsion between two
lone pairs is greater than the repulsion between a lone pair and a bond
pair, which in turn is greater than the repulsion between two bond pairs.
The repulsive interactions decrease in the order :LP-LP > LP-BP > BP-BP
 VALENCE SHELL ELECTRON PAIR
REPULSION (VSEPR) THEORY cont…
iii. The magnitude of repulsion between bonding pairs of electrons. depends on the
electronegativity difference between the central atom and the other atoms
iv. Double bonds cause more repulsion than single bonds, and triple bonds cause
more repulsion than a double bond. Repulsive forces decrease sharply with increasing
bond angle between the electron pairs.
Example: BF3 Molecule
 In BF3 the central B atom has the configuration : 1s2, 2s2, 2px1. During the bond
formation one 2s-electron is promoted to vacant 2py orbital. Thus, excited B
(configuration: 1s2, 2s1, 2Px1, 2p 1, 2p 0) has three unpaired eIectrons for bond
formation.
 With three fluorine atoms, the three bonds between B and F atoms should be
slightly different strengths, because in one, 2s; while in other, two 2p-orbital
electrons are involved. But in fact, all the three bonds is BF3 are of equal strength
with bond angle of 120°. ( refer to Structure of BF3 Molecule)