Theory Notes on Chemical Bonding-IV

Valence bond theories (VBT) 

It was proposed by Heitler and London and extended by Pauling and Slater.
The main points of the theory are 
(1) A covalent bond is formed by overlapping of atomic orbitals of valence shell of the two atoms.
(2) Only the orbitals which has singly occupied electrons can enter into overlapping process. The resulting
bond acquires a pair of electrons with opposite spins.
(3) The atoms with singly filled orbitals must come closer to one another with their axes in proper directions
for overlapping.
(4) Overlapping of orbitals result in decrease of energy.
(5) As a result of overlapping, there is maximum electron density somewhere between the two atoms.
(6) Greater the extent of overlapping higher is the strength of covalent bond.
(7) The amount of energy released per mole during overlapping is termed as bond energy.
(8) Electrons which are already paired in valency shell can enter into bond formation if they can be unpaired
first and shifted to vacant orbitals of slightly higher energy of same main energy shell. This point explains
the pentavalency of phosphorus, hexavalency of sulphur and hepta valency of halogens.

Two types of the bonds are formed between two atoms on account of overlapping 
(a) sigma bond (s) (b) Pi bond (p)
(a) sigma bond: A bond formed between two atoms by the overlap of single occupied orbitals along their
axes (end to end overlap) is called sigma (s) bond.
Electron cloud in this bond is symmetrical about the line joining the two nuclei of the two atoms. Sigma
bond can, thus be defined as “Bond orbital which is symmetrical about the line joining the two nuclei is
known as sigma bond.”
It is formed by headon or axial overlap.
(1) SS overlapping
(2) S  P overlapping
(3) PP Overlapping
Between the two orbitals of the same stability (i.e. having same energy) one more directionally concentrated
would form a stronger bond. If both are present in the same main energy shell dumbbell shaped p
orbitals will form stronger bond as compared to spherically symmetrical sorbital. When both are taking
part in same type of overlapping.

(b) π -bond:
π bonds are those which are formed by the sidewise or lateral overlapping of P  orbitals.
The Overlapping takes place at the side of two lobes and hence, the extent of overlapping is smaller.
Thus π bond is weaker than bond.

More is the overlapping, more is the decrease is energy and higher the energy released, stronger will be
the Covalent Bond.
Differences between  and  bonds.
Sigma (  ) bond Pi (  ) bond
1. It result from the end to end overlapping of two s It result from the sidewise (lateral) overlapping
orbitals or two porbitals or one s and one porbital. of two p orbitals.
2. Its bonded orbitals consist of a single electron Its bonded orbitals consist of two electron
cloud which is symmetrical about internuclear axis. clouds one is above and the other is below
the plane of participating atom.
3. More stronger Less stronger.
4. Bond energy ~ 80 kcals. ~ 65 kcals.
5. more stable. less stable.
6. Less reactive. More reactive.
7. Can be independently exist. Always exist along with a  bond.
8. Hybridization depends upon  bonds. Doesn’t depend.
9. The groups or atoms can undergo rotation about Due to resistance to rotation around the 
single sigma (  ) bond. bond the groups attached to it are not free
to rotate.
10. The  electrons are referred as localised bond. In  bond the electrons are held less firmly
thus can be easily dissociated or polarised
by an external charge and hence the  electron
are referred as mobile electrons.
11. The shape of the molecule is determined by the  bonding does not affect the shape of the
 bonds present in the molecule. molecule in which it occurs.
12.   bond can have independent existence.   bond always exists along with a  
bond.

If only single bond exist in a molecule, all will be of  type. In a double bond, One will be  and the other
will be π , In a triple bond, one will be  and other two will be π .
H–H O=O NN

C N
|
N C C  C  N
|
CN

π  bond is weaker & thus more reactive than σ bond.

1. Bond energy increases from a single bond to a triple bond.
Bond energy: Single bond < Double bond < Triple bond.

2. Bond strength increases from a single bond to triple bond.

Bond strength : Single bond < Double bond < Triple bond.

3. Bond length of a multiple bond ( double or triple) is always shorter than the corresponding single bond.
Bond Length: Single bond > Double bond > Triple bond

4. Reactivity of a multiple bond is always more than the single bond. This is due to the fact that π
electrons are mobile in nature.
Reactivity : Single bond < Double bond < Triple bond
1
B. L.
B.E.
CCCCC-C
       
Bond length increasing
        
Bond energy increasing