Chemical Bonding 5

Valence Bond Theory

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Chemical Bonding 5
Valence Bond Theory
Bond,Bond Length & Bond Order

BOND ENTHALPY
Bond Enthalpy

⮚ It is defined as the amount of energy required to break one mole of

bonds between two atoms in a gaseous state.

⮚ The unit of bond enthalpy is kJ mol–1. For example, the H – H bond

enthalpy in hydrogen molecule is 435.8 kJ mol–1.

H2(g) H (g)+ H (g) : Δ H = 435.8 kJ/mol

Bond Enthalpy

⮚ In case of polyatomic molecules, the measurement of bond strength is

more complicated.

⮚ For example : In case of H2O molecule, the enthalpy needed to break

the two O–H bonds is not the same.

⮚ Therefore in polyatomic molecules the term average bond enthalpy is

used.
Bond Enthalpy
H2O (g) + ; Δ H = 502 KJ/mol

+ ; Δ H = 427 KJ/mol

Average Bond Energy 502 + 427

=
2
= 464.5 KJ/mol
Bond Order

⮚ In the Lewis description of covalent bond, the Bond Order is given by

the number of bonds between the two atoms in a molecule.
Example: 1) H2 bond order = 1
2) O2 bond order = 2
3) N2 bond order = 3

⮚ Isoelectronic molecules and ions have identical bond orders.

Example: F2 and O2-2

Bond Order

⮚ Bond order ∝ bond enthalpy.

⮚ Bond order ∝
Bond Order

CONCEPTUAL QUESTION
⮚ Arrange the following in order of decreasing bond angles CH4,
NH3,H2O, BF3, C2H2

Sol:
C2H2(1800) > BF3(1200) > CH4(1090281) > NH3(1070) > H2O(104.50).
Which of the following has largest bond angle ?

a) NH3
b) PH3
c) AsH3
d) SbH3
The bond energy in halogens decreases in the order…

a) F2>Cl2>Br2>l2
b) Cl2>Br2>F2>l2
c) Cl2>F2>Br2>l2
d) F2>Br2>Cl2>l2
Carbon - Carbon bond length is least in…
1) C2H6
2) C6H6
3) C2H4
4) C2H2
Valence Bond Theory
Valence Bond Theory
Valence Bond Theory

1. Attractive Force between: 2. Repulsive Force

(i) Electron between:
eA and nucleus HB. (i) Electron
(ii) Electron eA and nucleus eB.
eB and nucleus HA. (ii) Electron
HB and nucleus HB.
Valence Bond Theory

Variation of Potential Energy

Valence Bond Theory
Valence Bond Theory

Positive Overlap
Valence Bond Theory

Negative Overlap
Valence Bond Theory

Zero Overlap
Valence Bond Theory

Heitler & London concept

1. Atoms must come

closer for
overlapping
Valence Bond Theory

Heitler & London

concept

2. Orbital Configuration

1
a. 1
A B

b. 1
1 +
A B

3. Extent of Overlapping ∝ strength of

bond
Valence Bond Theory

Pauling and Slater’s Extension

1. Extent of overlapping depends upon

a. Nature of Overlapping orbitals

b. Nature of Overlapping
A. More closer the valence shells are to the nucleus,

more will be the overlap.

B. Directional orbitals show more overlap.
Types Of Overlapping

Sigma Bond:
⮚ This type of covalent bond is formed by the end-on-end overlap of
bonding orbitals along the internuclear axis.

⮚ This is called as head on overlap or axial overlap.

Types Of Overlapping

S-S overlapping:
Y In this case, there is overlap of two half filled S-orbitals
Y overlapping
S-S
along the internuclear axis.
Z Z
↑
X +↑ + + X

s orbital s orbital

Y
Z

+ + X

s – s overlap
Types Of Overlapping

S-P overlapping: This type ofS-P overlap occurs half filled S-orbital of one
overlapping
atom & half filled P-orbitals of another atom.

+↑ +

s orbital
p orbital

s – p orbital
(Sigma bonds)
Types Of Overlapping

Y
P-P overlapping: This type of overlapping takes place between half filled
Z
P-orbitals of the two approaching atoms along their direction.

↑
↑ +
X
p orbital p orbital p – p overlap
(sigma bond
↑

Axial overlap)
↑

p subshell
+ P-P
overlapping

p orbital p orbital p – p overlap

(pi bond
Lateral
overlap)
Types Of Overlapping

Sigma (σ) bond – s-s overlapping

Types Of Overlapping

Sigma (σ) bond – s-p overlapping

Types Of Overlapping

Sigma (σ) bond – p-p overlapping

Types Of Overlapping

pi (π)
bond
Types Of Overlapping

Pi (π) bond
𝞼 Vs 𝛑 Bonds
Sigma (σ) bond Pi (π) bond
1. It is formed by end to end overlapping 1. It is formed by sidewise overlapping of
of half filled atomic orbitals. half filled p-orbitals only.
2. Overlapping takes place along 2. Overlapping takes place perpendicular
internuclear axis. to internuclear axis.
3. The extent of overlapping is large and 3. The extent of overlapping is small and
bond formed is stronger. bond formed is weaker.
4. The molecular orbital formed as a 4. The molecular orbital formed as a
result of overlapping is symmetrical result of overlapping consists of two
about the internuclear axis. lobes above and below the internuclear
axis.
5. There is free rotation about σ bond 5. There is no free rotation about π bond
and no geometrical isomers are and geometrical isomers are possible.
possible.
6. The bond can be present alone. 6. The bond is always formed in addition
to sigma (σ) bond.
7. s and p orbitals can participate in the 7. Only p-orbitals participate in the
formation of σ bond. formation of π bond.
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