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Valence Bond Theory

 Valence
Bond Theory
 Valence Bond Theory (V.B.T.)

 Linus Pauling  J.C. Slater

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 Valence Bond Theory (V.B.T.)

Remember what happens when

two atoms approach each other?

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 Valence Bond Theory (V.B.T.)

Attractive forces tend to

Repulsive forces tend to
bring the two atoms close
push them apart
to each other

eA
_
_
>

>

>
>

+ + +
HA HB
HA
>
>

>
>

new forces
_ old forces eB _
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 Potential Energy Curve

Internuclear distance, r (pm)

Potential energy (kJ/mol)

r0
0
r = 300

r = 150 H H

H H
- 435.8
r = 74

H H

Observed bond distance in H2

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 Orbital Overlap

Partial interpenetration
of atomic orbitals

Orbital overlapping

Electron pair is shared

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 Valence Bond Theory (V.B.T.)

When appropriately oriented

Covalent bond
atomic orbitals of the combining
formation occurs
atoms undergo overlapping

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 Conditions for Overlap

Each orbital should have one

Covalent Bond
electron with opposite spin

Coordinate One orbital should have a pair of

Bond electrons and other must be vacant

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 Note!!

All orbital overlappings do

not result in bond formation

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 Orbital Overlap

Types of Overlap

Positive Negative Zero

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 Orbital Overlap

Positive Overlapping

pz pz pz s

py
py px px
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 Orbital Overlap

Negative Overlapping

pz pz pz
s

py px px

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 Orbital Overlap

Zero Overlapping

px px py

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 Orbital Overlap

Types of overlaps

Positive Negative Zero

Bond will Bond will not

form form
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 Co-ordinate Bond or Dative Bond

Bond formed by Shared pair of electrons

sharing of electrons is contributed by only one
between two atoms of the two atoms

Coordinate bond once formed Covalent & coordination

cannot be distinguished from bond are same w.r.t.
covalent bond bond properties

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 How to Identify Coordinate Bond?

Different covalency Presence of

than usual coordinate bond

Example: N2O

+ -
N N O

Fourth bond formed by N is always coordinate

Third bond formed by O is always coordinate

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 Lewis Acid and Lewis Base

Lone pair donors are Lone pair acceptors

called Lewis bases are called Lewis
acids

H3N + H+ NH4+

Donor Acceptor

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 Co-ordinate Bond or Dative Bond

H +
H O H + H+ H O H

or H3O+

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 Covalent Bond

Sigma (σ)
Pi (𝛑) bond
bond

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 Sigma Bond

Head-on overlapping or Axial overlapping

Axis of orbitals are same

Sigma bond is formed
as their combining axis

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 Types of Head on Overlap

Sigma (σ) bond

s-s p-p s-p

overlap overlap overlap

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 Sigma Bond

⇂
+ ⇂

s orbital s orbital

↿⇂

s - s overlap
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 Sigma Bond

⇂
⇂
+

s orbital p orbital

↿⇂

s - p overlap
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 Sigma Bond

⇂
+ ⇂

p orbital p orbital

↿⇂

p - p overlap
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 Axial or Head-on Overlapping

Cylindrically symmetrical
about the internuclear
axis

Can undergo rotation about

the internuclear axis

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 Pi (𝛑) Bond

Sideways Overlapping

+ or

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 Lateral or sidewise Overlapping

Axes of the combining orbitals

𝛑 bond is formed are perpendicular to the
internuclear axis.

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 Lateral or sidewise Overlapping

Not cylindrically
symmetrical about the
internuclear axis

Cannot undergo rotation about

the internuclear axis

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 Note!!

Generally, 𝛑 bond between

two atoms is formed in
addition to a σ bond

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 Types of
π bond

p𝛑-p𝛑 overlap p𝛑-d𝛑 overlap d𝛑-d𝛑 overlap

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 p𝛑-p𝛑 Overlap

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 p𝛑-d𝛑 Overlap

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 d𝛑-d𝛑 Overlap

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 Bond Strength

In general, order of
strength of bond

𝛑 < 𝞂

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