CHE101 (B.Tech.

Chemistry Course)

Lecture - 23

Basic of Electron Displacement Effect

Edited By

Mr. Harminder Singh

Department of Chemistry
Lovely Professional University, Phagwara, Punjab, India.

E-mail: harminder.singh@lpu.co.in

The inductive effect arises in the organic molecules when some atom or group of different
electronegativity is attached to the carbon atom chain.

dX

d+
C

X is more electronegative

d+
Y

dC

Y is less electronegative

As a result, the electron pairs of the chain get displaced either towards it if it is more
electronegative then carbon or away from it in case it is less electronegative.
the electron displacement will lead to polarity( i.e. partial + and ve charge)

The permanent displacement of the electrons along the chain of carbon atoms due to the
presence of an atom or group of different electronegativity at the end of the chain is called
Inductive effect.
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Inductive effect

TYPES OF INDUCTIVE EFFECTS

ELECTRON
WITHDRAWING
GROUPS (-I effect)

dCl

d+
C

F, Cl, Br, N, O

ELECTRON
DONATING
GROUPS (+I effect)

d+
CH3

dC

R, CH3, B, Si

electronegative elements
alkyl groups and elements
take electron density
less electronegative than carbon
from cabon
donate electron density to carbon
These electron withdrawing and donating groups work through
the sigma bond system, unlike the similarly named resonance
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groups that work through the p system.

-I effect
- NO2 > -SO3H > -CN > -COOH > -F > -Cl > -Br > -I > -OCH3 > -C6H5 > -H
+I effect

(CH3)3C- > (CH3)2CH- > CH3- CH2- CH2- > CH3- CH2- > CH3- > -H

Applications of inductive effect:

Relative strength of organic acids
Relative basic strength of ammonia and primary amines

Inductive effect

INDUCTIVE EFFECTS
HALOACIDS

d- d+
C
Cl

Chlorine helps
to stabilize -CO2by withdrawing
electrons

d-

Cl

d+

O
O

d-

d+

d-

d+

C
O

The effect diminishes with distance

- it carries for about 3 bonds.

Inductive effect

Inductive Effects
Electronic effects that are transmitted through space and

through the bonds of a molecule

The effect gets weaker with increasing distance

Inductive effect

The

inductive effect

the electron-deficient carbon bearing the

positive charge polarizes electrons of the

adjacent sigma bonds toward it
the positive charge on the cation is not

localized on the trivalent carbon, but

delocalized over nearby atoms
the larger the volume over which the positive

charge is delocalized, the greater the stability

of the cation

Inductive effect

Inductive effect
Factors that Determine Acid StrengthInductive Effects

When electron density is pulled away from the negative charge

through bonds by very electronegative atoms, it is referred to as an
electron withdrawing inductive effect.
More electronegative atoms stabilize regions of high electron density
by an electron withdrawing inductive effect.
The more electronegative the atom and the closer it is to the site of the
negative charge, the greater the effect.

The acidity of HA increases with the presence of electron

withdrawing groups in A.

Electromeric effect
Electromeric effect

This is a temporary effect and takes place between two atoms

joined by a multiple bond, i.e., a double or triple bond. It occurs at
the requirements of the attacking reagent, and involves
instantaneous transfer of a shared pair of electrons of the multiple
bond to one of the linked atoms.
It is temporary in nature because the molecule acquires its original
electronic condition upon removal of the attacking reagent.

For example, consider the carbonyl group, >C=O, present in aldehydes and ketones.
When a negatively charged reagent say approaches the molecule seeking positive site, it
causes instantaneous shift of electron pair of carbonyl group to oxygen (more
electronegative than carbon). The carbon thus becomes deprived of its share in this
transferred-pair of electrons and acquires positive charge. In the meanwhile oxygen
takes complete control of the electron pair and becomes negatively charged. Therefore,
in the presence of attacking reagent, one bond is lost and this negatively charged
attacking reagent links to the carbon having positive charge.
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Electromeric effect

This phenomenon of movement of electrons from one atom to

another at the demand of attacking reagent in multi-bonded
atoms is called electromeric effect, denoted as E effect. The
electromeric shift of electrons takes place only at the moment of
reaction. Like the inductive effect, the electromeric effect is also
classified as +E and E:
+E- effect

When the transfer of electrons takes place towards the attacking reagent, it is
called + E (positive electromeric) effect. For example,

+E- effect

When the transfer of electrons takes place away from the

attacking reagent, it is called, -E (negative electromeric) effect.
For example,

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Electromeric effect
Ex.of application of electromeric effect:
Additions to Alkenes

Generally the reaction is exothermic because one p and one bond are
converted to two bonds

The p electrons of the double bond are loosely held and are a source of
electron density, i.e. they are nucleophilic
Alkenes react with electrophiles such as H+ from a hydrogen halide to form a
carbocation

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