INDUCTIVE EFFECT
The polarization of a σ bond due to electron withdrawing or electron donating effect of adjacent groups or atoms
is called inductive effect. Partially charged atoms inside the molecule may arise as a result of this redistribution,
which happens along sigma bonds.
OR
An inductive effect is the pull of electron density through sigma (σ) bonds caused by electronegativity differences
of atoms.
The C-Cl bond in CH3-CH2-CI is polarized due to electronegativity difference. The electrons are withdrawn by
the chlorine atom. Thus the first carbon atom gets partial positive charge. In turn, this carbon atom drags electron
density partially from the next carbon, which also gets partial positive charge. Thus the inductive effect is
transmitted through the carbon chain. But the inductive effect weakens away along the chain and is not significant
beyond 3rd carbon atom.
EXPLANATION:
When a σ-bond (single covalent bond) is formed between atoms of different electronegativity, the electron density
is shifted more toward the more electronegative atom of the bond.
This causes a permanent polarization where the more electronegative atom acquire (partial) negative charge (δ-)
and the other less electronegative atom has a slight (partial) positive charge (δ+).
This transmission of induced charges along a chain of sigma bonded carbon atoms is known as inductive effect.
SILENT FEATURES OF INDUCTIVE EFFECT
o It arises due to electronegativity difference between two atoms forming a sigma bond.
o It is transmitted through the sigma bonds.
o The magnitude of inductive effect decreases while moving away from the groups causing it.
o It is a permanent effect.
o It influences the chemical and physical properties of compounds.
TYPES OF INDUCTIVE EFFECT
The inductive effect is divided into two types depending on their strength of electron withdrawing or electron
releasing nature with respect to hydrogen.
1) Negative inductive effect (-I):
The electron withdrawing nature of groups or atoms is called as negative inductive effect. It is indicated by -I.
Following are the examples of groups in the decreasing order of their -I effect:
NH3+ > NO2 > CN > SO3H > CHO > CO > COOH > COCI > CONH2 > F > CI > Br > I > OH > OR > NH2 >
C6H5> H
2) Positive inductive effect (+I):
It refers to the electron releasing nature of the groups or atoms and is denoted by +I. Following are the examples
of groups in the decreasing order of their +I effect.
C(CH3)3 > CH(CH3)2 > CH2CH3 > CH3 > H
APPLICATIONS OF INDUCTIVE EFFECT
o Stability of carbonium ions:
The stability of carbonium ions increases with increase in number of alkyl groups due to their +I effect. The alkyl
groups release electrons to carbon, bearing positive charge and thus stabilizes the ion.
The order of stability of carbonium ions is :
o Stability of free radicals:
In the same way the stability of free radicals increases with increase in the number of alkyl groups.
Thus the stability of different free radicals is:
o Stability of carbanions:
However the stability of carbanions decreases with increase in the number of alkyl groups since the electron
donating alkyl groups destabilize the carbanions by increasing the electron density.
Thus the order of stability of carbanions is:
o Acidic strength of carboxylic acids and phenols:
The electron withdrawing groups (-1) decrease the negative charge on the carboxylate ion and thus by stabilizing
it. Hence the acidic strength increases when -I groups are present. However the +I groups decrease the acidic
strength. E.g.
i) The acidic strength increases with increase in the number of electron withdrawing Fluorine atoms as shown
below.
CH3COOH CH2FCOOH < CHF2COOH < CF3COOH
ii) Formic acid is stronger acid than acetic acid since the -CH3 group destabilizes the carboxylate ion.
On the same lines, the acidic strength of phenols increases when I groups are present on the ring.
E.g. The p-nitrophenol is stronger acid than phenol since the -NO2 group is a -I group and withdraws electron
density. Whereas the para-cresol is weaker acid than phenol since the -CH3 group shows positive (+1) inductive
effect.
Therefore the decreasing order of acidic strength is:
o Basic strength of amines:
The electron donating groups like alkyl groups increase the basic strength of amines whereas the electron
withdrawing groups like aryl groups decrease the basic nature. Therefore alkyl amines are stronger Lewi bases
than ammonia, whereas aryl amines are weaker than ammonia.
Thus the order of basic strength of alkyl and aryl amines with respect to ammonia is :
CH3NH2 > NH3 > C6H5NH2
In general, the inductive effect is less influencing than other effects like resonance effect and hyperconjugation.
E.g. The electron withdrawing nature of nitro group, -NO2 is mostly due to resonance effect rather than
the inductive effect.
But there are exceptions. For example, in cases of halogens, the negative inductive effect is more dominating than
positive resonance effect.
