University College of Pharmacy,

University of the Punjab, Lahore

INDUCTIVE EFFECT
Definition:
 Process of electron shift along the chain of atoms due to the presence of polar
covalent bond in a molecule is known as inductive effect.
 SIGMA ELECTRONS MOVE IN THIS PROCESS
 The inductive effect is an experimentally observable effect of the transmission
of charge through a chain of atoms in a molecule, resulting in a permanent dipole in
a bond.
 Inductive effect is an effect in which permanent polarization arises due to the partial
displacement of sigma electrons along carbon chain / carbon electrons towards most
electronegative atom along carbon chain.
e.g.

Bond Polarization:
Covalent bonds can be polarized depending on the relative electronegativity of the
atoms forming the bond. The electron cloud in a σ-bond between two unlike atoms is not
uniform and is slightly displaced towards the more electronegative of the two atoms. This
causes a permanent state of bond polarization, where the more electronegative atom has a
fractional negative charge (δ–) and the less electronegative atom has a fractional positive
charge (δ+).
For example, the water molecule H2O has an electronegative oxygen atom that
attracts a negative charge. This is indicated by δ- in the water molecule in the vicinity of the
O atom, as well as by a δ+ next to each of the two H atoms. The vector addition of the
individual bond dipole moments results in a net dipole moment for the molecule.
Types of inductive Effect:
 + I effect – electron donating groups
e.g., CH3, C2H5
C(CH3)3 > CH(CH3)2 > CH2CH3 > CH3- > H
 -I effect – electron withdrawing groups
e.g., - NO2, –CN
COCl > CONH2 > F > Cl > Br > I > -OH

Features of Inductive Effect:

 It arises due to Electronegativity difference between two atoms.

Muhammad Muneeb
D16M137
 University College of Pharmacy,
University of the Punjab, Lahore
 It is transmitted through sigma bond.
 Magnitude decreases while moving away from the electronegative atom.
 It is a permanent effect.
 It influences physical and chemical properties of the molecule.
 Chloroacetic acid is a stronger acid than acetic acid because
O O
Cl - CH2 C Cl-CH2 - C +
+ H
OH -I O

(Ka = 1.4 × 10-3)

O O
+
CH3-C CH3-C + H
OH +I O

(Ka = 1.75 × 10-5)

 The larger is the electron-withdrawing effect of a group, the greater is the –I

(inductive) effect.

F CH2 COOH (Ka = 2.5 × 10-3)

Br CH2 COOH (Ka = 1.3 × 10-3)

 Inductive effect is additive.

Cl3CCOOH (Ka = 2.3 × 10-1)

Cl2CHCOOH (Ka = 5.4 × 10-2)

 Since this effect is transmitted through a chain it becomes less effective with
distance.

ClCH2CH2COOH (Ka = 8.32 × 10-4) ; ClCH2CH2CH2COOH (Ka = 3.02× 10-5)

Relative Inductive Effects:

Relative inductive effects have been experimentally measured with reference to
hydrogen, in decreasing order of -I effect or increasing order of +I effect, as follows:

–NH3+ > –NO2 > –SO2R > –CN > –SO3H > –CHO > –CO > –COOH > –COCl> –CONH2 >

–F > –Cl > –Br > –I > –OR > -OH > –NH2 > –C6H5 > –CH=CH2 > –H

The strength of inductive effect is also dependent on the distance between the
substituent group and the main group that react; the greater the distance, the weaker the
effect.

Muhammad Muneeb
D16M137
 University College of Pharmacy,
University of the Punjab, Lahore
Inductive effects can be measured through the Hammett equation, which describes
the relationship between reaction rates and equilibrium constants with respect to
substituents.

Applications:
 It produces stability of Carbocations and Carbanions.

 It tells about acidic strength.

– H+ lost
– pH should be low
– negative charge should be less

Acidity and Basicity:

The inductive effect also plays a vital role in deciding the acidity and basicity of a
molecule. Groups having +I effect attached to a molecule increases the overall electron
density on the molecule and the molecule is able to donate electrons, making it basic.
Similarly, groups having -I effect attached to a molecule decreases the overall electron
density on the molecule making it electron deficient which results in its acidity. As the
number of -I groups attached to a molecule increases, its acidity increases; as the number of
+I groups on a molecule increases, its basicity increases.

Muhammad Muneeb
D16M137
 University College of Pharmacy,
University of the Punjab, Lahore

Examples:

Example 1:

The hybridization of carbon atoms C — C single bond in vinylacetylene is:

(A) sp3 - sp3 (B) sp - sp2 (C) sp2 - sp (D) sp3 – sp
1 2 3 4
H2C CH — C CH
Vinylacetylene
Example 2:

Allyl isocyanide has:

(A) 9 bonds and 4 bonds (B) 8 bonds and 5 bonds

+ –
(C) 8 bonds, 5 bonds and 4 non-bonding electrons H2C CH — CH2 — N C
Allyl isocyanide
(D) 9 bonds, 2 bonds and 2 non-bonding electrons

Muhammad Muneeb
D16M137
 University College of Pharmacy,
University of the Punjab, Lahore
Example 3:

Which one is the most acidic alpha hydrogen?

O O
O O

CH3 CCH2 CHO CH3CCH2 CCH3 CH3CCH2COOCH3

(A) (B) (C) (D) CH3CHO

O O Since e-withdrawing nature of CO<


H3C — C — CH2 — CH one keto and one gas varies as aldehyde > keto > ester
aldehydic carbonyl group.
O O
 Then most acidic a-H atom is present
H3C — C — CH2 C — CH3 two e-withdrawing keto
groups. in A. So, A is answer
O O

H3C — C — CH2 C — OCH3 keto and ester group.

O

H3C CH one aldehyde group.

Example 4:

The decreasing order of acidity among phenol, p-methylphenol, m-nitrophenol and

p-nitrophenol is:

(A) m-nitrophenol, p-nitrophenol, phenol, p-methylphenol

(B) p-nitrophenol, m-nitrophenol, phenol, p-methylphenol

(C) p-methylphenol, phenol, m-nitrophenol, p-nitrophenol

(D) phenol, p-methyl phenol, p-nitrophenol, m-nitrophenol

OH OH OH OH Electron withdrawing groups increase acidic strength
while electron donating group decreases the same.
NO2 So the proper decreasing order of acidic strength is:
CH3 NO2
+I –I –I, –R OH OH OH OH

> > >

NO2
NO2 CH3

Example 5:

In the following compounds, the order of basicity is:

(A) I > IV > II > I (B) II > I > IV > III (C) III > I > IV > II (D) IV > I > III > II

Muhammad Muneeb
D16M137
 University College of Pharmacy,
University of the Punjab, Lahore

N N N

H N H H
(I) (II) (III) (IV)

Between I and IV, IV is less basic because of the

N N
sp3
H sp2
I II
O
–I effect of oxygen atom. II is more basic than III
N N
as the lone pair on N-atom in III is not available
sp3 sp2
H H for protonation as it is involved in resonance.
IV III
Therefore, the correct order is I > IV > II > III

Example 6:

Account for the order acidity in the following compounds.

O
O  
H3C C CH2 COOH > CH3 CH2 COOH
CH3CCH2COOH CH3CH2COOH (a)
(A) (b)

In compound (a), electron-withdrawing keto group increases the acidic strength by

decreasing the O — H bond strength, while no such effect is there in compound (b).

HC CCH 2COOH H 2C = CHCH 2COOH

(B)

HC C CH2 COOH > CH2 CH CH2 COOH

Carbon atoms attached to triple bond is sp hybridised and more electron-

withdrawing than sp2 hybridised carbon atom.

Example 7:

Which of the following two amines is more basic and why?

CCl3CH2CH2CH2NH2 or CCl3CH2CH2NH2

Electron-withdrawing groups decrease the charge density on N-atom of organic

amines and hence decrease the basic strength. In Cl3C CH2 CH2 CH2 NH2, the electron
withdrawing — CCl3 is far apart from — NH2 group as compared to Cl3C CH2 CH2 NH2.

Hence, the former is more basic in nature.

Muhammad Muneeb
D16M137