Basic strength of Amines

Amines are basic in nature.

Due to the presence of lone pair of electrons on nitrogen atom which is available
for donation.
Aliphatic amines (alkyl amines) are more basic than ammonia.
Alkyl groups are electron releasing groups (+ I effect) which increase
electron density on nitrogen atom in alkyl amines. Increase in electron density
on nitrogen atom increases its basic strength. So alkyl amines are more basic
than ammonia

the expression for Kb and pkb of amines

the relation between pkb and basic strength

pk increases basic strength decreases.
b
is the relation between kb and basic strength
Kb increases basic strength also increases.

Aromatic amines (aryl amines) are less basic then ammonia.

In aromatic amines, nitrogen has a lone pair of elections which is
involved in resonance (+ R effect) and hence it is not free for
donation. Hence it is less basic than ammonia.

the order of basic strength of primary, secondary and

tertiary amines in gas phase
Tertiary > secondary > primary
In gas phase only inductive effect decides basic strength. In
tertiary amine there are three electron releasing groups, so
tertiary is most basic then secondary and primary.

the factors that affect basic strength of amines aqueous

solution?
1.Inductive effect of alkyl group
2.Solvation effect (hydrogen bonding)
3.Steric hindrance

For small CH3 group, 20 >10 >30 >NH3 [S > P > T]

Reason: For CH3 group, there is no steric hindrance to Hbonding. The stability of cation due to solvation effect >
inductive effect, hence 10 amine is more basic than 30
amine.

For big C2H5 group, 20 >30 >10 >NH3 [S > T > P]

Reason: For C2H5 group, there is steric hindrance to Hbonding. The stability of cation due to inductive effect >
solvation effect, hence 30 amine is more basic than 10
amine.

EDG (CH3, -OCH3), increases the basic strength

[increases the e- density on N].
EWG (NO2, halogen), decreases the basic strength
[decreases the e- density

Aliphatic amine > Benzyl amine >NH3 >Aromatic

amine
In gas phase, 30 >20 >10 amine > NH3
For small CH3 group, 20 >10 >30 >NH3 [S > P > T]
For big C2H5 group, 20 >30 >10 >NH3 [S > T > P]
EDG (CH3, -OCH3), increases the basic strength
EWG (NO2, halogen), decreases the basic strength

Arrange the following in decreasing order of their basic strength:

C6H5NH2, C2H5NH2, (C2H5)2NH, NH3
(C2H5)2NH > C2H5NH2 > NH3> C6H5NH2
Arrange the following in increasing order of their basic strength:
(i) C2H5NH2, C6H5NH2, NH3, C6H5CH2NH2and (C2H5)2NH
C6H5NH2 < NH3< C6H5CH2NH2< C2H5NH2 < (C2H5)2NH
(ii) C2H5NH2, (C2H5)2NH, (C2H5)3N, C6H5NH2
C6H5NH2< C2H5NH2< (C2H5)3N < (C2H5)2NH

(iii) In increasing order of basic strength:

(a) Aniline, p-nitroaniline and p-toluidine [CH3, B.S ; NO2 B.S]
p-nitroaniline < Aniline < p-toluidine
(b) C6H5NH2, C6H5NHCH3, C6H5CH2NH2.
C6H5NH2 < C6H5NHCH3 < C6H5CH2NH2
(iv) Decreasing order of basic strength in gas phase: C 2H5NH2,
(C2H5)2NH, (C2H5)3N, NH3 (C2H5)3N > (C2H5)2NH > C2H5NH2 > NH3
(v) In increasing order of boiling point: C2H5OH, (CH3)2NH, C2H5NH2
(CH3)2NH < C2H5NH2 < C2H5OH
(vi) In increasing order of solubility in water: C6H5NH2, (C2H5)2NH,
C2H5NH2.
C6H5NH2 < (C2H5)2NH < C2H5NH2

the effect of electron releasing group on basic strength of

amines
Electron releasing group (eg: CH3 , OCH3) increases basic
strength by increasing electron density on nitrogen atom.
the effect of electron withdrawing group on basic strength
of amines
Electron withdrawing group (eg: N02) decreases basic strength
by decreasing electron density on nitrogen atom.