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 K
b
and pk
b
of amines
the relation between pk
b
and basic strength
pk
b
increases basic strength decreases.
is the relation between k
b
and basic strength
K
b
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 CH
3
group, 2
0
>1
0
>3
0
>NH
3
[S > P > T]
Reason: For CH
3
group, there is no steric hindrance to H- bonding. The
stability of cation due to solvation effect > inductive effect, hence 1
0
amine
is more basic than 3
0
amine.

For big C
2
H
5
group, 2
0
>3
0
>1
0
>NH
3
[S > T > P]
Reason: For C
2
H
5
group, there is steric hindrance to H- bonding. The
stability of cation due to inductive effect > solvation effect, hence 3
0
amine
is more basic than 1
0
amine.

EDG (CH
3
, -OCH
3
), increases the basic strength [increases the e- density on
N].
EWG (NO
2
, halogen), decreases the basic strength [decreases the e-
density



Order of basic strength
Aliphatic amine > Benzyl amine >NH
3
>Aromatic amine
In gas phase, 3
0
>2
0
>1
0
amine > NH
3

For small CH
3
group, 2
0
>1
0
>3
0
>NH
3
[S > P > T]
For big C
2
H
5
group, 2
0
>3
0
>1
0
>NH
3
[S > T > P]
EDG (CH
3
, -OCH
3
), increases the basic strength

EWG (NO
2
, halogen), decreases the basic strength
Arrange the following in decreasing order of their basic strength:
C
6
H
5
NH
2
, C
2
H
5
NH
2
, (C
2
H
5
)
2
NH, NH
3

(C
2
H
5
)
2
NH > C
2
H
5
NH
2
> NH
3
> C
6
H
5
NH
2

Arrange the following in increasing order of their basic strength:
(i) C
2
H
5
NH
2
, C
6
H
5
NH
2
, NH
3
, C
6
H
5
CH
2
NH
2
and (C
2
H
5
)
2
NH
C
6
H
5
NH
2
< NH
3
< C
6
H
5
CH
2
NH
2
< C
2
H
5
NH
2
< (C
2
H
5
)
2
NH
(ii) C
2
H
5
NH
2
, (C
2
H
5
)
2
NH, (C
2
H
5
)
3
N, C
6
H
5
NH
2

C
6
H
5
NH
2
< C
2
H
5
NH
2
< (C
2
H
5
)
3
N < (C
2
H
5
)
2
NH


(iii) In increasing order of basic strength:
(a) Aniline, p-nitroaniline and p-toluidine [CH
3
, B.S ; NO
2
B.S]
p-nitroaniline < Aniline < p-toluidine
(b) C
6
H
5
NH
2
, C
6
H
5
NHCH
3
, C
6
H
5
CH
2
NH
2
.
C
6
H
5
NH
2
< C
6
H
5
NHCH
3
< C
6
H
5
CH
2
NH
2

(iv) Decreasing order of basic strength in gas phase: C
2
H
5
NH
2
,
(C
2
H
5
)
2
NH, (C
2
H
5
)
3
N, NH
3
(C
2
H
5
)
3
N > (C
2
H
5
)
2
NH > C
2
H
5
NH
2
> NH
3

(v) In increasing order of boiling point: C
2
H
5
OH, (CH
3
)
2
NH, C
2
H
5
NH
2

(CH
3
)
2
NH < C
2
H
5
NH
2
< C
2
H
5
OH
(vi) In increasing order of solubility in water: C
6
H
5
NH
2
, (C
2
H
5
)
2
NH,
C
2
H
5
NH
2
.
C
6
H
5
NH
2
< (C
2
H
5
)
2
NH < C
2
H
5
NH
2

the effect of electron releasing group on basic strength of
amines
Electron releasing group (eg: CH
3
, OCH
3
) 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: N0
2
) decreases basic strength
by decreasing electron density on nitrogen atom.