Basicity of Amines

 Amines are basic in nature due to lone pair of electrons present on Nitrogen. Hence
they behave as Lewis Bases.
NOTE: If a compound is able to donate electron pair easily, it is a strong base.
BUT if a compound is unable to donate electron pair easily, then it is a weak base.
 Amines are bases so they react with Acids to form Amine salts, for eg:

 Amine salts on treating with a base like NaOH give back the parent/starting
amine. For eg:

 Amine salts are soluble in water but insoluble in organic solvents like ether. This
reaction is the basis for the separation of amines from the non-basic organic
compounds insoluble in water.

BASICITY OF AMINES IN GASEOUS PHASE (ALIPHATIC AMINES)

In gaseous phase, Basicity of amine depends only on INDUCTIVE EFFECT
 Consider primary, secondary and tertiary amines:

 In Tertiary amine, 3 alkyl groups are present (showing +I effect). They increase
electron density on Nitrogen atom and makes the lone pair of electrons more available
for donation. Hence their basicity is high.
 In primary amine, only one alkyl group is present. It doesn’t increase electron density
on Nitrogen as much as compared to secondary or tertiary amine.
 Hence, ORDER OF BASICITY – TERTIARY AMINE > SECONDARY AMINE >
PRIMARY AMINE > AMMONIA.
  Ammonia is least basic, because it doesn’t have any alkyl groups attached to it.

BASICITY OF AMINES IN LIQUID (Aqueous) PHASE (ALIPHATIC AMINES)

In Liquid phase (solvent-water), Basicity of amine depends upon 3 factors:
 Inductive Effect
 Steric Hindrance
 Solvation Effect

1. INDUCTIVE EFFECT:
Greater dispersal/neutralisation of positive charge on ammonium cation, more is the
basicity of amine

 In tertiary amine, 3 alkyl groups donate electrons and disperse/neutralise

positive charge on Nitrogen more effectively as compared to secondary and
primary amines.
 So order of basicity is TERTIARY AMINE > SECONDARY AMINE >
PRIMARY AMINE

2. STERIC HINDRANCE:
Greater the stability of ammonium cation, more is the basicity of amine
  Due to the presence of 3 bulky alkyl groups in tertiary amine, Hydrogen
bonding doesn’t take place effectively. So the cation is less stable.
 In primary amine, only one alkyl group is present, so hydrogen bonding
takes place effectively and the cation formed is stable.
 Order of basicity is PRIMARY AMINE > SECONDARY AMINE >
TERTIARY AMINE.

3. SOLVATION EFFECT: Interaction between Solute (Amine) and Solvent (Water) is

solvation effect.
Greater interactions (number of hydrogen bonds) between Amine and Water → more
stable is the ammonium cation → more is the basicity of Amine.

 Primary ammonium cation can form 3 hydrogen bonds. Hence most stable.
 Secondary ammonium cation forms 2 hydrogen bonds.
 Tertiary ammonium cation forms 1 hydrogen bond. Hence least stable.
 So, Order of Basicity is PRIMARY AMINE > SECONDARY AMINE >
TERTIARY AMINE.

IMPORTANT: The order of basicity in case of Methyl substituted amines in aqueous

solvent:

Reason: Solvation effect dominates over Inductive effect (No Steric Hindrance)

IMPORTANT: The order of basicity in case of Ethyl substituted amines in aqueous

solvent:

Reason: Inductive effect dominates over Solvation effect (Due to Steric Hindrance)