Basicity of amines

Amines are derivatives of ammonia in which one or more hydrogen atoms have been replaced by
alkyl group.
i. Primary amines
In primary amines (10 amine), only one of the hydrogen atoms in the ammonia molecule has
been replaced. That means that the formula of the primary amine will be RNH2 where "R" is
an alkyl or aryl group.
ii. Secondary amines:
In a secondary amine (2° amine), two of the hydrogens in an ammonia molecule have been
replaced by alkyl or aryl group or both
iii. Tertiary amines:
In a tertiary amine (3° amine), all of the hydrogens in an ammonia molecule have been
replaced by hydrocarbon groups (alkyl or aryl group or both).
Examples:

Basicity of amines

 Amines are basic because they possess a pair of unshared electrons, which they can share
with other atoms. These unshared electrons create an electron density around the nitrogen
atom. The greater the electron density, the more basic the molecule.
 Groups that donate or supply electrons will increase the basicity of amines while groups
that decrease the electron density around the nitrogen decrease the basicity of the
molecule. - Due to this property of the alkyl group attached to the nitrogen of the amine,

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 the electron density around the nitrogen atom increases due to which its electron
releasing ability increases.
 Due to the greater and easier release of electrons in the alkyl amine, the molecule
becomes more basic than ammonia. - Whereas in ammonia, no such releasing group
attached. So, obviously the basicity of ammonia is much less than that of an alkyl amine.

The basicity amine in the gas phase and aqueous solutions are varies.

a. In the gas phase, the order of base strength is given below:

b. In aqueous solutions, the order of basicity

The differences in the basicity order in the gas phase and aqueous solutions are the result of
solvation effects. Amines in water solution exist as ammonium ions.

In water, the ammonium salts of primary and secondary amines undergo solvation effects (due to
hydrogen bonding) to a much greater degree than ammonium salts of tertiary amines. These
solvation effects increase the electron density on the amine nitrogen to a greater degree than the
inductive effect of alkyl groups.

When amines are dissolved in water, they form protonated amines. Also, the number of
possibilities of hydrogen bonding also increases. More the number of hydrogen bonding, more is
the hydration that is released in the process of the formation of hydrogen bonds. - The more the

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hydration energy of the molecule, more is the stability of the amine. Experiments have indicated,
in terms of hydration energy, that the tertiary amines are the least stable followed by the
secondary amines followed by the primary amine.

This can be explained on the basis of the following reactions.

In primary amine: RNH2 + H2O → RNH3 + OH

In secondary amine: R2NH + H2O → R2NH2 + OH

In tertiary amine: R3N + H2O → R2N + OH

So, the number of hydrogen bonds possible when primary amines are dissolved in water is the
greatest, implying that they are most stable species of amine, the least being the tertiary amines.

The combined effect of the pushing effect of the alkyl group (+I effect), steric hindrance and the
salvation of amines causes the basicity order to be: (basicity of tertiary is almost the same as that
of primary).

NH3< primary amine ~ tertiary amine < secondary amine

Basicity constant

Strong base (eg. NaOH and KOH) completely ionize in aqueous solution.Amines areweak base.
They are partially ionized in aqueous solution. Amines are weak base.

They are partially ionized in aqueous solution and an equilibrium is exist between the ionized
and unionized form.

The extent of ionization is described by an equilibrium constant Kb which is known as basicity

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Basicity constant describe the relative strength of a weak base. Stronger bases will have higher
numerical value of Kb (lower Pkb values).

Weaker bases will have lower numerical values of kb (Higher Pkb values).

Greater the number of electron releasing alkyl group, greater the availability of lone pair of
electrons and stronger the base.

Amines pKb
NH3 4.7
CH3NH2 3.4
(CH3)2NH 3.3
(CH3)3N 4.3

Dimethyl amine is stronger base than methylamine. Trimethylamine is weaker base than
dimethylamine and methylamine. Although in trimethylamine, the electron density is further
increased, the steric overcrowding of three methyl group makes the approach and bonding by
proton is relatively difficult. Electrons are there, but the path is blocked.

The size of an alkyl group is more than that of a hydrogen atom. So, an alkyl group would hinder
the attack of a hydrogen atom, thus decreasing the basicity of the molecule. - So, the more the
number of alkyl groups attached, lesser will be its basicity.

So, the decreasing order of basicity will be: Secondary amine > primary amine > tertiary
amine

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