METHODS OF PURIFICATION OF ORGANIC COMPOUNDS

Organic compounds obtained either from natural source or synthesized in the laboratory are
contaminated with impurities such as by products, reactants or associated compounds. Various
methods are used for the removal of impurities (Purification) . These methods depend on the
nature of the compound and the impurity present in it.
The common methods used for the purification of organic compounds are as follows:
1. Sublimation
2. Crystallisation
3. Distillation
4. Differential extraction and
5. Chromatography.
The purity of an organic compound is ascertained by determining its melting point or boiling
point. Most of the pure compounds have sharp melting and boiling points.

1. Sublimation:
The process of conversion of solid to vapour state directly by heating without passing
through the liquid state is called sublimation. When the vapours are cooled, the original

substance in the pure form is obtained.

This method is used for the separation of sublimable volatile compounds from non-sublimable
impurities.
In this method, the impure substance is placed in a dish and covered with an inverted funnel. The
dish is slowly heated. The solid substance vapourises and condenses on the walls of the funnel,
leaving the non-sublimable impurities in the dish
Ex: Benzoic acid, Naphthalene, Camphor, Iodine etc can be purified by this method.

2. Crystallisation:
Principle: It is based on the difference in the solubilities of the compound and the impurities in a
suitable solvent. In this method, Impure compound dissolved in a solvent is sparingly soluble at
low temperature, but appreciably soluble at high temperature.
In this method, the saturated solution of the impure organic compound in a suitable solvent at a
higher temperature is prepared. The solution so formed is filtered while hot to remove insoluble
impurity. The clear solution is cooled when the solid organic compound separates out in the form
of fine crystals and is removed by filtration. The solid is filtered and dried. The filtrate (mother
liquor ) contains impurities and small quantity of the compound.
After crystallization, if the sample contain colour which is often due to the presence of polar or
polymeric compounds(impurities) , then it is decolourised using activated carbon or activated
charcoal.
Activated charcoal is very finely divided carbon that provides high surface area to adsorb the
coloured impurities.
Ex: Benzoic acid can be purified by this method.

3. Distillation:
This method is used for purification of volatile liquids form non-volatile impurities. The process
of converting the liquid into vapours by heating and condensing the vapours back to give the
original liquid in the pure form by cooling is called distillation.
Several methods of distillation, such as simple distillation, fractional distillation , vacuum
distillation, steam distillation etc. are used.

SIMPLE DISTILLATION:
This method is used (i) to separate volatile liquids which boil without decomposition from non-
volatile impurities (ii) to separate the liquids having sufficient difference in their boiling points.
When the given impure liquid is heated to boiling point in a distillation flask, the liquid
vapourises at its boiling point and the vapours are condensed as they pass through the condenser.
The pure liquid is collected in the receiver while the non volatile impurities are left behind in the
distillation flask.
Simple distillation is also used for the separation of two or more miscible liquids provided their
boiling points differ by greater than 400C .
Here, Liquid mixture is taken in a round bottom flask and heated carefully. On boiling, the
vapours of lower boiling point component are formed first. The vapours formed are condensed
by using a condenser and the liquid is collected in a receiver. The vapours of the component with
higher boiling point distills later and the liquid can be collected separately.
Eg: Mixture of Chloroform (B.Pt 334 K) and Aniline (B.Pt 457K) can be separated by using
simple distillation.

FRACTIONAL DISTILLATION:
Fractional distillation is used to separate the two liquids in which the difference in the boiling
points of the two liquids is less than 400C.

In this method, the vapours of the liquid mixture is passed through a fractionating column(a
glass column packed with glass beads or specillay designed column) before condensation, which
is fitted over the mouth of the round bottom flask. Vapours of the low volatile component( high
boiling component) gets condensed in this column and return to the distillation flask, while the
vapours of the more volatile component (low boiling component ) reaches the top of the column.
A fractionating column provides many surfaces for heat exchange between the ascending
vapours and descending condensed liquid. Some of the condensing liquid in the fractionating
column obtains heat from the ascending vapours and revapourises. The vapours thus become
richer in low boiling component. The vapours of the low boiling component ascend to the top of
the column and pass through the condenser and the pure more volatile component (the compound
having lower boiling point ) is collected in the receiver.
After a series of successive distillations, the remaining liquid in the distillation flask gets
enriched in high boiling component. Each successive condensation and vaporization unit in the
fractionating column is called as theoretical plate.
Application:
On commercial scale, Fractional distillation is used to separate different fractions of crude oil in
Petroleum industry.
This method is also used to separate the mixture of Acetone (B.Pt 330K ) and Methanol (B.Pt
338K)

DISTILLATION UNDER REDUCED PRESSURE (VACUUM

DISTILLATION) :
This method is used to purify liquids having very high boiling points and those which
decompose at or below their boiling points.

Principle: These liquids are made to boil at a temperature lower than their normal boiling point
by reducing the pressure ( Lowering of pressure on the surface of the liquid lowers its boiling
point) in the round bottomed flask with the help of vacuum pump, without any decomposition.

Distillation of a liquid occurs when the vapour pressure of the liquid becomes equal to the
atmospheric pressure. In Vacuum distillation, the atmospheric pressure above the liquid mixture
is reduced causing evaporation of the liquid at a temperature less than its boiling point.
Distillation under reduced pressure is carried out in a specially designed distillation apparatus in
which the receiver is attached to the vacuum pump to reduce the pressure. The pressure is
measured with the help of manometer. When vacuum is applied the distillation occurs
approximately half of the boiling point of the liquid.
Ex: Separation of glycerol from spent-lye in the soap industry.

STEAM DISTILLATION:
Steam distillation is used for separating liquids which are immiscible with water and are steam
volatile, and have high vapour pressure (10-15mm of Hg at 373K).
Principle: The total vapour pressure above a mixture of two immiscible liquids is equal to sum
of the vapour pressures of the two component liquids . P = p1+ p2 where p1 is the vapour pressure
of the organic liquid and p2 is the vapour pressure due to water. The liquid boils when the sum of
vapour pressures of both the components becomes equal to the atmospheric pressure. Since p 1 is
lower than P, the organic liquid vapourises at a lower temperature than its boiling point.

Procedure: In this process, steam from a steam generator is passed through a heated flask
containing the liquid to be distilled. The organic liquid boils at a temperature much lower than its
boiling point and hence its decomposition is avoided. The mixture of steam and volatile organic
compound is condensed and collected. The compound is later separated from water by using a
separating funnel. Aniline is separated by this technique from aniline –water mixture.

4. Differential extraction: This method is used to separate an organic compound present in

aqueous solution by shaking it with a suitable organic solvent which is immiscible with water
and in which the organic compound is more soluble than in water. The organic solvent and the
aqueous solution should be immiscible with each other so that they form two distinct layers
which can be separated by separating funnel. The organic solvent is later removed by distillation
or by evaporation to get back the compound. Differential extraction is carried out by using a
separating funnel.