METHODS OF PURIFICATION

OF
ORGANIC COMPOUNDS

(1) SUBLIMATION:
Heat
Solid Vapour
Cool

This process is occasionally used for the

purification of solid organic compounds. Its use is necessarily
limited to those compounds which on heating pass readily and
directly from the solid to the vapour state, with a subsequent
ready reversal of this process when the vapour is cooled.

examples:
(1) Campher (2)Ammonium chloride (3) Anthracene (4) Naphthalene (5) solid SO2
(6) I 2 (7) Solid CO2
(2)CRYSTALLIZATION:
(1)SIMPLE CRYSTALLIZATION
Commercial purification of sugar by crystallization of the raw
sugar product which leaves impurities behind

(1) Impure solid

(2) Solvent added to solids
(3) Solution heated, on heating solubility increases to give saturated compound solution and filtered
(4) Saturate compound solution allowed to cool , on cooling this solution become super saturated so pure
compound crystallises out and is removed by filtration.
examples:
(A) Sugar from solution (B) Salt from solution (C) Alumn from solution
 (2)FRACTIONAL CRYSTALLIZATION
#Fractional crystallization is a method of refining substances based on differences in solubility.
#If a mixture of two or more substances in solution is allowed to crystallize, for example by allowing the
temperature of the solution to decrease, the precipitate will contain more of the least soluble substance.
#You are given a mixture containing 80 g of K2 SO4(s) and 80 g of KNO3(s) and are asked to produce
as much pure KNO3 as possible
• Step 1: Dissolve salts in 100 g distilled water at 80°C.
• By looking at the solubility curves, you will see that 100 g of
KNO3 and 170 g of K2 SO4 will dissolve at this temperature.
• Thus, everything will dissolve.
 Step 2: Cool the solution to 0°C.
• K2 SO4 • At 0°C about 150 g of K2 SO4 is soluble in 100 g of
water.
• We only dissolved 80 g of K2 SO4
so NONE of it has precipitated out.
• KNO3
• At 0°C only 12 g of KNO3
can remain in 100 g of water.
• We dissolved 80 g of KNO3
so (80g-12g=68g) of pure KNO3
precipitated from the solution.
 (3)DISTILLATION:
Mixture of liquids can be seprated by the difference in boiling point.
selective boiling and susequent condensation of a component in a liquid mixture.
(A) Simple distillation:
it involves the liquid mixture to the boiling point and immediately condensing the resulting vapours.
effective for mixtures where in the boiling point of the liquid are considerably different(minimum 250 c or
more)

examples:
(1) CHCl3  aniline
(2)R-O-R and Toluene
(3) Alcohol and water
 (B) Fractional distillation:
Method used when the difference between the boiling point of the liquids are very close to each other.
A fractionating column provides asending vapours and the desending condensed liqiud. some of the con-
densing liquid in fractionating column obtains heat from the asending vapours and revapories.the vapours
thus become richer in low boiling compound

examples
(1) Crude oil in petroleum
(2) BENZENE AND TOLUENE
(C)STEAM DISTILLATION:
#Many water insoluble compounds bothe solid and liquid may be readily purified by distillation in a
current of steam ,provided that the compound is volatile ,and the impurities non volatile, under these condi-
tions.
#used for sustance which are heat sensitive steam volatile and are immisible with water .
eample

(1)NITRO BENZENE (2) ORTHO NITRO PHENOL (3) SALICYLALDEHYDE

(4) ESSENTIAL OIL (5) TURPENTINE OIL (6) ORTHO HYDROXY ACETOPHENONE
(7) CHLOROBENZENE (8) NAPHTHALENE (9) PARA TOLUNITRILE
(D)VACCUM DISTILLATION/DISTILLATION UNDER RE-
DUCED PRESSURE:
#used for mixture having high boiling point and heat sensitive(compound which decompose at or below it’s
B.P.

EXAMPLES
(1) GLYCEROL FROM SPENT LYE IN SOAP INDUSTRY
(2) CONCENTRATION OF SUGAR CANE JUICE
(3) HYDROGEN PEROXIDE AND WATER
(E) AZEOTROPIC DISTILLATION:
seprating the components of an azeotropic mixture by distillation , it involves the use of specific techniques
to break the azeotropes.
the most common method of breaking an azeotrope invovels the addition of a material sepration agent that
has the ability to change the molecular interections between the components of the azeotrope.
the addition of such a material separation agent tends to alter the activity of the activity coefficient of the
components of the azeotropic mixture, thereby changing the relative volatility of the azeotropic mixture as a
whole.
ETHYL ALCOHOL AND WATER (AZEOTROPIC MIXTURE) is seprated by BENZENE/HEXANE/
CYCLOHEXANE/PENTANE/DIETHYL ETHER/ACETONE.
(4) DIFFRENTIAL EXTRACTION :
When an organic compound is present in an aqueous medium,
it is separated by shaking it with an organic solvent in which it
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
separatory funnel. The organic solvent is later removed by
distillation or by evaporation to get back the compound.
Differential extraction is carried out in a separatory funnel as
shown in Fig..
If the organic compound is less soluble in the organic solvent, a
very large quantity of solvent would be required to extract
even a very small quantity of the compound. The technique of
continuous extraction is employed in such cases. In this tech-
nique same solvent is repeatedly used for extraction of the
compound.