Completion of Esterification.

Because the esterification of an alcohol and an organic acid involves a reversible equilibrium,
these reactions usually do not go to completion. Conversions approaching 100% can often be
achieved by removing one of the products formed, either the ester or the water, provided the
esterification reaction is equilibrium limited and not rate limited.

A variety of distillation methods can be applied to afford ester and water product removal from
the esterification reaction. Other methods such as reactive extraction and reverse osmosis can
be used to remove the esterification products to maximize the reaction conversion. In general,
esterifications are divided into three broad classes, depending on the volatility of the esters:

1. When acid, ester and alcohol are non-volatile, the mixture is heated to about 200 oC to
drive off water. An inert gas can be bubbled through the mixture or vacuum can be
applied to speed up the removal. Another method of removal of water is to pass
superheated steam through the mixture. The steam agitates and carries off water with
it.
2. When either or both acid and alcohol are volatile, the reaction may be completed by
distilling out water produced in the reaction as an azeotrope. The azeotrope can be
a. Alcohol : water
b. Ester : Water

Generally an azeotrope is selected which has boiling point below 100 oC and which
condenses in two phases.

3. When both ester and alcohol are volatile and form azeotrope with water, then
additional steps have to be taken. For example esterification of acetic acid with ethanol.
a. Start with a mixture of ethanol and acetic acid with some sulfuric
acid
b. Heat until ester begins to distill out
c. Then mixture of ethanol and acetic acid is added at such a rate
that volume the reaction vessel remains constant.
d. The distillate has a composition of
83.2% Ethyl acetate
9% Ethanol
7.8 % Water

The boiling point of azeotrope is 70.3 oC much below than the boiling point of ethyl
acetate ( 77.15 oC) .
 If the ester is removed as quickly as it is formed, esterification goes on completion even
in the presence of water.

AZEOTROPES:

All most all alcohols ( C1 to C20) form azeotrope with water.

BINARY azeotrope has 2 liquids boiling at the same temperature. E.g Alcohol & water, Alcohol &
ester

TERNARY azeotrope has three liquids boiling at same temperature. E.g Alcohol ,water & ester.

 Ternary azeotrope boils lower than any of the individual constituent’s boiling point. Or
either of the binary azeotrope.
 Ternary azeotrope is collected as long as all the components are present
 Ternary azeotrope cannot be separated by simple distillation.
 First, alcohol is separated by washing with water.
 The remaining mixture is redistilled to collect ethyl acetate as it boils at 77.15 oC
 Water is removed by desiccants and chemical means