ESTERIFICATION

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 Topics to be covered
• Introduction
• Mechanism of Esterification
• Catalysts
• Completing Esterification

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 Introduction
• Esterification is the general name for a chemical
reaction in which two reactants (typically an alcohol
and an acid) form an ester as the reaction product.
• For example:

• For example, reaction of acetic acid with ethanol in

the presence of concentrated sulfuric acid as a
catalyst results in the formation of ethyl acetate
(ester).
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 Introduction
• Esterification is a reversible reaction and the
reverse reaction is called Hydrolysis.
• As a result of this reversibility, esterification
reactions are equilibrium reactions.
• The equilibrium conversion of reaction is not
altered by catalyst, only the rate of reaction is
increased.
• Esterification is the simplest and most often
performed organic transformations.
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 Mechanism of Reaction
• Esterification proceeds by attack of an
alcohol molecule on slightly positive
carbonyl carbon of acid.

• The larger this positive charge, the more

rapid the reaction will be.
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 Question???
• What will be the effect of different ‘R’
groups on the positive charge of carbonyl
carbon and also on the attack of alcohol
molecule on acid?

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 Mechanism of Reaction
• When an acid (HA) is added to esterification mixture, the
oxygen present will act as base and coordinate with acid.
• The mechanism can be written in two ways, depending
on which oxygen of carboxyl group acts as the base:

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 Mechanism of Reaction
• The alcohol oxygen can also act as a base toward
the acid. This reaction hinders esterification and
may lead to dehydration of alcohol.

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 Catalysts
• Hydrochloric and sulfuric acids are the catalysts most
commonly used.
• Sulfuric acid may cause the dehydration of alcohol if
used too much or at a high temperature.
• Perchloric and phosphoric acids can also be used as
catalysts. Phosphoric acid is less efficient but also less
destructive.
• The sulphonic acids are also desirable catalysts
because of their high efficiency, solubility in higher
alcohols and acids and less destructive action.

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 Completing Esterification
• Esterification is equilibrium reaction and obtaining
highest possible yield is always desirable.
• Various methods in which equilibrium is displaced by
removal of one of the reaction products have been
designed.
• One way is to remove the water as it is formed.
When acid, alcohol and ester are nonvolatile, the
mixture is heated to drive out the water.
• This removal of water can be further enhanced by
passing an inert gas through the mixture or by the
application of a vacuum.
• Glycerides of nonvolatile acids are made in this way.
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 Completing Esterification
• Another method of removing the water is to pass
superheated steam through the mixture and it carries off
the water as it is formed.
• When either or both the acid and the alcohol are volatile,
the water may be distilled out with one of the reactants
as an azeotrope.
• An inert solvent insoluble in water can also be added to
form an azeotrope with the water for example butyl
alcohol.
• The apparatus used for azeotropic esterification includes
a receiver in which phase separation occurs. Nonaqueous
phase will return to the esterification vessel while the
aqueous phase will be removed from the bottom.
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