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SaponiÞcation

Stanley B. Elliott
Bedford Ohio

Keywords

saponiÞcation

A special case of hydrolysis in which an ester is converted into an


alcohol and a salt of the appropriate acid by reaction with an alkali.
Though the operation has numerous applications throughout the
chemical industry, it is noteworthy because some 80% of standard
soap is prepared by this method. The esters may be of mono-
or polybasic acids and mono- or polyhydric alcohols, the physical
conditions under which the reaction occurs being suitably varied to
secure an adequate rate. The alkali most commonly used is sodium
hydroxide, because of cost and water solubility, but other appropriate
alkaline materials are suitable.
Since the preparation of soap is typical of a fairly complex reaction,
chemically, and since it is common, it serves as a useful example
of the saponiÞcation operation. The complication, of course, occurs
because the usual esters used for soap are the glycerol esters of fatty
acids, saturated and unsaturated. Thus the saponiÞcation of stearin
(glycerol tristearate) is commonly shown as follows:

Actually, the saponiÞcation appears to progress stepwise, the Þrst


hydrolytic reaction taking place as follows:

Van Nostrand’s Encyclopedia of Chemistry, Copyright © 2005 John Wiley & Sons, Inc. 1
The diglyceride formed is subsequently split to the monoglyceride,
which Þnally is converted to glycerol, if sufÞcient alkali is present.
Thus, the reaction is a bimolecular one rather than quadrimolecular,
as is commonly indicated. In actual practice, the fats used are
complex glycerides of a number of saturated and unsaturated acids,
rather than the stearin shown here.
Technologically, the saponiÞcation operation varies in degree of
difÞculty depending on the ester. The reaction rate differs for
different esters, for one thing, bu another determining factor is the
contact area possible between the alkali and the ester. In the case
mentioned above, the fat at the start is insoluble and immiscible in
water, so that reaction in a nonagitated vessel would be very slow,
occurring only at the limited interface.
Though saponiÞcation is the dominant reaction when the techniques
described above are used, in many instances side reactions may
occur which may profoundly modify the products. Oxidation, of
course, is one of the more obvious things to guard against, since
many times the esters being treated are unsaturated. Both isomer-
ization and polymerization, however, may occur under the alkaline
conditions obtaining, the unconjugated polyethenoid acids becom-
ing conjugated during treatment. This especially appears to be true
in the case of highly unsaturated compounds. However, by properly
controlling reactants and conditions, saponiÞcation remains a very
ßexible and useful industrial and laboratory operation possible of
wide application and at low cost.
See also Soaps.