Fischer Esterification

The basic reaction for ester formation is the synthesis reaction between glacial acetic acid
and alcohol, under acid catalysis (concentrated sulfuric acid). One of the reasons why the
reaction is run this way is because the reaction is in equilibrium, and is subject to Le Chateliers
principle, a system at equilibrium adjusts so as to minimize any stress applied to it. Because
the reaction

, the

is undergoing an exergonic reaction, which favors the

product. Therefore, the reaction shifts to the right. The catalysis does not influence the
equilibrium and only decreases the activation energy, resulting in faster rate of reaction. In the
reaction of glacial acetic acid and isopentanol, the equilibrium can be shifted in various ways
such as: increasing the concentration of glacial acetic acid, or increasing the concentration of
isopentanol, remove isopentyl acetate from the system, or remove water from the system. In
order to obtain a high yield of ester, a large excess of glacial acetic acid will be used to push the
equilibrium to the right.
After the refluxed reaction mixture has been cooled, 5% aqueous sodium bicarbonate is
used to separate the aqueous mixture from the organic layer. The reason why sodium bicarbonate
was used is because it removes excess acetic acid and sulfuric acid in the mixture through the
process of acid-base reaction. Sodium bicarbonate will then lead to the formation of salt, which
is water soluble and is insoluble in the organic layer. Since acetic acid is removed from the
organic phase, it leaves only remaining alcohol and the organic layer, along with the impurities.
In order to remove as much water as possible; a drying agent (granular sodium sulfate) was used.
Once the reaction mixture is finished and the crude carboxylic ester is obtained, distillation
process will then be performed in order to purify the crude mixture and obtain its boiling point.
Distillation method is used because it separates the differing boiling points of the desired
products from the possible contaminants; since some products can be less volatile than others.
The obtained percent yield from the synthesis of glacial acetic acid and isopentanol is
approximately 12.542% (Theoretical yield= 1.749 g; Obtained yield= 0.225 g). One of the
possibilities why it might be very low is probably due to pipetting errors while the aqueous layer
was being separated from the organic layer, since some of the organic layers were removed
together with the aqueous layer. Another possibility might be when the purified ester was being
extracted from the Hickman stillhead, since not all liquid esters were removed and put in the vial
to be weighed.
The identity of the product from the synthesis of glacial acetic acid and isopentanol is
isopentyl acetate. However, it is not as pure as it is wanted, due to the low boiling point obtained,
weak peaks on the IR spectrum, and few unrelated peaks on the NMR. The obtained boiling
point was . The theoretical boiling point of isopentyl acetate is ( )
which is much higher than the obtained boiling point, resulting in 15.493% error. One of the
possible reasons why, is because of the separation of aqueous layer and organic layer via
pipetting. It may have some impurities left even after using granular sodium sulfate to remove
excess water. The result of the IR spectrum shows most of the significant peaks but it is not
composed of strong peaks as it were supposed to be, because the solution is not as concentrated
when the IR was performed. The NMR result shows all the important signals and peaks that
identifies the carboxylic ester as isopentyl acetate; however, there are few small unrelated peaks
that may be traced to acetic acid contamination. Overall, the result identifies the product of the
synthesis reaction as isopentyl acetate but the experimental results suggest that the experiment
performed, can still be improved.
References
Padias, A. (2013). Making The Connections. (2nd ed.). Plymouth, MI: Hayden-McNeil
Publishing.
Padias, A. (2013). Organic Chemistry Laboratory Manual. (4th ed., pp. 01-06). Plymouth, MI:
Hayden-McNeil Publishing.
Isopentyl acetate. (n.d.). Retrieved from
http://www.helsinki.fi/kemia/opettaja/aineistot/hyonteistenkemiaa/english/isopentyl
acetate_webpage.htm