Amanda Nadine V.

Lazo 19B
Ch 22 G May 7, 2019
Experiment 7: Preparation of Benzyl Acetate

Introduction
Fischer esterification is a form of esterification which involves carboxylic acid and
alcohol in the presence of an acid catalyst (1). Carboxylic acid is not a strong enough
electrophile and therefore is too unreactive for the alcohol to attack it. Thus the reaction can
only proceed when the carboxylic acid is protonated by an acid which then activates it and
enables it to be attacked by the alcohol (1).
In this experiment, Benzyl acetate, which is used for things such as synthetic
flavoring for the taste and aroma of apples, peaches and pears, is prepared through the
Fischer esterification of benzyl alcohol and acetic acid with sulfuric acid as a catalyst. The
aim of the experiment is to be able to properly perform the Fischer esterification reaction and
yield the maximum amount of pure benzyl acetate.

Method
First, around 5.5 ml of acetic acid and ~2 ml of concentrated H2SO4 were added to a
round bottom flask. Benzyl alcohol was then slowly added into the mixture and the mixture
was then swirled. Next, the round bottom flask was attached to a reflux setup and the mixture
was heated for an hour. After heating, the round bottom flask was let to cool down before
decanting its contents into a separatory funnel. The round bottom flask was then washed with
15 ml of distilled water and this was used to wash the mixture in the separatory funnel as
well. The organic layer was then drained into a flask and the aqueous layer was discarded.
Then, the organic layer was washed with 10 ml of 5% NaHCO and 10 ml of 10% NaCl. The
organic layer was then decanted once more into an Erlenmeyer flask and dried over sodium
sulfate. A chromic acid qualitative test was then performed to check for the presence of
benzyl alcohol, while a Hydroxamic acid test was performed to test for the presence of benzyl
acetate.

Results

Table 1. Summary of Raw data

Reagent Amount added

Water 15 ml

Acetic Acid 5.5 ml

Benzyl Alcohol 4.5 ml

H2SO4 ~2 ml

5%NaHCO 10 ml

10% NaCl 10 ml

Table 2. Summary of Product Weight

Sample/Material First Decant Second Decant
Empty Flask 41.38g

Organic Layer + Flask 44.60g 42.34g

Final Sample 0.96g

Table 3. Qualitative test Results

Qualitative Test Result

Chromic Acid Negative

Hydroxamic Acid Positive

Discussion
In this experiment, a final yield of 100% is not to be expected. This is due to a number
of reasons such as first, the reaction is an equilibrium reaction and will therefore always have
some unreacted sample (1). Second, transferring the product from one glassware to another
for the duration of the experiment to complete each step will incur sample loss as some
product will be left behind in the glassware (ATQ1). In this experiment however, the final
sample yield was very low with only a percent yield of 15.36%*. With benzyl alcohol being
the limiting reagent* the calculated theoretical yield for this experiment was only 72%*.
Though a percent yield of 72% does not seem too high, it is a lot considering the percent
yield of 15.36%. It is possible that this low percent yield is due to different factors such as
evaporation of sample during heating. However, for this particular experiment, it is possible
that most of the sample was lost due to the formation of solid byproducts. These solid
byproducts were difficult to decant as they stuck to the bottom of the flasks or would not
decant from the separatory funnel, hence much sample was lost.
Though the final yield was quite low, the purity of the benzyl acetate was good. As
seen in table 3, the sample tested negative for the Chromic acid test, while it tested positive
for the Hydroxamic acid test. The Chromic acid test was meant to test for the presence of
benzyl alcohol, thus a negative result indicated that there was no benzyl alcohol left in the
sample. The Hydroxamic acid test was to test for the presence of benzyl acetate, and hence a
positive test indicated that the sample contained benzyl acetate. These qualitative test results
indicated that the final sample was a more or less pure sample of benzyl acetate (ATQ2).
If distillation were used to try to separate benzyl alcohol and benzyl acetate, it would
have been quite difficult. The boiling points of benzyl alcohol and benzyl acetate are quite
near each other 205 °C and 214 °C respectively (2). Aside from their boiling points being
very close, they are also quite high thus it would take a long time to reach the desired
temperature. Liquid-liquid extraction is preferred as it works on the difference in densities of
the two reagents. If distillation was used first, the mixture in the receiving flask would not be
a pure sample of benzyl acetate (ATQ3).
There are two derivatives of acetic acid that can be reacted with benzyl alcohol to
form benzyl acetate; these are acetic anhydride and acid chloride (3). These derivatives
however are much more reactive on their own as compared to carboxylic acid which needs to
be protonated before reacting with benzyl alcohol. Thus, these two other synthetic routes may
produce side products thus affecting the purity of the final yield (3). Aside from that, acetic
acid is much cheaper to use for the synthesis of benzyl acetate through Fischer esterification
(ATQ4).
Sample Calculations

Determining Limiting Reagent:

Acetic Acid

(5.5ml x 1.05g/ml) x (1mol acetic acid / 60.05g) x (1mol benzyl alcohol / 1mol acetic acid) =
0.0962mol benzyl alcohol

Benzyl Alcohol

(4.5ml x 0.789g/mol) x (1mol benzyl alcohol / 46.068g) x (1mol acetic acid / 1mol benzyl
alcohol) = 0.077mol acetic acid

Benzyl Alcohol = limiting reagent

Theoretical Yield:

(4.5g benzyl alcohol x 108.138g/mol) x 150.17g/mol benzyl acetate = 6.25g benzyl acetate

Percent Yield:

(Actual Yield / Theoretical Yield) x 100

(0.96 / 6.25) x 100 = 0.1536 or 15.36%

Conclusion
The experiment was successful in synthesizing benzyl acetate from benzyl alcohol
through Fischer esterification. This is supported by the results of the qualitative tests which
indicate a pure sample of benzyl acetate. However, the yield was not maximized as proven by
the 15.36 percent yield of the final product. This was due to perhaps the formation of solid
byproducts, the result of multiple transfers from one glassware to another, or sample loss due
to evaporation during heating.

References:
(1)Yanza ERS. Survey of Organic Chemistry Laboratory Manual. Department of Chemistry,
Ateneo de Manila University; 2014.

(2) PubChem [Internet]. National Center for Biotechnology Information. PubChem

Compound Database. U.S. National Library of Medicine; [cited 2019May6].
Available from: https://pubchem.ncbi.nlm.nih.gov/

(3)Guidote A, del Rosario D, Abuzo A. Experiencing Organic Chemistry. Quezon City:

Office of
Research and Publications, Ateneo de Manila University; 2005.