Marjory Joy R.

Castillo 6B
Fischer Esterification of Benzyl Acetate February 7, 2020

Data and Results

Table 1. Physical properties of the product vs benzyl acetate

Product Benzyl Acetate

Mass 2.17 g
N/A
Theoretical Yield 6.32 g
Appearance Clear, colorless Clear, colorless
Odor Sweet, fruity Fruity odor, apple
Density 1.09 1.04
Percent Yield 34.3% N/A

Table 2. Qualitative test results of the product

Test Result (+/-) Remarks

Chromic Acid Test - No alcohol present
Hydroxamic Acid Test Not tested N/A

Discussion
In this experiment, benzyl acetate was prepared from the acid-catalyzed Fischer
esterification of benzyl alcohol and acetic acid. A low yield of 34.3% (Table 1) was obtained
despite the attempt to maximize the formation of product through a reflux setup. The product
tested negative for Chromic acid test which indicates the absence of alcohol. [AtQ2]
However, due to the unavailability of resources in the laboratory, the confirmatory test for
esters -- hydroxamic acid test was not performed.
The mechanism of Fischer esterification (Figure 1) illustrates how an acid like
sulfuric acid first enhances the reactivity of acetic acid before the nucleophilic attack of
benzyl alcohol takes place to produce benzyl acetate. (1) Evidently, the reaction is reversible.
By virtue of Le Chatelier’s principle, the formation of the product is favored by adding
benzyl alcohol in excess or by removing the product immediately as it forms. However, these
methods are proved to be expensive, wasteful of reagents, and difficult. (2) Alcohols are
expensive and cannot be used unsparingly in the laboratory and separating benzyl acetate
immediately from the crude product is difficult as benzyl acetate has a higher boiling point
than its precursors. (3) Alternatively, a reflux setup was used in this experiment because it
essentially drives the reaction forward and prevents product loss. For this reason, 100% yield
is expected. (4) [AtQ 1] Since the result of the experiment is contradictory to this assumption,
the poor yield can be attributed to the inefficient liquid-liquid extraction with 10% sodium
bicarbonate (NaHCO3) and10% sodium chloride (NaCl). The organic layer and aqueous layer
were not properly separated due to emulsions. There was also product loss during sample
transfer.
Liquid-liquid extraction with 10% NaHCO3 was employed to neutralize any unreacted
acid that may affect the purity of the ester. For example, if alcohol was still present in the
refluxed solution, it can be protonated by acids to yield oxonium ions since alcohols are
weakly basic. (5) In extraction, the organic layer was expected to be denser than the aqueous
layer but when the experiment was performed, three layers were formed inside the separatory
funnel. Half of the more viscous layer was above, and the other half was below the more
transparent layer. The organic layer was then identified to be the more viscous layer as its
calculated density is closer to that of benzyl acetate. To enhance the efficiency of extraction
by increasing the ionic strength of the aqueous layer, the organic layer was salted out with
10% NaCl. Aside from drying the product over sodium sulfate, salting out also removes
excess water and helps prevent hydrolysis of the product. It is important to prevent hydrolysis
because excess water reverts the ester to its reactants. [AtQ2] This is also the reason why
distillation must be done after extraction: if water is not removed from the crude ester, the
receiving flask will contain a mixture of acetic acid, benzyl alcohol, and benzyl acetate.
[AtQ3]
Due to lack of time, the isolation of the ester from the crude product through
distillation was not performed. However, the Chromic acid test resulted negative for alcohol
so it can be assumed that the esterification reaction was successful. It is important to keep the
system in equilibrium and prevent proceeding too much to completion because this will
hydrolyze benzyl acetate. The disruption in equilibrium then makes the reaction irreversible
as opposed to the characteristic reversibility of Fischer esterification. (6)
For future experiments, it is recommended to start the experiment early because the
reagents will still be refluxed for an hour and distillation will still be performed for isolation
of the ester. The separatory funnel must also be shook moderately during extraction to avoid
accumulation of emulsions. Acetic acid derivatives like acetic anhydride and acetyl chloride
also reacts well with benzyl alcohol and can be used to obtain a better yield. (7) But such
synthetic routes are seldom followed because both are kinetically controlled, and side
products are formed from the multiple reaction sites occurring. Acid chlorides also evolves
toxic gases. (8)

Accidents and Near Misses

In the extraction with 10% NaHCO3, three layers instead of two formed inside the
separatory funnel. This caused confusion in identifying which the organic layer was. This
was resolved by getting the respective densities and comparing it to that of benzyl acetate.
Meanwhile, upon weighing the mass and measuring the volume of the layers, product loss
could not be avoided during sample transfer from one glassware to another.

Sample Calculation

A. Mass
mass=( mass vial + product )−mass vial

¿ 27.91 g−25.74 g

¿ 2.17 g
B. Theoretical Yield

1 mol C7 H 8 O 1 mol C9 H 10 O 2 150.17 g C9 H 10 O 2

4.55 g C 7 H 8 O× × ×
108.14 g C 7 H 8 O 1mol C 7 H 8 O 1mol C 9 H 10 O 2
 ¿ 6.32 g C 9 H 10 O2
C. Percent Yield
actual yield
% Yield= ×100
theoretical yield

2.17 g
¿ ×100
6.32 g

¿ 34.3 %

References

1) McMurry, J. Organic Chemistry, 8th ed.; Brooks/Cole Cengage Learning: Belmont,

CA, 2012.
2) De Guzman, J. V. Synthesis of Benzyl Acetate Through Fischer Esterification
Reaction. dissertation, Department of Chemical Engineering: Diliman, Quezon City,
2015.
3) Preparation of Benzyl Acetate. Survey of Organic Chemistry Laboratory Manual.
Ateneo De Manila University, 2020.
4) Nichols, L. Reflux. Chemistry Libretexts. https://tinyurl.com/rlvu32s. (accessed Feb
11, 2020).
5) McMurry, J. Organic Chemistry, 7th ed.; Brooks/Cole Cengage Learning: Belmont,
CA, 2008.
6) Bewick, S., et.al. The Equilibrium Constant - A Measure of How Far a Reaction
Goes. https://tinyurl.com/ukat7kq (accessed Feb 12, 2020).
7) Farmer, S. Acid Anhydrides react with alcohols to form esters.
https://tinyurl.com/u43v7r8 (accessed Feb 12, 2020).
8) Tingle, J. Reports: Esterification. American Chemical Journal. 35: 368–369. (accessed
Feb 12, 2020)