SYNTHESIS OF BENZYL ACETATE THROUGH FISCHER

ESTERIFICATION REACTION
J. V. DE GUZMAN
DEPARTMENT OF CHEMICAL ENGINEERING, COLLEGE OF ENGINEERING
UNIVERSITY OF THE PHILIPPINES, DILIMAN QUEZON CITY, PHILIPPINES
DATE PERFORMED:

APRIL 8, 2015

INSTRUCTORS NAME: ALLAN KENNETH REGUNTON

ABSTRACT
Synthesis of esters holds significance in the food, beverage, cosmetic
industry and medicine because of the presence of ester functional group in natural
flavors, fragrances and biomolecules. The purpose of this experiment is to
synthesize benzyl acetate through Fischer esterification occurring through a
nucleophilic acyl substitution mechanism. This method employs the acid-catalyzed
reaction of benzyl alcohol with acetic acid to produce benzyl acetate responsible for
the characteristic odor of peaches. Le Chateliers principle regarding the effects of
reactant concentration and temperature were also employed to increase the
percentage ester yield. The obtained percentage yield is 94.3% which also agrees
with the results obtained by Ganeshpure, et. al. [7], thus implying the effectivity of
using Fischer esterification as an efficient method of preparing esters in research
and industry. Experimental results also showed that increasing the length of the
reflux time can increase the extent of the esterification reaction as compared with
the results obtained by Samal. [4]
_____________________________________________________________________________________________
_________________________________

INTRODUCTION
Esters are carboxylic acid derivatives
where the hydroxy group (-OH) of a
carboxylic acid is replaced by an
alkoxy group (-OR). Esters are
considered being the most widespread
naturally-occurring compounds. Many
simple esters are pleasant-smelling
liquids and are responsible for the
fragrant odors of flowers and fruits
such as banana, pineapple and peach.
Ester linkages are also found in many
biologically important molecules and
animal fats. [1]

Esters are polar molecules because of

the presence of a carbonyl group (C=O) which has an electronegative
oxygen atom that withdraws electrons
from the carbonyl carbon. It leaves the
carbonyl carbon partially positive and
the carbonyl oxygen to be partially
negative. Thus, esters are mainly
governed by dipole-dipole interaction.
However, because of the alkoxy group
that tends to stabilize the partially
positive charge of the carbonyl carbon
attached to it, esters become less
1

polar than alcohols of the same

molecular weight and cannot form
ester-ester hydrogen bonds [1]. As
such, they are less soluble in water
and
have
lower
boiling
points
compared to alcohol and carboxylic
acids. Esters of low molecular weights
are also very volatile thus enabling us
to smell them. [3]
Esters can be synthesized from a
carboxylate anion (RCOO-) reaction
with a primary alkyl halide through an
SN2 reaction mechanism. They can
also be prepared from the reaction of
an alcohol with a carboxylic acid
(RCOOH). The method was developed
in 1895 by Fischer and Speier who
discovered that heating a carboxylic
acid in alcohol solution containing a
strong acid catalyst yields an ester [1].
This reaction was later called as the
Fischer esterification reaction shown
below in Figure 1.
+ R-

H+

Figure
1.
General
esterification reaction

Fischer

The general Fischer esterification

reaction
is
described
by
the
substitution of the hydrogen in the
hydroxide substituent of carbonyl
carbon into the alkyl group of the
alcohol. This reaction is carried out at
acidic conditions and it takes a
nucleophilic acyl substitution pathway.
Fischer esterification reaction is the
most generally useful method of
synthesizing esters because it gives a
relatively high yield [1]. Compared to
the method using a carboxylate salt
and primary alkyl halide reactants,
Fischer esterification only uses readily

available and cheaper reagents such

as alcohol and carboxylic acid.
Methods of synthesizing esters are
important not only in the study of
these compounds but also in the fields
of medicine and industry. Given that
esters give the characteristic pleasant
smell of fruits and flowers and are also
responsible to the taste of some
naturally-occurring flavors, they were
industrially synthesized in order to
mimic natural odors and flavors [3]. As
such, methods of preparing esters
hold significance in various industries
such as food, beverage, perfume and
cosmetics
industry.
In
medicine,
preparation of esters is also important
in studying biomolecules containing
ester functional groups.
This experiment focuses on the
preparation of benzyl acetate, an ester
that gives the characteristic fruity
smell of peach, using the Fischer
esterification reaction method. This is
done by reacting benzyl alcohol with
acetic acid at an acidic medium then
refluxed to yield the benzyl acetate.
The experiment aims to explore the
reflux
technique,
the
physical
properties
of
ester
and
the
nucleophilic
acyl
substitution
mechanism of the reaction which are
also used in many carboxylic acids and
derivatives reaction. It also aims to
evaluate the efficiency of Fischer
esterification
as
a
method
of
synthesizing esters.
METHODOLOGY
In a 25-ml round bottom flask, 9.36 ml
of benzyl alcohol (0.09 mol) was mixed
with 5.15 ml (0.09 mol) of acetic acid.
Boiling chips were put inside the flask.
2

The mixture was acidified by adding 3

drops of concentrated sulfuric acid
while solution was being gently
swirled. A reflux set-up was then
constructed by attaching a reflux
condenser to the reaction flask as
presented in Figure 2.

aqueous layer, solid NaHCO 3 was

added. Sodium bicarbonate was added
until
the
unreacted
acid
was
completely removed in the solution,
indicated when it no longer forms
effervescence. The washed organic
layer was then dried by adding 3
spatula-full of anhydrous Na2SO4. The
dried organic layer was decanted into
a pre-weighed vial then weighed.
RESULTS AND DISCUSSION

[a]

Figure 2. Reflux set-up

The mixture was refluxed for 60
minutes. After refluxing the mixture, it
was cooled to room temperature and
then
transferred
into
a
30-ml
separatory funnel. The remaining
sample adhering in the flask was
obtained by washing the reaction flask
with cold distilled water and adding
the washings to the separatory funnel
until the volume of the aqueous layer
was twice that of the organic layer.
The two layers were stratified by
shaking the mixture and to further
hasten layer separation, 5 drops of a
saturated solution of NaCl was added.
The bottom aqueous layer that
separated was removed. The organic
layer obtained was washed by adding
to it fresh cold distilled water for
further removal of polar impurities.
Saturated solution of NaCl was again
added to force the removal of the
added water in the organic layer. The
organic layer was washed thrice and in
the third wash before removing the

Benzyl
alcohol
was
reacted
in
equimolar amounts with acetic acid.
According to Samal[4], higher yields of
ester can be obtained if the alcohol is
added in excess and kept the
carboxylic acid as the limiting reactant
that is at 1:10 ratio of acid and alcohol
respectively. As suggested by Samal,
this method can increase the yield of
ester to around 90%. It is supported
by Le Chateliers principle, where
increasing the amounts of reactants
drives the equilibrium of the reaction
(Figure 1) towards the formation of
products and thus ensures a high yield
of esters. However, the drawback of
this method is that the excess alcohol
reactant can be difficult and tedious to
separate from the crude ester product
thus affecting its purity. It is also
considered wasteful of reagents.
It is mentioned before that Fischer
esterification
reaction
occurs
at
nucleophilic
acyl
substitution
mechanism and this is shown in Figure
3 below.

with a carboxylic acid is considered an

endothermic reaction as presented by
the energy diagram in Figure 4.

Figure
4.
Esterification
From Figure 3, the carbonyl oxygen is
protonated by the added strong acid
thus activating the carboxylic acid (A
B). The protonated oxygen tends to
withdraw the electrons from the
carbonyl bond to stabilize itself giving
a partially positive charge to the
carbonyl carbon. As such, acid
catalyzes the reaction by making the
carboxylic acid more reactive towards
nucleophilic attack. The incoming
nucleophile is the benzyl alcohol and
the lone pair of its oxygen attacks the
carbonyl carbon to give a tetrahedral
intermediate (BC). The intermediate
(C) with an unstable protonated
oxygen will want to stabilize itself by
transferring a proton from one oxygen
atom to another to yield the second
tetrahedral intermediate and converts
the OH group into a good leaving
group (CD). Water abstracts the
hydrogen from the hydroxyl group and
expulsion of H2O regenerates the acid
catalyst and gives the ester product
(DE).
The general esterification reaction
occurring when an alcohol is reacted

Energy

Diagram

of

Esterification
is
an
endergonic,
reversible reaction characterized by a
very high activation energy barrier [6].
As such, when alcohol and carboxylic
acid are simply mixed, no products will
be formed because of the relatively
small rate of reaction. The rate of
esterification
reaction
can
be
increased
by
increasing
the
concentration of hydronium ions in the
mixture. The hydronium ions catalyze
the reaction by making the carbonyl
carbon susceptible to nucleophilic
attack. It affects the kinetics of the
reaction by lowering the activation
energy thereby increasing the reaction
rate. As such, the mixture of alcohol
and carboxylic acid was acidified by
adding
a
small
amount
of
concentrated sulfuric acid
Before heating the mixture, boiling
chips were added in the reaction flask
in order to prevent bumping. Bumping
is characterized by formation of very
large bubbles that sometimes erupt
violently when the solution becomes
superheated. It must be avoided
because it brings the risk of breaking
the glassware and loss of material.
4

Boiling chips produce a steady stream

of fine air bubbles when heated in a
solvent. It prevents bumping from
occurring since the stream of bubbles
and turbulence produced breaks up
the large bubbles of gases in the
solution
being
heated.
It
thus
promotes smooth boiling of the
solution. Boiling chips must be added
in the liquid before heating has begun,
otherwise, the boiling chips suddenly
placed in a superheated solution will
cause the liquid to boil at once. As a
result, the solution will splash entirely
out of the flask violently. [2]
The mixture of benzyl alcohol and
acetic acid in acidic medium was then
allowed
to
react
at
elevated
temperature
for
60
minutes.
Increasing the temperature of an
endothermic
reaction,
by
Le
Chateliers principle, also drives the
reaction towards product formation. It
is heated for a long time period to
maximize the reaction extent. Because
of the long period required for heating,
reflux technique has been employed
since this technique allows untended
heating of mixture for a long time
period without loss of any reagents or
products. A condenser is attached to
the reaction flask and as such, when
vapors of reagent or solvent escape
out, they are condensed back to liquid
whenever they touch the walls of the
condenser and goes back again into
the flask. [5]
After the solution was refluxed, it was
cooled to room temperature before
doing any purification technique
because the product, ester, is a very
volatile compound and loss of product

can result if it is not cooled. Since the

crude ester product can also contain
unreacted
acid,
acid-catalyzed
hydrolysis of the ester product can
occur at high temperature.
The crude ester obtained was then
separated from polar impurities and
water which is another product of
reaction. These are removed by
adding a saturated solution of NaCl.
Addition of a solution with high ion
concentration such as saturated NaCl
increases the ionic strength of the
aqueous layer. Because the organic
layer is nonpolar, it will be very
immiscible with a solution of high ionic
strength or very polar such that
separation of aqueous and organic
layer can be observed. [2]
After the organic layer was washed
completely, solid NaHCO3 was added
in order to neutralize any unreacted
acid. Solid sodium bicarbonate has
been used so that water will not be
introduced into the ester product.
Sodium bicarbonate is a weaker acid
and upon reaction with the unreacted
acid catalyst, it produces carbonic acid
that can readily dissociate into water
and carbon dioxide as shown by the
formation of effervescence over the
solution. Formation of water in this
step also explains why NaHCO 3 is
added before removing the aqueous
layer in the last washing and before
drying
the
organic
layer
with
anhydrous salt. Sodium bicarbonate
has been chosen over NaOH to
neutralize the acid because NaOH is a
strong base that can induce hydrolysis
of the ester product back to

carboxylate in a process called

saponification shown in Figure 5.
+

HOR
Figure 5. General base-induced ester
hydrolysis reaction
As such, using NaOH as a base to
neutralize the acid can only decrease
the percentage yield by converting the
ester product into a carboxylate.
Water adhering in the mixture and
formed from acid-base reaction of acid
and bicarbonate is removed by drying
the organic layer with anhydrous
Na2SO4 that absorbs the water
present.
The
product
must
be
thoroughly dried since ester in the
presence of water can result to
hydrolyzation, the reverse reaction of
esterification. [1] This is also the reason
why absolute ethanol is used in
preparing esters with ethanol as the
starting alcohol. Esters are being
introduced with too much water if
ethanol solution is used instead of
absolute, causing it to hydrolyze back
to its starting material which is
carboxylic acid.
The dried ester was decanted into a
pre-weighed vial then weighed to
determine the percentage yield. The
results obtained are tabulated in Table
1 below tabulated in Table 1.
Table 1: Yield for the synthesis of benzyl
acetate
Fruity, peachOdor
like
:

Color
:

Clear,
yellowish

Wt of benzyl acetate, 12.74

g
:
Mole of benzyl acetate, 0.08464
mol :
0.09
Mole of benzyl acetate, 0.09
mol :
Mole of acetic acid, mol
:

Theo.
Yield,
mol 0.09
:
%
yield 94.3%
:
The physical properties of the
obtained crude product coincide with
the physical properties of benzyl
acetate. This implies the successful
conversion of benzyl alcohol and
carboxylic acid into benzyl acetate.
The resulting percentage yield is very
high, 94.3%, implying the success of
the
synthesis
using
Fischer
esterification
method.
The
high
percentage yield obtained in using
esterification
as
a
method
of
synthesizing esters also agrees with
the results obtained by Ganeshpure,
et.al [7] regarding their study of Fischer
esterification efficiency in synthesizing
esters at industrial scale.
According to Samar [4] that generally,
esterification of alcohol and carboxylic
acid at 1:1 ratio refluxed for 45
minutes will only produce around 70%
of yield. However, from the results of
the
experiment,
the
equimolar
reaction of benzyl alcohol with acetic
acid refluxed for 60 minutes gives a
percentage yield of 94.3%. It can
therefore
be
inferred
that
the
difference observed between the
obtained percentage yields is because
of the length of reflux time. Based
from
the
energy
diagram
of
esterification presented in Figure 4,
6

the reaction is endothermic and as

such by Le Chateliers principle,
elevating the temperature also favors
the formation of more products. This
also agrees with the study made by
Ahmed-Zeki et.al[6] wherein increasing
the temperature increases the rate
constant of the esterification reaction.
The longer reflux time ensures that all
the reactants were converted into
products. As such, increasing the
reflux time of the esterification
process can also be used as a method
in increasing the yield aside from the
generally used method of using a
large excess amount of alcohol that
can affect the purity of the ester
product. Both methods can also give a
percentage yield greater than 90%.

Based from the relatively high

percentage
yield
obtained
in
synthesizing ester through Fischer
esterification, it can be implied that
experimental
errors
are
almost
avoided
throughout
experiment
conduction. It can also be implied that
the Fischer esterification method is
efficient for macro and micro scale
production of esters to give synthetic
flavors and scents. The results
obtained also shows that changing the
length of the reflux time can affect the
extent of the esterification reaction, as
compared with the study of Samal[4]
and that increasing the concentration
of reactants can give a higher
percentage yield as supported by Le
Chateliers principle.

Another method that can be used to

favor the forward reaction is to
remove one of the products as soon as
it is formed. By Le Chateliers
principle,
decreasing
the
concentration or amount of products
shifts the reaction towards the
formation of more products in order to
attain equilibrium again. Since one of
the products formed is water, the
reflux set-up can be modified such
that water is being continuously
removed as it is formed, thereby
increasing the yield of ester. [4]

CONCLUSION
RECOMMENDATION

The obtained product may have

contained
unreacted
amount
of
alcohol that is not eliminated when the
organic layer is washed. The alcohol
impurity can be removed by purifying
the crude ester product through the
distillation
technique
given
the
difference of the boiling points of
esters and alcohols.

AND

Synthesis of esters is important not

only in the study of them but also in
the fields of industry and medicine
because of the relationship of esters
with natural flavors, scents and
biomolecules. The most generally used
method of preparing esters is through
Fischer
esterification
occurring
through
a
nucleophilic
acyl
substitution
mechanism.
The
esterification
reaction
is
an
endothermic reaction accompanied by
a high activation energy barrier such
that the reaction proceeds only at an
acid-catalyzed
condition.
The
esterification reaction is a reversible
reaction and as such, compounds such
as water and strong bases that can
induce the reverse of esterification or
hydrolysis
process,
are
nearly
removed in the purification stage of
7

the crude product. The obtained

percentage yield of the product is
94.3% which is relatively high implying
the success of experiment conduction
and set-ups and the efficiency of
Fischer esterification as a method in
synthesizing
esters.
The
results
obtained also shows that changing the
length of the reflux time can affect the
extent of the esterification reaction.
The
percentage
yield
of
ester
synthesis can also be increased
through direct application of Le
Chateliers law wherein increasing the
amount of reactants favors the
formation of ester product.
Distillation of the dried ester product
can also be done in order to remove
the unreacted alcohol impurities from
the crude ester. Removing water as it
is being formed in the reaction can
also increase the percentage yield by
shifting the equilibrium towards the
formation of more products. A simple
set-up
can
be
constructed
by
modifying the reflux set-up that
enables separation and removal of
water as the reaction proceeds.
REFERENCES
[1]

McMurry, J. (2008). Organic

Chemistry 7th ed. Chapter 10:
Organohalides,
Chapter
11:
Reactions of Alkyl Halides:
Nucleophilic Substitutions and
Eliminations & Chapter 17:
Alcohols
and
Phenols.
Brooks/Cole, Cengage Learning:
Belmont, pg. 344, 362-380 &
618.

Introduction
to
Organic
Laboratory Techniques. Part
Five: The Techniques. Saunders
College Publishing: Orlando, pp573-574, 641-642, 657, 659.
[3]

Heiss, R. Flavorful Foods.

ChemMatters Online. American
Chemical
Society.
[Online].
2011.
Retrieved
from:
https://www.acs.org/content/acs
/en/education/resources/highsch
ool/chemmatters/pastissues/archive-20112012/flavorfulfood.html
(accessed April 16, 2015).

[4]

Samal. Esters. University of

Massachusetts. [Online]. 2014.
Retrieved
from:
http://people.chem.umass.edu/s
amal/269/ester.pdf
(accessed
April 16, 2015).

[5]

Department
of
Chemistry
University of Calgary. Reflux
and the Reflux Condenser.
[Online].
Retrieved
from:
http://www.chem.ucalgary.ca/co
urses/351/laboratory/reflux.pdf
(accessed April 16, 2015)

[6] Ahmed-Zeki, et. al. Kinetic Study

of Esterification Reaction. AlKhwarizmi Engineering Journal.
2010, 6, 2, pp-33-42.
[7] Ganeshpure, et. al. Arkivoc. 2007,
(viii), pp-273-278.
Image Sources
[a]http://www.chem.ucalgary.ca/course
s/351/laboratory/reflux.pdf

[2] Pavia, D., Lampman, G., Kriz, G.

and
Engel
R.
(1995).
8

APPENDIX
Calculation of Percentage Yield

wt of vial with pdctwt of empty vial=28.82 g16.08 g=12.74 g : wt of benzyl acetate obtained
12.74 g of benzyl acetate x

1 mol benzyl acetate

=0.08464 mol benzyl acetate=actual yield
150.17 g of benzyl acetate

Theoretical conversion:

0.09 mol of benzyl alcohol x

1 mol benzyl acetate

x=0.09 mol benzyl acetate=theoretical yield
1 mol benzyl alcohol

Actual yield:

amt of tbutylCl obtained

0.08464 mo l
x 100 =
x 100 =94.26 : Percentage yield
theoretical amt of tbutCl yield
0.09 mol