CHM146L Organic Chemistry 2 Laboratory

1st Quarter SY 2015-2016

Synthesis of Ethyl Acetate

Miranda, Marilyn A.1, Maquiling, Kenth Roger A.2
1Professor, 2Student, CHM146L/A1, School of Chemical Engineering and Chemistry, Mapúa Institute of Technology

ABSTRACT

Esters are organic compounds of great importance that are derived from an acid in which at least one hydroxyl group is
replaced by an alkoxy group. Various methods are used in the synthesis of esters such as SN2 reactions or alkylation of
carboxylate salts, esterification of carboxylic acids, alcoholysis of acyl chlorides and acid anhydrides, trans-esterification and
others. For this experiment, Fischer esterification was employed for the synthesis of ethyl acetate. Fischer esterification is
done by refluxing a carboxylic acid and an alcohol in the presence of an acid catalyst. It is an example of nucleophilic acyl
substitution, with the following events: 1) proton transfer from acid catalyst to carbonyl oxygen increases electrophilicity of
carbonyl carbon; 2) the carbonyl carbon is then attacked by the nucleophilic oxygen atom of the alcohol; 3) proton transfer
from the oxonium ion to a second molecule of the alcohol gives an activated complex; 4) protonation of one of the hydroxyl
groups of the activated complex gives a new oxonium ion; and 5) loss of water from this oxonium ion and subsequent
deprotonation gives the ester. The use of ethanol, a primary alcohol with acetic acid and sulfuric acid suit the requirements for
a Fischer esterification process. To ensure the success, Le Chatelier’s principle was applied: an excess alcohol was supplied
in the reaction and the subsequent removal of water molecules in the solution through reflux favored the formation of ester.
Successive separatory and purification methods were employed in order to come up with a purified ethyl acetate. Extraction
was used to separate it from the aqueous layer and NaHCO3 was employed to neutralize the left H2SO4. Finally, since some
ethanol might have remained unreacted, distillation was performed on the crude product to obtain a purified ethyl acetate. As
the results on the experiment showed that a distillate (ethyl acetate) was obtained within 77-79ºC with 71.34% yield, it can be
said that the synthesis of an ester, ethyl acetate was successfully demonstrated. Meanwhile, the losses of the product can be
addressed in the purification steps.

Keywords: esters, Fischer esterification, ethanol, acetic acid, sulfuric acid, reflux, ethyl acetate, Le Chatelier’s principle

INTRODUCTION

Esters comprise an group is replaced by an alkoxy group. Usually, they are

essential class of organic
compounds, and probably,
the most-loved of them all
due to its characteristic
pleasant smell, a property
most of them has. They
are often found in fruits
and flowers and are Figure 1. Esters in biological systems:
naturally occurring in vesicular membranes.
biological systems which
include glycerides – fatty acid esters of glycerol and a main
class of lipids that makes up animal fats and vegetable oils;
pheromones; and in our DNA molecules – phosphodiesters.
Besides from those, some are also quite known for their
explosive properties with the likes of nitro esters such as
nitroglycerin, while some are even considered important
plastics, the polyesters and are used widely in industry as
solvents, flame retardants, gasoline and oil additives and
insecticides. Esters are derived from an acid, may it be
organic or inorganic, in which at least one of the hydroxyl
derived from a carboxylic acid and alcohol, hence esters
are also considered carboxylic derivatives.
Figure 2. A carboxylate ester. R and R' denote any alkyl or aryl group.
Containing a carbonyl center, esters exhibit 120 °C-C-O
and O-C-O angles. And very much unlike amides, esters
are flexible functional groups structurally speaking, due to
the low barrier of rotation about the C-O-C bonds. Their
flexibility and low polarity are demonstrated in their physical
properties; they tend to be less rigid (lower melting point)
and more volatile (lower boiling point) than the
corresponding amides. Small esters have boiling points
which are similar to those of aldehydes and ketones with
the same number of carbon atoms. Esters, like aldehydes
and ketones, are polar molecules and so have dipole-dipole
interactions as well as van der Waals dispersion forces.

Experiment 6 | Group 5 | September 15, 2015 1 of 6

 CHM146L Organic Chemistry 2 Laboratory
1st Quarter SY 2015-2016
However, they do not form ester-ester hydrogen bonds, so
their boiling points are significantly lower than those of an
acid with the same number of carbon atoms. Moreover,
small esters are fairly soluble in water but solubility
decreases with increasing chain length as depicted below.
Table 1. Solubility of some esters in water.
Solubility (g per
Ester Formula
100 g of water)
ethyl methanoate HCOOCH2CH3 10.5
ethyl ethanoate CH3COOCH2CH3 8.7
ethyl propanoate CH3CH2COOCH2CH3 1.7
This trend is brought about by the fact that esters cannot
hydrogen bond with each other, although they could with
water molecules. As one of the hydrogen atom in water
becomes partially-positive, it can be effectively attracted to
one of the lone pairs on one of the oxygen atoms in the
ester, thereby forming a hydrogen bond. Forming these
intermolecular attractions (dispersion forces and dipole-
dipole attractions are also present) esters are effectively
solvated, but as the chain length increases, the
hydrocarbon region forces itself between water molecules,
offsetting the solvation and breaking the hydrogen bonds
between water molecules, furthermore, the water molecules
are forced into an alignment along the chain, decreasing
the entropy in the system. Making solvation a process
which is thermodynamically less favorable, thus, solubility
decreases.
Esters can be prepared via various methods, examples are
SN2 reactions or alkylation of carboxylate salts,
esterification of carboxylic acids, alcoholysis of acyl
chlorides and acid anhydrides and trans-esterification. Out
of these, it is via SN2 reactions and esterification of
carboxylic acids that esters are usually prepared.
Figure 4. Various methods for the synthesis of esters.
Experiment 6 | Group 5 | September 15, 2015
When treated with a strong base followed by an alkyl
halide, carboxylic acids are converted into esters:
Figure 5. Preparation of esters via SN2 reactions.
The carboxylic acid is first deprotonated to yield a
carboxylate ion, which then functions as a nucleophile and
attacks the alkyl halide in an SN2 process. The expected
limitations of SN2 processes therefore apply. Specifically,
tertiary alkyl halides cannot be used. In cases that an alkyl
chloride is used, an iodide salt can catalyze the reaction,
Finkelstein reaction. In addition, in difficult cases, the silver
carboxylate may be used, since the silver ion coordinates to
the halide aiding its departure and improving the reaction
rate. The employment of highly polar aprotic solvents such
as DMF can be of help in this type of reaction as it suffers
from anion availability problems.
Carboxylic acid esters, formula RCOOR′ (R and R′ are any
organic combining groups), are commonly prepared by
reaction of carboxylic acids and alcohols in the presence of
hydrochloric acid or sulfuric acid, a process called Fischer
esterification. In the reaction the hydroxyl group (OH) of
the carboxylic acid is ultimately replaced by the alkoxy
group (R′O) of alcohol as shown on the mechanism below.
Figure 3. Fischer Esterification general reaction.
.
Figure 6. Fischer Esterification process.
2 of 6
 CHM146L Organic Chemistry 2 Laboratory
1st Quarter SY 2015-2016

The accepted mechanism clearly depicts a nucleophilic acyl METHODOLOGY

substitution that takes place under acidic conditions. The
carbonyl oxygen is first protonated making the carbonyl
carbon more electrophile which is susceptible to the attack
of the alcohol (oxygen atom), which then gains a positive
charge. The positive charge is then removed via
deprotonation and the OH group of is converted to a better
leaving group via proton transfer. The carbonyl group then
reforms, expelling water in the process. The positive charge
on the carbonyl oxygen is finally removed via
deprotonation.
The Fischer esterification process is reversible and can be
controlled by exploiting Le Châtelier’s principle. That is,
formation of the ester can be favored either by using an
excess of the alcohol (i.e., using the alcohol as the solvent)
or by removing water from the reaction mixture as it is
formed.
Figure 7. Reversibility of Fischer Esterification.
Comparing the two approaches discussed in the synthesis
of ester, the Fischer esterification is the method of choice.
The primary advantages of Fischer esterification compared
to other esterification processes are based on its relative
simplicity. Straightforward acidic conditions can be used if
acid-sensitive functional groups are not an issue; sulfuric
acid can be used; softer acids can be used with longer
reaction times. Because the reagents used are direct, there
is less environmental impact in terms of waste products and
harmfulness of the reagents. Also it is primarily a
thermodynamically-controlled process which means that the
most stable ester would form as the major product due to its
slowness. This can be a desirable trait if there are multiple
reaction sites and side product esters to be avoided. In
contrast, rapid reactions involving acid anhydrides or acid
chlorides are often kinetically-controlled.
Table 2. Reagents used in the experiment.
Reagents Structure
Ethyl Alcohol
Glacial Acetic Acid
Sulfuric Acid NaOH
Sodium Bicarbonate NaHCO3
Sodium Chloride NaCl
Magnesium Sulfate MgSO4
The materials that were used for the current experiment
were quick fit, vial, beaker and hot plate. For the reagents,
the synthesis of ethyl acetate required ethyl alcohol, glacial
acetic acid, concentrated sulfuric acid, 5% aqueous
NaHCO3, saturated aqueous NaCl and anhydrous MgSO4.
The procedure was straightforward and it proceeded as
follows: 1) Fischer esterification; 2) Extraction; and 3)
Distillation.
A 10 mL of ethyl alcohol and 15 mL of glacial acetic acid
were placed in a round bottom flask. Next, 3 mL of
concentrated sulfuric acid was added to the mixture with
shaking and then glass beads were supplemented in order
to distribute the heat on the sample equally. A reflux set up
was assembled and the mixture was heated to boiling for
an hour as shown on figure 8. The sample turned into dark
red from being colorless after an hour process of reflux.

In the present experiment, it aimed to synthesize an ester

via Fischer esterification using glacial acetic acid and
ethanol under acidic conditions (sulfuric acid) and in
understanding the mechanism of preparing ester.

Figure 8. Reflux set-up for Fischer esterification.

Now that the ester has been synthesized, purification of the

product came next. This was done through successive
extraction methods and finally distillation. Before the

Experiment 6 | Group 5 | September 15, 2015 3 of 6

 CHM146L Organic Chemistry 2 Laboratory
1st Quarter SY 2015-2016
mixture was transferred to a separatory funnel, it was
cooled down to room temperature. After, 37 mL of cold
water was added and the washing was added to the
separatory funnel as well to reduce loss of the product. The
funnel was then stoppered and shaken properly for several
times. The funnel was allowed to stand for about three
minutes to stabilize the layers. As the two layers separated,
the aqueous layer was drawn off and discarded.
The organic layer extracted, which now contained the crude
ester also had some acetic acid in it. To remove this acetic
acid, another extraction was done to the crude ester with
5% aqueous NaHCO3. The lower layer was discarded each
extraction with the NaHCO3. The washing was repeated
until the solution became basic.
Figure 9. Extraction of the crude ester using 5% NaHCO3.
After the solution became basic, the organic layer was
extracted with 25 mL of distilled water. 5 mL of saturated
aqueous NaCl was also added to facilitate separation. The
aqueous layer was drawn off and the organic layer was
transferred to the Erlenmeyer flask, then dried with 2 grams
of anhydrous magnesium sulfate. The crude ester was
allowed to stand for 15 minutes until it became a clear
liquid. By pipetting, the ester was separated from the
drying agent. And it was finally distilled, having the receiver
placed in an ice bath for the concluding purification step.
Liquid compound, presumably ethyl acetate was obtained
boiling between 77 ºC to 79 ºC. The weight of the purified
product was then measured and the percentage yield was
calculated.
Experiment 6 | Group 5 | September 15, 2015
RESULTS AND DISCUSSIONS
Table 3. Data on the synthesis of ethyl acetate.
Weight of crude product, g 3.07 g
Weight of pure product, g 2.19 g
% Recovery 71.34%
Boiling Point of the Purified
77ºC-79ºC
Product
Figure 10. General overview on the synthesis of ethyl acetate using
acetic acid and ethanol under acidic conditions.
In the experiment, an ester – ethyl acetate, was
synthesized using ethyl alcohol, acetic acid and sulfuric
acid (acidic condition) via Fischer esterification process and
was then further separated and purified using successive
extractions and distillation approaches. Fischer
esterification is a special type of esterification wherein a
carboxylic acid and an alcohol are refluxed in the presence
of an acid catalyst. In our set-up, the sulfuric acid served as
the acid catalyst with a primary purpose to make possible
for a nucleophilic acyl substitution based on the
electrophilicity of the carbonyl carbon and the
nucleophilicity of an alcohol. This is very critical because
alcohol such as ethanol is a weak nucleophile, thus it is
needed to protonate the carbonyl oxygen in order make the
carbonyl carbon electrophile due to the withdrawal of
electron rich region toward the carbonyl oxygen due to its
electronegativity. Moreover, since most carboxylic acids are
suitable for the reaction, only the alcohol is the main
concern. Alcohol used should generally be a primary
(ethanol) or secondary alkyl. Tertiary alcohols are prone
4 of 6
 CHM146L Organic Chemistry 2 Laboratory
1st Quarter SY 2015-2016
to elimination, and phenols are usually too unreactive to
give useful yields.
Figure 11. Acid catalysis of sulfuric acid in the reaction.
Figure 12. Mechanism of the synthesis of ethyl acetate.
As the carbonyl carbon is attacked by the nucleophilic
oxygen atom of alcohol (ethanol in our case), a proton
transfer from the oxonium ion to a second molecule of the
Experiment 6 | Group 5 | September 15, 2015
alcohol give rise to an activated complex. The hydroxyl
group of the activated complex is then protonated to give a
new oxonium ion. Now that a good leaving group is present,
the carbonyl group reforms, expelling water from the
oxonium ion and the subsequent deprotonation gives the
ethyl acetate.
Figure 13. Color change on the sample during reflux.
During and after the reflux process, it was observed the
sample had changed its color, which further signified that
the synthesis of ethyl acetate was happening. Moreover, all
reaction in the synthesis were reversible and had not
controlled in favor with the ester formation, would have led
to the reformation of acetic acid and the ethanol. This was
done considering Le Chatelier’s principle, which states that:
“a change in one of the variables that describe a system at
equilibrium produces a shift in the position of the equilibrium
that counteracts the effect of the change.” In the
experiment, the concentration of ethanol was changed to
shift the equilibrium forward, favoring the formation of ester.
Excess alcohol was used making the acetic acid the limiting
reagent. Another method that can was employed is the
removal of water that formed in the process. Having water
would result in the hydrolysis of the ester, which is a
reverse reaction. This was done by refluxing the solution
sample to evaporate water or another is the use of drying
agents.
To purify the ester formed, several steps were done. It is
important to note that the process was catalyzed by sulfuric
acid, and some of this acid was left unreacted. Thus,
sodium bicarbonate was used to neutralize it in the
successive extractions. The use of NaHCO3 over NaOH is
critical since CO2 is formed when sulfuric acid is reacted
with sodium bicarbonate and not with sodium hydroxide.
The carbon dioxide formed is a sign that there is acid that
reacts with the NaHCO3 added to the solution.
A final purification step was employed to the crude product
to ensure the purity of the ethyl acetate. Since an excess of
ethanol was possible, it was removed through distillation
process. Results tabulated on table 3 shows that distillate
was collected within 77-79ºC and a 71.34% yield was
obtained. The other ethyl acetate synthesized might have
5 of 6
 CHM146L Organic Chemistry 2 Laboratory
1st Quarter SY 2015-2016
lost in the purification processes. Finally, the presence of a
pleasant smell on the product concludes that indeed an
ester was synthesized.
CONCLUSIONS AND RECOMMENDATIONS
Esters, which are organic compounds of great importance,
and have characteristic pleasant smells, are derived from
an acid in which at least one hydroxyl group is replaced by
an alkoxy group. Various methods are used in the synthesis
of esters such as SN2 reactions or alkylation of carboxylate
salts, esterification of carboxylic acids, alcoholysis of acyl
chlorides and acid anhydrides, trans-esterification and
others. For this experiment, Fischer esterification was
employed for the synthesis of ethyl acetate.
Fischer esterification is done by refluxing a carboxylic acid
and an alcohol in the presence of an acid catalyst. It is an
example of nucleophilic acyl substitution based on the
electrophilicity of the carbonyl carbon and the
nucleophilicity of an alcohol. The following events happen in
the said reaction: 1) proton transfer from acid catalyst
to carbonyl oxygen increases electrophilicity of carbonyl
carbon; 2) the carbonyl carbon is then attacked by
the nucleophilic oxygen atom of the alcohol; 3) proton transfer
from the oxonium ion to a second molecule of the alcohol
gives an activated complex; 4) protonation of one of the
hydroxyl groups of the activated complex gives a new oxonium
ion; and 5) loss of water from this oxonium ion and subsequent
deprotonation gives the ester.
Most carboxylic acids are suitable for the reaction, but the
alcohol should generally be a primary or secondary alkyl.
Tertiary alcohols are prone to elimination, and phenols are
usually too unreactive to give useful yields. Hence the use
of ethanol, a primary alcohol with acetic acid and sulfuric
acid, as acid catalyst, suit the requirements for a Fischer
esterification process. To ensure the success of the
synthesis, Le Chatelier’s principle was applied, wherein an
excess alcohol was supplied in the reaction and the
subsequent removal of water molecules in the solution
through reflux favored the formation of ester. Moreover,
successive separatory and purification methods were
employed in order to come up with a purified ethyl acetate.
Since ester are relatively insoluble in water, extraction was
used to separate it from the aqueous layer. Also, since an
excess of sulfuric acid is apparent, neutralization of
NaHCO3 made sure that no presence of acid was left in the
purified ester. Finally, since some ethanol might have
Experiment 6 | Group 5 | September 15, 2015
remained unreacted, distillation was performed on the
crude product to obtain a purified ethyl acetate.
The advantages of Fischer esterification is that the process
is straightforward and the reagents used are well
characterized which reduces adverse environmental
impacts. Also it is primarily a thermodynamically-controlled
process: because of its slowness, the most stable ester tends
to be the major product. This can be a desirable trait if there
are multiple reaction sites and side product esters to be
avoided. In contrast, rapid reactions involving acid anhydrides
or acid chlorides are often kinetically-controlled. Moreover, its
disadvantages are mainly its thermodynamic reversibility
and relatively slow reaction rates.
In conclusion, as the results on the experiment showed that
a distillate (ethyl acetate) was obtained within 77-79ºC with
71.34% yield, it can be said that the synthesis of an ester,
ethyl acetate was successfully demonstrated. Meanwhile,
the losses of the product can be addressed in the
purification steps.
REFERENCES
(1) Caracas, C., & Largoza M. (2013). Nucleophilic acyl
substitution: The synthesis of esters. Retrieved
September 11, 2015 from
https://www.academia.edu/4635235/Nucleophilic_
Acyl_Substitution
(2) Castillo, B. (2015). Synthesis of ethyl acetate. Retrieved
September 14,2015 from
file:///C:/Users/asus/Desktop/Chm146L-
Experiment-6.pdf
(3) Chang, R., & Goldsby K. (2014). General chemistry (7th
ed.). New York, NY: McGraw-Hill Companies, Inc.
(4) Chemspider (n.d.) Structure search. Retrieved
September 12, 2015 from
http://www.chemspider.com/StructureSearch.asp
(5) Jerry, M., & Smith M. (2007). Advanced organic
chemistry, reactions, mechanisms, and structure
(6th ed.). Hoboken, NJ: John Wiley & Sons, Inc.
(6) Klein D.R. (2011). Organic chemistry. Danvers, MA:
John Wiley & Sons, Inc.
(7) Wilbraham, A., Staley, D., Matta M., & Waterman E.
(2003). Addison-Wesley chemistry. Jurong,
Singapore: Pearson Education (Asia) Pte Ltd.
(8) University of California Davis (n.d.). Synthesis of esters.
Retrieved September 12, 2015 from
http://chemwiki.ucdavis.edu/Organic_Chemistry/Es
ters/Synthesis_of_Esters
6 of 6