LABORATORY EXPERIMENT

pubs.acs.org/jchemeduc

Kinetics of Ethyl Acetate Synthesis Catalyzed by Acidic Resins

Bruno M. Antunes, Sim~ao P. Cardoso, Carlos M. Silva, and In^es Portugal*
Department of Chemistry, CICECO, University of Aveiro, Campus Universitario de Santiago, 3810-193 Aveiro, Portugal

bS Supporting Information
ABSTRACT: A low-cost experiment to carry out the second-order reversible
reaction of acetic acid esterification with ethanol to produce ethyl acetate is
presented to illustrate concepts of kinetics and reactor modeling. The reaction is
performed in a batch reactor, and the acetic acid concentration is measured by
acid
base titration versus time. The experimental data are used to optimize the
specific rate constant of the direct reaction, which is the unique parameter of
the model; the rate constant for the inverse reaction is expressed in terms of the
equilibrium constant. Good representations are generally obtained: the absolute
average relative deviation found in this work is only 2.86%. After the experiment,
students may carry out simulations for distinct operating conditions. The
experimental data for short times are also analyzed approximately by using the
classical approach for irreversible second-order reactions.
KEYWORDS: Upper-Division Undergraduate, Chemical Engineering, Labora-
tory Instruction, Physical Chemistry, Computer-Based Learning, Hands-On
Learning/Manipulatives, Equilibrium, Esters, Kinetics, Laboratory Equipment/
Apparatus

E sters are an important class of organic compounds with

application in a variety of products such as solvents,
plasticizers, pharmaceuticals, pesticides, and fragrances1 and
as intermediaries in chemical syntheses.2 They are essentially
produced by the reaction of carboxylic acids with alcohols.
These reactions are slow and reversible; hence, catalysts are
usually required. Amberlyst 15 is one of the most active resins
used in this type of reaction due to the acidic nature of the
sulfonic groups. According to Calvar et al.,3 the reaction
time under equivalent experimental conditions reduces from
dozens of days to just some hours after the introduction of
catalyst.
The esterification of acetic acid with ethanol to produce
ethyl acetate is a simple reaction that can be used to illustrate
concepts of kinetics and reactor modeling to undergraduate
chemical and chemical engineering students. Accordingly,
an esterification experiment is carried out in the laboratory
course intended to provide hands-on experience on separa-
tions, reaction, and control. The laboratory course meets
6 h each week. Students, divided into groups of three,
perform the lab exercise in the first week, and in the second
week, they finalize calculations and simulations in the com-
puter room.
The esterification of acetic acid with ethanol is conducted in
a batch reactor in the presence of Amberlyst 15, and the
conversion is followed by acid
base titration. The reac-
tion model is proposed, and the experimental results are
used to determine its unique parameter, namely, the
specific rate constant of the direct reaction. Although
many undergraduate kinetic experiments are available for
instructors, they usually do not deal with reversible reactions
or use them under conditions where they perform almost
irreversibly.4 This experiment intends to fulfill this gap,
giving the students an opportunity to improve skills in this
subject.
’ THEORETICAL BACKGROUND
The esterification of acetic acid (A) with ethanol (B) to
produce ethyl acetate (C) and water (D) is a second-order
reversible reaction that may be represented by the following
chemical equation:
AþB a CþD
Accordingly, the expression for the rate law, r, is


1
r ¼ kdir CA CB
kinv CC CD ¼ kdir CA CB
CC CD ð1Þ
KC
where kdir and kinv are the kinetic constants of the direct and
inverse reactions, respectively; Cj is the molar concentration of
species j; and KC = kdir/kinv is the equilibrium constant expressed
in concentrations.5
When the reaction is carried out in a batch reactor but the
volume of the withdrawn samples is significant, the process
should be modeled as semicontinuous to include volume varia-
tion. For instance, sampling may be represented approxi-
mately by a continuous volumetric flow rate Q. Accordingly,
Published: June 02, 2011

Copyright r 2011 American Chemical Society and

Division of Chemical Education, Inc. 1178 dx.doi.org/10.1021/ed100471j | J. Chem. Educ. 2011, 88, 1178–1181
Journal of Chemical Education LABORATORY EXPERIMENT

the necessary materials balances are5

d
rj W ¼ QCj þ ðCj V Þ ð2Þ
dt

dV
0¼Qþ ð3Þ
dt
where rj = νjr is the rate of formation of component j, whose
stoichiometric coefficient is νj (positive for products, negative for
reactants, and null for inert components), V is the reacting fluid
volume, and W is the mass of catalyst in the reactor. The previous
equations may be combined to give


dCj 1 W
¼ νj kdir CA CB
CC CD ð4Þ
dt KC V
For the reaction under study, the four material balances reduce to


dCA 1 W
¼
kdir CA CB
CC CD ð5Þ
dt KC V

CA
CA0 ¼ CB
CB0 ¼ CC0
CC ¼ CD0
CD ð6Þ

where CA0, CB0, CC0, and CD0 are the initial concentrations of
each species.
Equations 3, 5, and 6, with initial values CA0 and V0, may be
numerically solved to obtain all concentrations and volume over
time. The unique parameter of the model is kdir, because KC may
be obtained from thermodynamic principles (see the Supporting
Information). The equilibrium concentrations Cj,eq may be
predicted with the model for high reaction times. Alternatively,
they can be obtained from the equilibrium expression and eq 6 by
first computing CA,eq from
CC, eq CD, eq
KC ¼
CA, eq CB, eq
ðCC0 þ CA0
CA, eq Þ  ðCD0 þ CA0
CA, eq Þ
¼ ð7Þ
CA, eq  ðCB0
CA0 þ CA, eq Þ
’ EXPERIMENTAL SECTION
The reactions are performed in a 0.250 dm3 isothermic batch
reactor schematically presented in Figure 1. In a typical experi-
ment, using equimolar concentration of both reactants (8.53
mol/dm3), ethanol (0.082 dm3) and 18.00 g of Amberlyst 15
(wet) catalyst (Rohm and Haas, 39389-20-3) are added to the
reactor and heated to the desired temperature (78 °C). Stirring
speed is adjusted to 900 rpm and preheated acetic acid (0.080
dm3) is added to the reactor. This instant is taken as time zero
and the reaction is followed by titration of unreacted acetic acid
in 1 cm3 aliquots, using NaOH and phenolphthalein as indicator.
The concentration of the sodium hydroxide solution is adjusted
during experiment to reduce errors.
To ensure the absence of external mass-transfer resistances, a
stirring speed of 900 rpm was used. An average particle diameter
of 0.463 mm is sufficient to eliminate internal mass-transfer
resistances.3,6 Catalyst mass was chosen to reach equilibrium
concentration in a 3 h period. At the end of the experiment, the
resin was recovered by decantation, washed with acetone and
water, and regenerated with a solution of HCl (1 mol/dm3) for
1 h; finally, it was washed with water until neutral.
1179
Figure 1. Schematic representation of the experimental setup.
’ HAZARDS
Acetic acid (CAS#: 64-19-7) is corrosive and causes severe
irritation and burns. Proper attention and caution should be
taken when handling ethanol (CAS#: 64-17-5), as it is flammable
and irritating to eyes, respiratory system, and skin. Ethyl acetate
(CAS#: 141-78-6) is harmful if swallowed, is irritant and vapors
may cause drowsiness. NaOH (CAS registry number: 1310-73-
2) is very corrosive, which causes severe burns in skin and eye
damage; harmful by ingestion or by inhalation of dust. HCl (CAS
registry number: 7647-01-0) is extremely corrosive, causes
serious burns; toxic, harmful by inhalation, ingestion, and
through skin contact. Gloves and safety glasses are needed during
the lab exercise. Students must review the materials safety data
sheet for each chemical before starting the experiment and are
instructed to collect wastes in specific tanks to be subsequently
treated.
’ RESULTS AND DISCUSSION
Students plot the acetic acid concentration in the reactor
versus time (Figure 2). Note that these results were found for an
initial equimolar mixture of acetic acid and ethanol with CA0 =
8.53 mol/dm3. From this figure, students are able to draw some
typical conclusions and discuss equilibrium compositions. The
experimental data are monotonically decreasing, because acetic
acid is a reactant and no products were introduced initially in the
reactor. Moreover, complete conversion cannot be attained,
because this is an equilibrium reaction. Students must be aware
that, although Amberlyst 15 speeds up the reaction, it never
determines the endpoint of the esterification, which is governed
by thermodynamics. Hence, the final acetic acid concentration
may be predicted by a simple equilibrium calculation. From
Figure 2, CA,eq = 3.20 mol/dm3, which coincides with the value
computed from eq 7. Also, from experimental data one obtains
KC = 2.67, which is very close to the calculated theoretical value,
KC = 2.76 (see the Supporting Information). These values at
dx.doi.org/10.1021/ed100471j |J. Chem. Educ. 2011, 88, 1178–1181
Journal of Chemical Education
Figure 2. Concentration of acetic acid versus time.
Figure 3. Slope of the linear fitting to the initial points (five points).
78 °C are within those found in the literature at 80 °C, namely,
2.252 and 3.45.3
Concerning modeling, the results graphed in Figure 2 prove
that the initial value problem given by eqs 3, 5, and 6 represents
data accurately. The rate constant, kdir, has been fitted to the
experimental data by simultaneous optimization and numerical
integration to yield kdir = 4.35  10
5 dm6/(mol min g) with an
average absolute relative deviation AARD = 2.86%. Instructors
and students can utilize the Matlab code provided in the
Supporting Information to carry out all calculations. The objec-
tive function adopted for the optimization is
nX
data
exp 2
Fobj ¼ ðCcalc
A, i
CA, i Þ
i¼1
It is interesting and pedagogically useful to discuss with the
class the possibility of interpreting the experimental data by the
well-documented approach for irreversible second-order reac-
tions. In fact, because initially CA, CB . CC, CD, one may
consider r = kdirCACB (see eq 1). For an equimolar feed mixture,
it reduces to r = kdirCA2, giving rise to the classical analytical
solution:5
1 1 W
¼ þ kdir t
CA CA0 V
Therefore, by plotting the foremost experimental points in 1/CA
versus t coordinates, it is possible to determine kdir approximately
by the slope of the linear fitting. In this work, five points have
been tested, from which kdir = 3.56  10
5 dm6/(mol min g) is
obtained; from the data in Figure 3, the slope = kdirW/V = 3.95 
10
3 dm3/(mol min). It is worth noting the reliable result
obtained when compared with the former non-approximated
LABORATORY EXPERIMENT
value, kdir = 4.35  10
5 dm6/(mol min g) (only 18.2% inferior).
Despite the clearly approximated nature of the calculations, such
rate constant may be taken as a first guess of the real value.
’ HOMEWORK EXERCISE
Students are asked to answer the following questions at home
or on the second week of the lab exercise.
1. Derive eqs 5 and 6.
2. Neglect the variation of the reacting volume due to
sampling (i.e., Q = 0) and recalculate kdir. Compare and
discuss results.
3. Simulate the reaction for different catalyst load and reacting
volume.
4. Simulate the reaction for different initial concentrations of
all species.
’ CONCLUSIONS
A low-cost experiment where the esterification of acetic acid
with ethanol is catalyzed by Amberlyst 15 in a batch reactor is
presented to analyze the trend of concentrations versus time,
determine the specific rate constant of the direct reaction (kdir),
and simulate the reaction for different operating conditions. The
experimental results are interpreted using the rigorous model for
the reversible second-order reaction. Calculated results are in
good agreement with experimental points, as the absolute
average relative deviation is 2.86%; the rate constant obtained
at 78 °C is kdir = 4.35  10
5 dm6/(mol min g). For comparison,
kdir is also obtained approximately by assuming that the reaction
is irreversible of second-order, which is only true for very
short times.
In the whole, this work gives the students an opportunity to
deal with catalytic heterogeneous reversible reactions, and devel-
op modeling and simulation skills.
’ ASSOCIATED CONTENT
bS Supporting Information
Table with properties and constants of all components;
calculation of both thermodynamic and mass-action law equilib-
rium constants; notes about titration; pictures of the experi-
mental setup; equipment list; Matlab computer codes (version
ð8Þ 7.8.0) for the optimization of the rate constant (kdir_opt.m) and
for the reaction simulation for distinct experimental conditions
(simul.m). This material is available via the Internet at http://
pubs.acs.org.
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: inesport@ua.pt.
ð9Þ ’ ACKNOWLEDGMENT
Bruno M. Antunes wishes to express his gratitude to Fundac-~ao
para a Ci^encia e Tecnologia (Portugal) for the grant provided
(SFRH/BD/66805/2009).
’ REFERENCES
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(3) Calvar, N.; Gonzalez, B.; Dominguez, A. Chem. Eng. Process.
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(5) Fogler, H. S. Elements of Chemical Reaction Engineering, 4th ed.;
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