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Kinetics of Ethyl Acetate Synthesis Catalyzed by Acidic Resins PDF
Kinetics of Ethyl Acetate Synthesis Catalyzed by Acidic Resins PDF
pubs.acs.org/jchemeduc
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
acidbase 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
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
’ 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.
Figure 2. Concentration of acetic acid versus time.
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 = 4.35 105 dm6/(mol min g). For comparison,
Figure 3. Slope of the linear fitting to the initial points (five points).
kdir is also obtained approximately by assuming that the reaction
is irreversible of second-order, which is only true for very
78 °C are within those found in the literature at 80 °C, namely,
short times.
2.252 and 3.45.3
In the whole, this work gives the students an opportunity to
Concerning modeling, the results graphed in Figure 2 prove
deal with catalytic heterogeneous reversible reactions, and devel-
that the initial value problem given by eqs 3, 5, and 6 represents
op modeling and simulation skills.
data accurately. The rate constant, kdir, has been fitted to the
experimental data by simultaneous optimization and numerical
integration to yield kdir = 4.35 105 dm6/(mol min g) with an ’ ASSOCIATED CONTENT
average absolute relative deviation AARD = 2.86%. Instructors
and students can utilize the Matlab code provided in the bS Supporting Information
Supporting Information to carry out all calculations. The objec- Table with properties and constants of all components;
tive function adopted for the optimization is calculation of both thermodynamic and mass-action law equilib-
rium constants; notes about titration; pictures of the experi-
nX
data mental setup; equipment list; Matlab computer codes (version
exp 2
Fobj ¼ ðCcalc
A, i CA, i Þ ð8Þ 7.8.0) for the optimization of the rate constant (kdir_opt.m) and
i¼1 for the reaction simulation for distinct experimental conditions
It is interesting and pedagogically useful to discuss with the (simul.m). This material is available via the Internet at http://
class the possibility of interpreting the experimental data by the pubs.acs.org.
well-documented approach for irreversible second-order reac-
tions. In fact, because initially CA, CB . CC, CD, one may ’ AUTHOR INFORMATION
consider r = kdirCACB (see eq 1). For an equimolar feed mixture,
it reduces to r = kdirCA2, giving rise to the classical analytical Corresponding Author
solution:5 *E-mail: inesport@ua.pt.
1 1 W
¼ þ kdir t ð9Þ ’ ACKNOWLEDGMENT
CA CA0 V
Therefore, by plotting the foremost experimental points in 1/CA Bruno M. Antunes wishes to express his gratitude to Fundac-~ao
versus t coordinates, it is possible to determine kdir approximately para a Ci^encia e Tecnologia (Portugal) for the grant provided
by the slope of the linear fitting. In this work, five points have (SFRH/BD/66805/2009).
been tested, from which kdir = 3.56 105 dm6/(mol min g) is
obtained; from the data in Figure 3, the slope = kdirW/V = 3.95 ’ REFERENCES
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