Ind. Eng. Chem. Res.

2000, 39, 2601-2611 2601

Reaction Kinetics and Chemical Equilibrium of Homogeneously and

Heterogeneously Catalyzed Acetic Acid Esterification with Methanol
and Methyl Acetate Hydrolysis
T. Po1 pken, L. Go1 tze,† and J. Gmehling*
Carl von OssietzkysUniversität Oldenburg, Technische Chemie, P.O. Box 2503, D-26111 Oldenburg, Germany

The reaction kinetics and chemical equilibrium of the reversible esterification of methanol with
acetic acid were investigated. This system is of major importance as a model reaction for reactive
distillation. The reaction has been catalyzed both homogeneously by acetic acid itself and
heterogeneously by an acidic ion-exchange resin (Amberlyst 15). The chemical equilibrium
composition was measured for various temperatures and starting compositions of the reactants
and products. Kinetic information was obtained at temperatures between 303.15 and 343.15 K
at various starting compositions covering concentration ranges from the stoichiometric regime
to the dilute regions. Both the esterification and the hydrolysis reaction were investigated to
yield a model which is applicable for any starting composition. The homogeneous reaction has
been described with a simple power-law model. The use of activities in the kinetic model instead
of mole fractions results in a much smaller residual error. To compare pseudohomogeneous and
adsorption-based kinetic models for the heterogeneously catalyzed reaction, independent binary
liquid adsorption experiments were used to fit the adsorption constants to keep the number of
adjustable parameters the same for each model. The use of activities instead of mole fractions
results in a slight improvement of the kinetic model only, while incorporating adsorption
information into the kinetic model results in a much better fit. The chemical equilibrium
composition calculated from the kinetic model is in agreement with the measured chemical
equilibrium.

Introduction (PVA), and acetic acid and methanol can be recycled on

Methyl acetate synthesis by esterification of acetic
acid with methanol, and the backward reaction, the
hydrolysis of methyl acetate, have recently received
growing interest as a model reaction for reactive distil-
lation.1 Reactive distillation offers distinct advantages
over the conventional approach of performing the reac-
tion and separation sequentially. Examples are reduced
capital and operating costs due to higher conversion and
reduction of the extent of parallel and consecutive
reactions resulting in a higher selectivity. Its major
drawback is that the chemical reaction has to have
significant conversion at distillation temperatures, which
limits the range of applicability somewhat. Reactive
distillation has been identified as being suitable for the
methyl acetate system for different processes, namely,
the synthesis of methyl acetate,2,3 the hydrolysis of
methyl acetate,4-6 and the recovery of dilute acetic acid
from wastewater.7,8 The methyl acetate process not only
has been the first process employing the concept of
reactive distillation9 when esters gained commercial
importance in the late 1920s10 but also was the first
process being adapted to a large industrial scale.2 Today,
the hydrolysis of methyl acetate to acetic acid and
methanol is of major importance because methyl acetate
is a byproduct during the synthesis of poly(vinyl alcohol)
* To whom correspondence should be addressed. Phone:
+49-441-7983831.Fax: +49-441-7983330.E-mail: gmehling@tech.
chem.uni-oldenburg.de.
† Present address: Sulzer Chemtech Ltd., Separation and
Reaction Technology, P.O. Box 65, CH-8404 Winterthur,
Switzerland.
10.1021/ie000063q CCC: $19.00 © 2000 American Chemical Society
Published on Web 06/17/2000
site into the process.
Although the reaction is known to proceed rather
slowly, most reactive distillation modeling and simula-
tions considering this reaction have been performed
assuming chemical equilibrium. It has been shown by
Bessling et al.1 that the error introduced by assuming
infinitely fast reaction kinetics is relatively small at
atmospheric pressure and high catalyst mass. By op-
erating reactive distillation columns at reduced pressure
and thus reduced temperature, one is able to study the
effect of reaction kinetics on the performance of a
reactive distillation column and gain more insight into
the process. This knowledge is of great importance for
the design of reactive distillation columns for esterifi-
cation reactions, especially for higher esters, where
reaction kinetics is usually slower than that for the
methyl acetate system. Another advantage of the methyl
acetate system is that the miscibility gap in the methyl
acetate-water system disappears upon the addition of
small amounts of methanol and/or acetic acid, which
results in the absence of a second liquid phase in the
reactive distillation column under normal operating
conditions. This simplifies column modeling and allows
the investigation of the backward reaction kinetics
under homogeneous conditions.
Because in modern reactive distillation processes a
structured or random packing is employed, it is desir-
able to use a rate-based model. To apply a rate-based
model for the simulation and design of a reactive
distillation process, a reliable knowledge of the reaction
2602 Ind. Eng. Chem. Res., Vol. 39, No. 7, 2000
kinetics and the chemical equilibrium is required be-
sides the mass-transfer characteristics, vapor-liquid
equilibrium, and the various pure component properties.
When the equilibrium-stage model is used, knowledge
of reaction kinetics is desirable to relax the often-made
simplifying assumption of chemical equilibrium.
The kinetics of this esterification reaction has been
investigated to some extent in the past. The reaction
has been studied in terms of heterogeneous catalysis
by various ion-exchange resins7,8,11-13 or homogeneous
catalysis by strong acids, like hydrogen chloride14 or
hydrogen iodide.15 To the best of our knowledge, all
investigations published either covered only a limited
temperature range,13 covered a limited concentration
range,8,14 or suffered from side reactions with the
catalyst.15 In some of the published models, the back-
ward reaction has not been considered, which is a valid
assumption if one operates with a large excess of one
reactant7,8,14 and at low conversion, but not when one
operates at nearly stoichiometric concentrations, as in
the case of reactive distillation processes for the syn-
thesis or the hydrolysis of methyl acetate. Our group
already reported kinetic data for this system in the
past,3,16,17 which were fitted to a considerably smaller
database than that in the present work. In this work,
we extend the range of the data from the stoichiometric
regime into the more diluted regions, as they are
encountered in reactive distillation processes, where the
reactants are fed in a countercurrent fashion into the
column. Also, a comparison of different kinetic models
and an independent investigation of chemical equilib-
rium is presented. This work should therefore ensure a
reliable modeling of reaction kinetics in the methyl
acetate system catalyzed by Amberlyst 15 or similar ion-
exchange resins.
Experimental Section
Chemicals. Acetic acid and methanol used were of
analytical grade (99.8%, Scharlau), the water was
bidistilled, and the methyl acetate was reaction grade
(99.7% purity, as determined by gas chromatography,
Riedel-de-Haën). For the titrimetric analysis, Titrisol
(1.0 and 0.1 N sodium hydroxide, E. Merck) was used.
The chemicals were used without further purification
except for drying over a molecular sieve.
Catalyst. The macroreticular ion-exchange resin
Amberlyst 15 (wet) (Rohm and Haas Co.) was selected
as the catalyst. The catalyst was washed once with
methanol and then several times with water until the
supernatant liquid was colorless to remove impurities.
In some experiments, the catalyst was used wet, while
in others it was used after being dried. In all cases, the
water content of the catalyst was determined after the
kinetic experiment by drying of the catalyst at 90 °C
under vacuum until the mass remained constant (usu-
ally 2 days). Drying at higher temperatures involves the
risk of loosing sulfonic acid sites in the form of SO3
because of desulfonization of the polystyrene matrix of
the catalyst.
The ion-exchange capacity of the resin was deter-
mined by total exchange with sodium chloride solution
and subsequent titration. A value of 4.77 ( 0.01 mequiv
of H+‚g-1 of dry catalyst was obtained, which compares
well with the value of 4.75 mequiv‚g-1 given by the
manufacturer. A sieve analysis of the commercial resin
using mesh widths of 1.20, 1.12, 0.80, 0.63, 0.40, and
0.20 mm gave the distribution of pellet diameters (Table
Table 1. Size Distribution of Commercial Amberlyst 15
diameter range (mm) mass fraction
>1.12 0.037
1.00...1.12 0.211
0.80...1.00 0.403
0.63...0.80 0.242
0.40...0.63 0.102
0.20...0.40 0.004
<0.20 0.0003
1). The calculated mean diameter of the resin beads was
0.86 mm. For the investigation of possible mass-transfer
resistance effects, a sample of the catalyst was ground
and sieved to a diameter smaller than 63 µm.
Measurements for the Determination of Chemi-
cal Equilibrium. The experiments were carried out by
placing the desired amount of reactants (total 2.5 g,
different compositions) and vacuum-dry catalyst (about
10 mg) in a 5-cm3 glass vial, which was then sealed and
placed in a thermostat at a given temperature with an
accuracy of (0.1 K for 1-3 weeks. To check if the
chemical equilibrium was reached within analytical
error, each experiment contained samples to undergo
net esterification and samples to undergo net hydrolysis.
Some of these samples were composed in a way to give
the same equilibrium composition. Values reported
satisfy this criterion. Just before analysis, the vials were
cooled rapidly to about 255 K and opened, and the liquid
phase was transferred into a 1-cm3 glass vial. This was
placed into the cooled (274 K) sample tray of an
automatic sampler (HP 7673) and analyzed by gas
chromatography (HP 5890 with TCD; H2 as the carrier
gas at 70 cm3‚min-1; Porapak-QS 1.25 m × 1/8 in.;
temperature program, 383 K for 2.5 min, rate of 10
K‚min-1 to 443 K, held for 6.5 min; typical retention
times: water, 2.3 min, methanol, 4.5 min, methyl
acetate, 10.5 min, and acetic acid, 11.7 min).
Measurements for the Determination of Reac-
tion Kinetics. Apparatus. The experiments were con-
ducted in a thermostated glass reactor with a volume
of 500 cm3. The temperature of the heating jacket was
kept constant within (0.1 K. The temperature of the
reaction mixture was measured by a thermocouple
against ice water. The stirrer was plate-type and the
speed was variable between 100 and 800 rpm. To
improve mixing, a baffle was installed. Furthermore, a
reflux condenser was used to avoid loss of volatile
compounds. The outlets of the reactor not connected to
the condenser were heated electrically to avoid conden-
sation. Liquid samples of about 1 cm3 were taken using
a syringe and weighed (accuracy of the balance: (0.001
g).
Experimental Procedure. Methanol, or in the case of
the hydrolysis reaction water, was heated together with
the catalyst to the desired reaction temperature. Acetic
acid, or for the reverse reaction methyl acetate, was
heated in a separate vessel. When the liquid in the
reactor reached the desired reaction temperature, the
second reactant was added to the reactor. The stirrer
and the time measurement were started immediately.
Samples were then taken according to the sampling
program. During each experiment, between 15 and 45
samples were taken.
Analysis. All reactants added to the reactor were
weighed with an accuracy of (0.001 g. During the
experiments the acetic acid concentration of the samples
was determined by potentiometric titration with sodium
hydroxide solution (Kyoto Electronics, model AT-200).
 Ind. Eng. Chem. Res., Vol. 39, No. 7, 2000 2603

Table 2. UNIQUAC ri and qi Values19 Table 3. UNIQUAC Parameters Used for the Calculation
of Activity Coefficients (Eq 1)
component ri qi
i j aij (K) bij cij (K-1)
acetic acid 2.2024 2.0720
methanol 1.4311 1.4320 acetic acid methanol 390.26 0.970 39 -3.0613 × 10-3
methyl acetate 2.8042 2.5760 methanol acetic acid 65.245 -2.034 6 3.1570 × 10-3
water 0.9200 1.4000 acetic acid methyl -62.186 -0.436 37 2.7235 × 10-4
acetate
methyl acetic acid 81.848 1.116 2 -1.3309 × 10-3
With knowledge of the stoichiometry, the concentrations acetate
of the other reactants were calculated from the acetic acetic acid water 422.38 -0.051 007 -2.4019 × 10-4
acid concentration. The results were in good agreement water acetic acid -98.120 -0.29355 -7.6741 × 10-5
with preliminary gas-chromatographic determinations, methanol methyl 62.972 -0.710 11 1.1670 × 10-3
acetate
which also ensured the absence of side reactions. methyl methanol 326.20 0.724 76 -2.3547 × 10-3
Measurement Program. Fourteen runs for the reaction acetate
without catalyst and 50 runs for the reaction catalyzed methanol water -575.68 3.145 3 -6.0713 × 10-3
water methanol 219.04 -2.058 5 7.0149 × 10-3
by Amberlyst 15 were performed with variations in the methyl water 593.70 0.010 143 -2.1609 × 10-3
ratio of the reactants and the temperature (303.15- acetate
343.15 K). For the catalyzed runs, additionally, the water methyl acetate -265.83 0.962 95 2.0113 × 10-4
amount of catalyst was varied. The absence of external
mass-transfer resistance was ensured by a stirrer speed
sufficient to allow a complete suspension of the catalyst.
Additionally, the stirrer speed was varied between 100
and 560 rpm. No influence of the stirrer speed on the
kinetics could be detected above 170 rpm. Therefore, all
experiments reported were conducted with a stirrer
speed of at least 170 rpm, usually 250 rpm. The
influence of pore diffusion was checked in supplemen-
tary tests with sieved fractions of the catalyst having a
narrow distributed pellet diameter. Most of the experi-
ments were continued until chemical equilibrium was
reached.

Calculation of Liquid-Phase Activities

The activity coefficients, γi, necessary to account for
the real behavior of the liquid phase were calculated Figure 1. Chemical equilibrium constants Ka (O) and best fit of
using the UNIQUAC equation.18 A polynomial temper- our data (solid line), compared with an estimation based on eq 3
ature dependence of the interaction parameter and thermodynamic data (dashed line, short dashes). The correla-
tion given by Song et al.13 is included (dashed line, long dashes)
together with their mean values of Ka (0, from kinetic data) for
∆uij(T) ) aij + bijT + cijT2 (1) the individual temperatures. Song et al. included a value of Ka at
373 K given by Menschutkin28 in their correlation.
was included in the model. The r and q values of the
pure components (Table 2) were taken from the litera- Table 4. Standard Enthalpies and Standard Gibbs
Energies of Formation
ture.19 Interaction parameters were fitted simulta-
neously to vapor-liquid equilibrium (VLE), activity component source ∆h°f (kJ‚mol-1) ∆g°f (kJ‚mol-1)
coefficient at infinite dilution (γ∞), and heat of mixing acetic acid ref 20 -484.09 -389.23
(hE) data. The data originated from the Dortmund Data methanol ref 21 -239.11 -166.89
Bank, Version 1998, which was kindly placed at our methyl acetate ref 21 -442.79 -328.39
disposal by DDBST GmbH, Oldenburg, Germany. For water ref 20 -285.83 -237.14
the reactive systems (methanol-acetic acid and methyl
acetate-water), additional VLE and hE measurements and the standard Gibbs energy of reaction ∆g°r by
were carried out by our group. These data will be
reported elsewhere soon. The resulting parameters are ln Ka(T0) ) -∆g°r/RT0 (3a)
reported in Table 3.
and the integrated form of the van’t Hoff equation,

Chemical Equilibrium Composition
To obtain reliable knowledge about the chemical
equilibrium, independent experiments were carried out
as described in the Experimental Section. The tabulated
results are available as Supporting Information. Figure
1 shows the results as a plot of the natural logarithm
of the equilibrium constant Ka
Ka ) ∏aiν ) ∏xiν × ∏γiν
i i i
(2)
versus the inverse of the absolute temperature. The
slope and intercept of the linear regression of the data
are related to the standard enthalpy of reaction ∆h°r
( )
∆h°r 1 1
ln Ka(T) ) ln Ka(T0) - - (3b)
R T T0
if a constant enthalpy of reaction is assumed, which is
reasonable because of the relatively small temperature
interval investigated.
This allows one to compare the results against an
estimation based on tabulated values of the standard
enthalpy of formation and the standard Gibbs energy
of formation of the individual reactants from the litera-
ture,20,21 which are given in Table 4. The resulting
values for ∆h°r and ∆g°r are listed in Table 5. The
dotted line in Figure 1 shows the resulting temperature
2604 Ind. Eng. Chem. Res., Vol. 39, No. 7, 2000

Table 5. Standard Enthalpies and Standard Gibbs Table 6. Summary of the Experiments without Catalyst
Energies of Reaction Added
source ∆h°r (kJ‚mol-1) ∆g°r (kJ‚mol-1) initial mole numbers
run temperature duration
from heats of formation (Table 4) -5.42 -9.41 number (K) (days) HOAc MeOH MeOAc H 2O
from linear regression (Figure 1) -5.67 -9.06 1 313.15 34 1.1840 1.1645 0 0
from Song’s correlation -6.51 -8.60 2 313.15 11 1.2934 0.6701 0 0
3 323.15 8 1.2150 1.2085 0 0
dependence of the equilibrium constant. However, one 4 323.15 8 1.4496 1.3914 0 0
should be aware that a small error in ∆g°f or ∆h°f 5 323.15 11 0.3814 0 1.7003 1.7597
causes a relatively large error in ∆g°r or ∆h°r due to 6 323.15 13 0.8944 0.2488 0.4011 0.5311
7 323.15 25 0.7933 0 0.5474 1.3108
the small magnitude of the values of these thermody- 8 328.15 20 2.7327 2.7278 0 0
namic properties. 9 333.15 3 1.4035 1.4033 0 0
The dashed line shows the correlation given by Song 10 333.15 6 1.2533 2.3720 0 0
et al.,13 along with their mean values of Ka for the 11 333.15 3 1.2102 0.5637 0.0710 0.1948
individual temperatures. The slopes of the three lines 12 333.15 15 0.8330 0 0.5641 1.2869
13 321.65 6 1.4373 0.1573 1.1350 1.3968
in Figure 1 are rather similar, indicating an agreement 14 321.65 1 1.4167 0.1317 1.1644 1.4417
of the different standard enthalpies of reaction. The
values are given in Table 5 together with the ∆g°r where xi denotes the mole fraction of component i, νi its
values, which also show good agreement.
stoichiometric coefficient, ai the activity of component i
(with ai ) xiγi), and k1 and k-1 the rate constants of the
Development of a Kinetic Model esterification and the hydrolysis reaction, respectively.
As a first step, the reaction kinetics without added The exponent R will be explained below in more detail.
catalyst is being modeled. The resulting model is then The temperature dependence of the rate constants is
incorporated into the model for the ion-exchange cata- expressed by Arrhenius’ law
lyzed reaction, to account for the homogeneously cata-

( )
lyzed reaction in the liquid phase. -EA,i
ki ) k0i exp (7)
Fitting Procedure
RT

The kinetic equations are integrated numerically by
a fourth-order Runge-Kutta method. The calculated
weight fractions of acetic acid are compared with the
experimental ones, giving the mean relative deviation
all samples
Four adjustable parameters, namely, the pre-exponen-
tial factors k01 and k-1
0
and the energies of activation
EA,1 and EA,-1, have to be fitted. The term aRHOAc
accounts for the activity of the protons in the mixture,

∑ | wHOAc,calc - wHOAc,exp
wHOAc,exp
| which are the catalyst for both the esterification and
the hydrolysis reaction. Depending on the assumptions
about the catalytic mechanism, R may show a value of
Frel ) × 100% (4) 0.5 or unity. On one hand, if one assumes that the
nsamples catalysis occurs via solvated protons and the dissociation
of acetic acid can be described by the Brønsted equilib-
and the mean squared deviation: rium constant Ka, then
all samples

∑ (wHOAc,calc - wHOAc,exp)2
Fabs2 ) (5)
nsamples
Parameters are fitted by minimization of Fabs2 using the
Simplex-Nelder-Mead method,22 while the values of
Frel, obtained with the fitted parameters, are reported
as residual error in Tables 7 and 11.
Homogeneous Reaction
In a first step, the homogeneous system was investi-
gated. In this case, the reaction occurs by catalysis of
acetic acid. The esterification reaction and the hydroly-
sis reaction were investigated at temperatures between
313.15 and 333.15 K. A summary of the experiments is
given in Table 6. With the last two experiments, the
chemical equilibrium composition was verified because
even after weeks, chemical equilibrium was not reached.
The resulting composition profiles versus time were
used to fit the parameters of the following kinetic
equation,
1 dxi
r) ) aRHOAc(k1aHOAcaMeOH - k-1aMeOAcaH2O) (6)
νi dt
Ka )
aH+aAcO- xH+xAcO-
≈ )
xH+2
(8)
aHOAc aHOAc aHOAc
and hence
xH+ ≈ xaHOAcKa (9)
This assumption would lead to an exponent of R ) 0.5
in eq 6, when xKa is incorporated into the kinetic
constants.
On the other hand, if one assumes catalysis by
undissociated acetic acid, giving a reaction of two
molecules of acetic acid with one molecule of methanol
for the esterification reaction, and a reaction of one
molecule of methyl acetate, water, and acetic acid for
the hydrolysis reaction, this would lead to an exponent
of R ) 1 in eq 6. Formally, this corresponds to a
trimolecular reaction.
To distinguish between these two possibilities, all
data were fitted once with a value of R ) 0.5 and once
with R ) 1. Finally, R was included in the fitting
procedure as a fifth adjustable parameter. All optimiza-
tions have been run with the assumption of ideal liquid-

Table 7. Parameters and Residual Errors of the Different Kinetic Models Used To Fit the Experimental Data without
Catalyst Added
mean relative
exponent R activities error (%) k01 (s-1)
0.5 ideal 4.9 6.57 × 104
0.5 UNIQUAC 4.0 1.30 × 105
1 ideal 3.1 2.54 × 106
1 UNIQUAC 2.2 5.11 × 105
1.406 ideal 2.2 2.42 × 106
1.056 UNIQUAC 2.2 6.06 × 105
Figure 2. Arrhenius diagram of the rate constants for the
esterification reaction k1 (b) and the hydrolysis reaction (O) of the
homogeneous reaction catalyzed by acetic acid (eq 6, R ) 1, activity
coefficients calculated by UNIQUAC). The lines represent the
result of the overall fit (compare Table 7).
phase behavior (γi ) 1.0, this means ai ) xi) and with
values for γi calculated from the UNIQUAC equation
and thus accounting for the real liquid-phase behavior.
The results of the fitting procedure are reported in Table
7. To ensure that the global minimum was found, the
optimization was restarted at least three times with
different initial parameters.
As can be seen from Table 7, the best results for a
fixed value of R were obtained with a value of R ) 1 for
ideal and nonideal behavior. Accounting for the real
liquid-phase behavior always resulted in a smaller
residual error. For the case of R ) 1 and liquid-phase
activities being calculated by UNIQUAC, the validity
of the kinetic model has been assessed by fitting only
k1 and k-1 to all experimental data at the same
temperature. Without experiments 13 and 14 from
Table 6, for which no meaningful fit was obtained
because of the near-absence of net reaction, four pairs
of k1/k-1 values for the different temperatures were
obtained. The natural logarithm of these values is
plotted in Figure 2 versus the inverse temperature, thus
giving an Arrhenius plot. Rate constants calculated from
the overall fit (row 4 in Table 7) are included as lines.
From the plot, it is obvious that the temperature
dependence of the rate constants can be described by
Arrhenius’ law and that the overall fit is able to
represent the data. To demonstrate that the model is
capable of giving a reasonable representation of the
experimental data, four experiments at 323.15 K with
very different initial compositions are plotted in Figure
3 together with the calculated concentration course. As
can be seen from the figure, the model is able to describe
not only the esterification but also the hydrolysis
reaction.
When R was fitted, a value of about unity was
obtained, taking into account the real behavior by the
Ind. Eng. Chem. Res., Vol. 39, No. 7, 2000 2605
EA,1 (kJ‚mol-1) 0
k-1 (s-1) EA,-1 (kJ‚mol-1)
60.4 1.02 × 107 79.1
61.6 1.00 × 107 82.2
62.5 1.00 × 107 77.3
63.5 9.83 × 106 80.2
67.3 9.27 × 106 75.8
63.8 9.84 × 106 80.0
Figure 3. Experimental values for the acetic acid concentration
(weight fraction) of four runs without catalyst added (0, run 3; 4,
run 5; ), run 6; O, run 7; compare Table 6) and calculated course
(eq 6, R ) 1, activity coefficients calculated by UNIQUAC).
UNIQUAC model. This emphasizes the importance of
taking into account the real liquid-phase behavior to
obtain consistent results. For consistency, we recom-
mend using UNIQUAC and a value of R ) 1. This
corresponds formally to catalysis by molecular acetic
acid, not solvated protons. This result is consistent with
results published by Williamson and Hinshelwood.23
Heterogeneously Catalyzed Reaction
Preliminary experiments were used to determine a
sufficient stirrer speed to ensure the absence of external
mass-transfer limitations. Additionally, some experi-
ments to assess intraparticle mass transfer were con-
ducted by using different sieve fractions of the commer-
cial catalyst and using sieved samples of ground catalyst.
For sieve fractions of the commercial catalyst, no effect
of the pellet size on the reaction kinetics was observed,
which is consistent with the fact that pellets of Am-
berlyst 15 are composed of very small microspheres,24
which are similar in size. When the catalyst was ground
in a ceramic mill and sieved to smaller than 63 µm, an
increase in the rate by a factor of about 2 was observed.
This indicates indeed a mass-transfer limitation, which
is only of importance when the catalyst is subjected to
grinding or abrasion. To avoid abrasion, no magnetic
stirrer, but a plate-type stirrer, was used in our work.
Neither the data of Song et al.,13 which were obtained
using a magnetic stirrer, nor our data obtained with a
magnetic stirrer or with a ground catalyst were included
in our fitting procedure. The error introduced by the
abrasion of the resin should be small, though, because
the mass fraction of the smaller particles is relatively
low. Because the aim of this work is to present a kinetic
expression for use in reactive distillation, where the
catalyst is packed into structured packing elements and
2606 Ind. Eng. Chem. Res., Vol. 39, No. 7, 2000

Table 8. Summary of the Experiments with Amberlyst 15 as Catalyst

run mass of dry initial mole numbers (mol)

number temperature (K) catalyst (g) duration (h) HOAc MeOH MeOAc H2O
1 304.25 18.27 23.4 1.557 1.557 0 1.014
2 303.45 31.54 23.3 1.993 2.012 0 0
3 313.63 8.84 2.0 1.621 1.618 0 0.542
4 313.14 3.81 23.4 1.646 1.608 0 0.234
5 313.00 5.76 31.6 3.589 1.591 0 0.354
6 323.00 7.17 5.6 1.997 1.999 0 0.427
7 323.15 7.71 6.4 2.031 1.982 0 0
8 323.00 7.31 4.8 1.996 2.090 0 0.441
9 323.00 6.70 5.0 2.006 2.017 0 0.363
10 323.00 23.80 5.1 2.003 2.049 0 1.485
11 323.08 8.18 17.7 1.656 1.626 0 0.502
12 323.06 8.55 18.8 1.642 1.621 0 0.524
13 323.06 17.10 21.1 1.632 1.627 0 1.049
14 323.00 3.54 23.0 2.050 1.019 0 0.217
15 323.00 8.67 3.2 1.539 2.921 0 0.531
16 323.15 7.15 5.9 0.428 3.588 0 0.440
17 333.14 4.25 23.2 1.669 1.642 0 0.261
18 333.12 8.19 20.3 1.670 1.646 0 0.502
19 333.13 17.71 20.1 1.661 1.604 0 1.087
20 333.20 23.38 4.9 1.562 1.549 0 1.230
21 304.25 18.66 23.4 0 0.367 1.614 1.546
22 313.30 17.61 19.7 0 0 1.621 2.801
23 313.00 5.70 95.1 0 0 2.539 4.156
24 323.08 17.13 18.5 0 0 1.648 2.698
25 323.15 29.52 3.7 0 0.432 1.812 1.897
26 333.03 17.78 20.9 0 0 1.623 2.785
27 323.15 12.97 6.5 2.001 2.009 0 0
28 323.15 27.61 6.5 2.012 2.008 0 0
29 323.15 36.95 6.5 2.003 1.992 0 0
30 323.15 46.35 6.5 2.015 1.998 0 0
31 323.15 55.37 3.7 2.004 2.015 0 0
32 323.15 5.02 6.5 0.246 4.761 0 0
33 323.15 7.20 6.2 0.431 3.579 0 0
34 323.15 6.14 7.1 1.008 4.073 0 0
35 323.15 5.61 5.4 2.721 0.730 0 0
36 323.15 11.19 6.2 3.590 0.387 0 0
37 323.15 5.89 1.8 3.088 0.142 0 0
38 323.15 4.32 70.6 0 0 0.595 5.400
39 323.15 4.35 24.6 0 0 1.005 3.991
40 323.15 6.65 5.4 0 0 1.997 0.499
41 323.15 5.27 4.5 0 0 1.795 0.198
42 313.15 20.73 24.5 0 0 0.898 9.362
43 323.15 20.54 5.4 0.897 0.901 0 8.454
44 323.15 59.68 1.3 0 0 0.613 5.417
45 333.15 20.49 5.4 0 0 0.904 9.366
46 343.15 21.18 3.5 0.894 0.901 0 8.517
47 313.49 17.60 21.1 1.483 0 0.640 1.477
48 313.45 17.58 19.0 1.012 0 0.956 2.328
49 333.05 17.66 15.8 0.654 1.580 0.800 1.281
50 333.09 17.58 19.0 0.459 0.149 0.934 3.866
thus not subjected to abrasion, it is justified to neglect hydrolysis reaction (Table 8). Besides the temperature
this possible mass-transfer effect. The reader should be for the esterification (experiments 1-20) and hydrolysis
aware that all activation energies for the heteroge- (experiments 21-26) reaction, the amount of catalyst
neously catalyzed reaction presented in this work are (experiments 27-31), the initial reactant ratio for the
apparent activation energies, not the true values for the esterification (experiments 32-37), and the hydrolysis
chemical reaction. (experiments 38-41) reaction were varied at 323 K.
We also checked the applicability of the model pre- Finally, some experiments (42-46) were performed in
sented by Song et al.13 by calculating the concentration the presence of excess water, which permitted the
course of acetic acid from their model and comparing temperature to be raised to 343 K without boiling, and
them with our experimental results. Their model de- for initial compositions near chemical equilibrium (ex-
scribes the reaction quite well when the experimental periments 47-50).
conditions are similar to theirs, that is, esterification According to the data presented by Song et al.,13 the
reaction and in the presence of 8-22 wt % of wet side reaction, the condensation of two molecules of
catalyst. However, the hydrolysis reaction is not de- methanol to form dimethyl ether, does not occur in an
scribed by their model with the required accuracy, as appreciable amount in the temperature range covered
are experiments with considerably less catalyst or dry in this work and is therefore neglected.
catalyst. Therefore, it seems appropriate to propose a Thereactionhasbeendescribedbothwithapseudohomo-
model with parameters based on a larger experimental geneous model6-8,11 and with adsorption-based models.13
database without these limitations. Therefore, a comparison of both models is presented.
Our database includes experimental data from 303 On one hand, theoretical support for the pseudohomo-
to 333 K for both the esterification reaction and the geneous model comes from the fact that the polymeric

catalyst swells in contact with polar solvents such as
water or methanol by more than 50% of its dry volume.
This should facilitate diffusion in the polymer matrix
and make the polymer-bound sulfonic acid groups
readily accessible for the reactants. On the other hand,
the swelling is highly selective,13,25 which was confirmed
by our experiments. This makes an adsorption-based
model suitable, even if on a molecular scale, adsorption
seems not to be the best description for the phenomenon.
Pseudohomogeneous Model
First of all, the pseudohomogeneous model should be
considered, which can be written as
1 dni
r) ) mcat(k1aHOAcaMeOH - k-1aMeOAcaH2O) (10)
νi dt
where the ion-exchange resin is thought to act as a
source of solvated protons. As for the homogeneous
reaction, the model parameters were fitted to the
experimental data by the Simplex-Nelder-Mead method,
minimizing Fabs2. The resulting parameters are given
in Table 11 both for assuming ideal liquid-phase be-
havior and considering liquid-phase activities using the
UNIQUAC model. Also, the results of calculating the
concentration course with the model of Song et al.13 are
given. For this model, the calculation was performed
with the parameters reported by Song et al. and also
with parameters fitted to our data.
The pseudohomogeneous model is clearly not the best
choice. An adsorption-based model, such as the model
of Song et al., seems to be a better choice because the
residual error can be halved when compared with the
pseudohomogeneous model, when the parameters of the
model of Song et al. are fitted to our data.
Adsorption-Based Model
A rigorous modeling of the solvent uptake by a
swelling polymer would involve modeling of the polymer-
phase activities by an appropriate model, for example,
a modified Flory-Huggins model.25 The condition of
isoactivity between the liquid and polymer phase would
then yield the swelling equilibrium. However, for densely
cross-linked resins bearing highly polar groups on
almost every monomer (Amberlyst 15 has a degree of
functionalization of about 88%), these effects are poorly
understood and do not yield consistent results.25 For this
reason, we will stay with the adsorption-based modeling
until a reliable model applicable to this system has been
developed.
To further improve the modeling of the reaction
kinetics, the Langmuir-Hinshelwood-Hougen-Watson
(LHHW) model of Song et al. should be modified. A
critical assumption in their adsorption model is that a
constant adsorbed amount is assumed, the value of
which is not given in the article. Furthermore, they did
not use a constant value for the fit of all binary
adsorption data because they fitted this value for each
binary system separately.26 It is necessary to fit the
adsorption constants to independent data.13 If they are
fitted together with the kinetic constants, an extremely
good fitting result with very poor extrapolation capabili-
ties is obtained.
The results of our measurements of the swelling ratio,
which is the volume of solvent-equilibrated resin divided
Ind. Eng. Chem. Res., Vol. 39, No. 7, 2000 2607
Table 9. Experimental Swelling Ratios Obtained for the
Pure Components and Adsorbed Volumes, Masses, and
Moles per Gram of Dry Amberlyst 15 at 298 K
adsorbed adsorbed adsorbed
swelling volume mass amount
component ratio (cm3‚g-1) (g‚g-1) (mmol‚g-1)
acetic acid 1.43 0.307 0.319 5.31
methanol 1.55 0.393 0.309 9.60
methyl acetate 1.40 0.286 0.265 3.58
water 1.67 0.479 0.478 26.5
by the dry volume of the resin, in a sealed graduated
cylinder (accuracy, (0.25 cm3) are reported in Table 9.
The values given are mean values of four to five
experiments conducted at 298 K. The accuracy of the
data is estimated to be about (5%. Assuming that the
resin bed’s volume changes in the same way as the
volumes of the individual resin microspheres, adsorbed
volumes can be calculated from the swelling ratio. Also
assuming ideal mixing, that is, no excess volume, the
adsorbed mass and amount per gram of catalyst can be
calculated. The values are given in Table 9.
It is obvious from Table 9 that the assumption of a
constant amount adsorbed is not suitable because there
is an order of magnitude difference between the values
for methyl acetate and water. A better choice would be
the assumption of constant adsorbed mass, for which
the values for the individual compounds are similar. For
this reason, the equations given by Song et al. are
modified to allow for a constant adsorbed mass.
From the overall mass balance of the binary liquid-
phase adsorption in a system of total solvent weight,
m0, and catalyst mass, mcat, with the overall weight
fraction, w01, and the equilibrium liquid-phase weight
fraction, wL1 , of solvent 1, it follows for the adsorbed
masses of solvents 1 and 2, mS1 and mS2 , analogous to
Kipling27
m0(w01 - wL1 ) mS1 wL2 - mS2 wL1
) (11)
mcat mcat
Assuming Langmuir-type adsorption based on mass, the
following relation for the mass coverage mSi /mS can be
obtained, with mS being the total adsorbed mass and ai
the liquid-phase activities:
mSi Kiai
) (12)
mS 1+ ∑j Kjaj
Combining eqs 11 and 12 for the binary case, the
following relation is obtained,
m0(w01 - wL1 ) L
mS K1a1w2 - K2a2w1
L
) (13)
mcat mcat 1 + K1a1 + K2a2
which can readily be used to fit the equilibrium con-
stants Ki and the total adsorbed mass mS/mcat to binary
adsorption data, for example, by the Simplex-Nelder-
Mead method.22 This is done with the four nonreactive
sets of binary adsorption data, which were also obtained
using a sealed graduated cylinder to obtain the swelling
ratio information, which is not included in this model
but might be useful for developing a more reliable
polymer swelling model. The total adsorbed mass per
catalyst mass, mS/mcat, is kept the same for all binary
2608 Ind. Eng. Chem. Res., Vol. 39, No. 7, 2000

Figure 4. Relative adsorption of water from water-acetic acid
(O) and water-methanol (0) mixtures on Amberlyst 15 and
calculated dependence assuming constant adsorbed mass.
Figure 6. Arrhenius diagram of the rate constants for the
esterification reaction k1 (b) and the hydrolysis reaction (O) of the
heterogeneously catalyzed reaction (eq 16, activity coefficients
calculated by UNIQUAC). The lines represent the results of the
overall fit (compare Table 11).

1 dni
r) ) mcat(k1xSHOAcxSMeOH - k-1xSMeOAcxH
S
2O
) (14)
νi dt

where

mSi /Mi
xSi ) (15)
∑j (mSj /Mj)

represents the mole fractions of the reactants in the

adsorbate phase yields

Figure 5. Relative adsorption of methanol from a mixture of

methanol and methyl acetate (O) and relative adsorption of acetic
acid from a mixture of acetic acid and methyl acetate (0) on
Amberlyst 15 and calculated dependence assuming constant
adsorbed mass.
Table 10. Results of the Regression for the Nonreactive
Binary Adsorption Data at 298 K
Equilibrium Adsorbed Mass
mS/mcat ) 0.95
Adsorption Equilibrium Constants
KHOAc ) 3.15
KMeOH ) 5.64
KMeOAc ) 4.15
KH2O ) 5.24
systems. The data are presented in Figures 4 and 5 and
are available as Supporting Information. The results of
a fit of all four adsorption equilibrium constants to all
of the data are included in Figures 4 and 5 and
summarized in Table 10. The fit reproduces the data
within experimental accuracy. The comparatively high
value obtained for mS/mcat might be explainable by the
increase in the swelling ratio when the liquid phase is
a mixture instead of a pure solvent.
r)
1 dni
νi dt
) mcat
(
k1a′HOAca′MeOH - k-1a′MeOAca′H2O
(a′HOAc + a′MeOH + a′MeOAc + a′H2O)2 )
Ki ai
with a′i ) (16)
Mi
with Mi denoting the molar mass of component i,
whereby the rate constants k1 and k-1 are temperature
dependent, as described by eq 7.
For this model, the Arrhenius diagram shown in
Figure 6 has been constructed by fitting simultaneously
all experimental data at a given temperature and
plotting the natural logarithm of the resulting values
for ki against the reciprocal temperature. Also included
in the plot is the result for the fit of the four variables
k01, k-1
0
, EA,1, and EA,-1 as lines, the result of which is
given in the last row of Table 11. The agreement of the
overall fit and the results obtained for the individual
temperatures is good, as is the linearity.
Figure 7 shows results of a fit of eq 16 to single
experiments, where only k1 was fitted and k-1 was
calculated from our chemical equilibrium correlation by
the relation

In contrast to the work of Song et al.,13 all four aMeOAcaH2O k1KHOAcKMeOHMMeOAcMH2O

adsorption constants are known at this point and none
of them needs to be included as adjustable parameters
in the fit to the kinetic data. Thus, the adsorption is
being modeled truly independent from the kinetic fit.
Combining this adsorption model (eq 12) with a
kinetic model of the form
Ka ) ) (17)
aHOAcaMeOH k-1KMeOAcKH2OMHOAcMMeOH
which can be obtained from eq 16 when the reaction rate
r is set to zero.
In these experiments, the mass of added catalyst was
varied to ensure the applicability of the model also at
 Ind. Eng. Chem. Res., Vol. 39, No. 7, 2000 2609

Table 11. Parameters and Residual Errors of the Different Kinetic Models Used To Fit the Experimental Data with
Amberlyst 15 as the Catalyst
mean relative k01 EA,1 k-10 EA,-1
model error (%) (mol‚g-1‚s-1) (kJ‚mol-1) (mol‚ g-1‚s-1) (kJ‚mol-1)
pseudohomogeneous, 14.6 1.648 × 104 47.98 1.161 × 105 58.60
ideal liquid phase
pseudohomogeneous, 13.9 2.961 × 104 49.19 1.348 × 106 69.23
activities by UNIQUAC
Song’s model with original parameters, 10.4 3.985 × 106 52.28 use Ka given by Song et al.
activities by UNIQUAC
Song’s model, parameters fitted, 6.7 5.312 × 107 58.25 use Ka from this work
activities by UNIQUAC
eq 16 5.4 8.497 × 106 60.47 6.127 × 105 63.73

Figure 7. Rate constant of the esterification reaction k1 (b) at
323 K versus catalyst mass for experiments 7 and 27-31. Only k1
has been fitted for each run using the known chemical equilibrium
constant from Figure 1. The line represents the result of the overall
fit (compare Table 11).
Figure 9. Experimental values (O) for the acetic acid concentra-
tion and predicted course by the pseudohomogeneous model (eq
10, dashed lines, activity coefficients by UNIQUAC) and eq 16
(solid lines). Five runs (experiments 25 and 38-41) of the
heterogeneously catalyzed hydrolysis reaction with varying initial
reactant ratios are shown.

Table 12. Standard Enthalpies and Standard Gibbs

Energies of Reaction Obtained from the Kinetic
Parameters
kinetic model ∆h°r (kJ‚mol-1) ∆g°r (kJ‚mol-1)
pseudohomogeneous, -20.04 -10.57
activities by UNIQUAC
eq 16 -3.26 -8.37

homogeneous model. Both models use the same number

Figure 8. Experimental values (O) for the acetic acid concentra-
tion and predicted course by the pseudohomogeneous model (eq
10, dashed lines, activity coefficients by UNIQUAC) and eq 16
(solid lines). Seven runs (experiments 7 and 32-37) of the
heterogeneously catalyzed esterification with varying initial re-
actant ratios are shown.
high catalyst concentrations. It can be seen from Figure
7 that the assumption of a linear dependence of the rate
on the mass of catalyst is valid.
To demonstrate the validity of the model in the
diluted concentration range, the concentration courses
of experiments with varying initial molar ratios are
presented in Figure 8 for the esterification reaction and
in Figure 9 for the hydrolysis reaction. Also included is
the concentration course calculated from eq 16 and from
the pseudohomogeneous model. Obviously, eq 16 de-
scribes the kinetic data better than the simple pseudo-
of adjustable parameters for the fit, that is, k01, k-1
0
,
EA,1, and EA,-1 because the adsorption constants Ki have
been fitted independently to binary adsorption data. An
attempt of fitting the four kinetic parameters and the
four adsorption constants to kinetic data only resulted
in very small residual errors, but also in a very poor
extrapolability of the model to experimental data not
included in the fitting procedure.
The consistency between kinetics and chemical equi-
librium can be checked by calculating Ka from the
following equation,
aMeOAcaH2O k1
Ka ) ) (18)
aHOAcaMeOH k-1
for the pseudohomogeneous model with activities and
from eq 17 for the adsorption-based model. If Ka is
substituted by eq 3, the heats of formation can be
calculated from the kinetic parameters in Table 11. The
results are shown in Table 12. A comparison with Song’s
model is not possible because it needs the adsorption
constant of methyl acetate as an additional parameter
and, furthermore, the chemical equilibrium constant Ka
2610 Ind. Eng. Chem. Res., Vol. 39, No. 7, 2000
is included in the kinetic equation. In a comparison with
Table 5, one can see how obvious it is that the value for
∆h°r obtained from the adsorption-based kinetics shows
better agreement between kinetics and thermodynamics
than that of the pseudohomogeneous model. The values
for ∆g°r agree well for both kinetic models, meaning
that the magnitude of Ka at 298.15 K, which depends
only on ∆g°r, is represented well by both kinetic mod-
els, but the temperature dependence of Ka, which is
governed by ∆h°r, deviates somewhat from the value
obtained from thermodynamic information.
Conclusions
The design of reactive distillation columns requires
reliable kinetic data besides other information, like
phase equilibrium data, chemical equilibrium data,
transport property data, or the various pure component
properties. In this work, kinetic expressions for the
methyl acetate system are presented with parameters
fitted to a fairly large database covering both the
esterification and the hydrolysis reaction. For the
homogeneous reaction, the kinetic fit is improved by
using activities instead of mole fractions. The reaction
follows a rate expression that suggests catalysis by
molecular acetic acid instead of by solvated protons. This
is consistent with the results from Williamson and
Hinshelwood.23 The magnitude of the homogeneous
reaction rate shows that this reaction can be neglected
in reactive distillation columns, unless very high liquid
holdups are present.
For the heterogeneously catalyzed reaction, the use
of activities alone in a pseudohomogeneous model
improves the fit only slightly. Taking the liquid-phase
nonideality into account is obviously not sufficient to
describe the heterogeneous kinetics. The interaction
between the solid catalyst and the reactants has to be
considered in the model. Despite the fact that a precise
and thermodynamically consistent treatment of systems
involving swelling ion-exchange resins is not available,
a good fit of the kinetic experiments can be obtained
using an adsorption-based model. Following the concept
of Song et al.,13 independent adsorption experiments
were used to determine the adsorption equilibrium
constants which are then incorporated into the kinetic
expression. Including adsorption information leads to
a much better description of the kinetic results. Using
an adsorption expression based on adsorbed mass
instead of adsorbed amount results in further improve-
ment of the fitting result. The resulting model (eq 16)
can easily be incorporated into commercial simulators.
Additionally, this model provides better agreement
between kinetics and thermodynamics (chemical equi-
librium) than the pseudohomogeneous model.
Acknowledgment
We are grateful for the generous financial support
provided by Sulzer Chemtech Ltd. (Winterthur, Swit-
zerland) and the “Fonds der Chemischen Industrie” by
granting a scholarship to T.P. We also would like to
thank Robert Geisler, Peter Kunze, and Sven Steini-
geweg for performing some of the kinetic experiments.
Supporting Information Available: Tables of
experimental data for the chemical equilibrium compo-
sition, the different kinetic runs, and the results of the
adsorption experiments (24 pages) is available free of
charge via the Internet at http://pubs.acs.org.
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Revised manuscript received April 6, 2000
Accepted April 11, 2000
IE000063Q