Ind. Eng. Chem. Res.

2006, 45, 1869-1874 1869

Reaction Kinetics of the Homogeneously Catalyzed Esterification of 1-Butanol

with Acetic Acid in a Wide Range of Initial Compositions
Sascha Grob and Hans Hasse*
Institute of Thermodynamics and Thermal Process Engineering, UniVersity of Stuttgart,
D-70550 Stuttgart, Germany

The reaction kinetics of the reversible liquid-phase esterification of acetic acid with 1-butanol was investigated
at temperatures between 353.15 and 393.15 K using sulfuric acid as catalyst. The main goal of the work was
to study the influence of the initial composition on the reaction rate constants of that industrially important
reaction. It is shown that the reaction rate is faster in butyl acetate-rich mixtures than in water-rich mixtures.
The experiments were carried out in a batch reactor using quantitative online 1H NMR spectroscopy for
analysis. For describing the results, a second-order reaction kinetic model in activities or fugacities, respectively,
is used, which is consistent with a recently developed thermodynamic model of phase and reaction equilibrium.
Different thermodynamic models are compared: NRTL, UNIQUAC, and PC-SAFT. All of them can
successfully correlate the kinetic data, but none allows a prediction of the concentration dependence of the
reaction rate constants. The results show that introducing activities of the reacting components alone is not
sufficient for predicting the concentration dependence of the reaction rate constants as the composition of the
reacting mixture has a strong influence on the activity of the catalyst itself.

Introduction Comprehensive experimental data on the reaction kinetics of

The design of reactive separation processes requires reliable
models which consistently describe not only phase and reaction
equilibrium but also reaction kinetics. Information on reaction
kinetics is often missing, but even if it is available, usually only
data for a single or only a few initial compositions are known.
While reaction rate constants determined from such experiments
may be sufficient for the design of standard reactors, this is
generally not the case for reactive separation processes, like
reactive distillation, where the reaction often takes place in a
large area of the composition space. In such applications, the
influence of the overall composition on the reaction rate is
important; see ref 1. However, systematic studies of that effect
are lacking. In particular, comprehensive experimental studies
that would allow an investigation of the modeling of that
influence are not available in the literature.
It is known that the use of activities in reaction equilibrium
modeling (i.e., activity based equilibrium constants Ka) allows
predicting the influence of the mixture composition on the
numbers of equilibrium constants expressed in terms of mole
fractions Kx; see ref 2. That approach can be extended to reaction
kinetic modeling. The key question is then the following: can
the influence of mixture composition on the reaction rate be
predicted by using activities instead of concentrations? The
activity based approach has the additional advantage that the
reaction kinetic model gives thermodynamically consistent
predictions of reaction equilibrium.
The present paper addresses these open questions. For the
study, a strongly nonideal test systemsthe esterification of acetic
acid (HAc) with 1-butanol (Bu) to 1-butyl acetate (BuAc) and
water (H2O)swas chosen:
HAc + Bu T BuAc + H2O (I)
The basic findings obtained here from the studies of that test
system are assumed to also hold for many other reactions.
* To whom correspondence should be addressed. Phone: +49-711-
685-6105. Fax: +49-711-685-6140. E-mail: hasse@itt.uni-stuttgart.de.
10.1021/ie050789s CCC: $33.50 © 2006 American Chemical Society
Published on Web 02/16/2006
the esterification (I) in the homogeneous liquid phase using
sulfuric acid (SAc) catalyst are reported. The focus is on the
dependence of reaction kinetics on the composition of the
mixture, but the study also includes experiments at different
temperatures and catalyst concentrations.
Activity and fugacity based approaches are tested for model-
ing the reaction kinetic data. The modeling work is based on a
recent study on consistent thermodynamic modeling phase and
reaction equilibria in the reactive system (I).2 As phase equilibria
in the studied system are always modeled with activities based
on mole fractions, that approach was also used by Grob and
Hasse2 for developing their thermodynamic consistent model
of the reaction equilibrium. It is adopted in the present paper
for modeling reaction kinetics. It was not in the scope of the
present work to study the well-known molarity (i.e., volume)
based approaches for reaction kinetic modeling. This would have
been either thermodynamically inconsistent (using the molarity
itself), or a very high experimental and theoretical effort would
have been necessary to develop a thermodynamically consistent
activity model based on molarities. The latter would, e.g., have
required using information on the composition dependence of
a mixture’s excess volume.
There is a comparatively large number of studies available
in the literature which report on the kinetics of reaction I. None
of these, however, were made with aims similar to those of the
present work, in which reaction I is merely used as a test case
for kinetic modeling studies. These, however, must be based
on comprehensive information of the reaction at various
conditions. Early work on reaction I was generally focused on
homogeneous reaction kinetics, e.g., the work of Leyes and
Othmer.3 Later, a number of studies were stimulated by
investigations of homogeneously catalyzed reactive distillation,
e.g., those of Hartig and Regner.4 More recently, work on
reaction I was often done on the background of studies on
heterogeneously catalyzed reactive distillation.5-14 Other mo-
tivations to study reaction I were interest in reactions in liquid
two phase systems,15 for online reaction monitoring,16 catalyst
1870 Ind. Eng. Chem. Res., Vol. 45, No. 6, 2006
Figure 1. Experimental setup for reaction monitoring by NMR spectroscopy
in a flow cell in stopped flow mode: (V1) sample inlet check valve; (NMR)
flow probe, thermostated (dotted lines); (V2 and V4) pressure relief
membrane valves; (V3) purge valve; (V5) manual pressure relief valve;
(V6) check valve; (V7) shut off valve; (V8) reducing valve; (He) helium
gas cylinder. The tubing used was the following: 1/16 in. PEEK poly-
(etheretherketone) or 1/8 in. transparent poly(tetrafluoroethylene) (PTFE)
for observation of meniscus.
studies17-20 or catalyst screening studies, and the correlation of
the results with quantitative structure-property relationships.21
Materials and Methods
a. Chemicals and Preparation of Samples. Acetic acid,
1-butanol, 1-butyl acetate, and sulfuric acid were p.a. (analytical
grade) grade (HAc 99.8% (acidmetric), Bu 99.8% (GC), BuAc
99.5% (GC), SAc 96%). Water was bidistilled. In preparing
the samples, the minimum amount of each reactive substance
was 5.0 g (weighing accuracy 0.001 g). The minimum amount
of sulfuric acid was 0.1 g.
b. Reaction Kinetics by Online 1H NMR Spectroscopy.
Online 1H NMR spectroscopy was chosen for reaction monitor-
ing as that method allows one to obtain accurate information
on sample composition in less than 10 s.22 An alternative to
that method would be gas chromatography (GC). Both methods
were recently used by Hasse and Grob2 for quantitative analysis
of the system studied here. It was shown in that work that both
methods yield data with comparable accuracy. However, a GC
run takes about 20 min; NMR spectroscopy is faster by 2 orders
of magnitude and the method of choice for studying reaction
kinetics.
The experiments were conducted in a 95 µL NMR flow cell
(Varian, Palo Alto, CA) which was used in a stop flow mode
as batch reactor and was filled with a syringe. As experiments
above the normal boiling point of the mixtures were also carried
out, the NMR flow cell was pressurized with helium to about
5 bar. The experimental setup is shown in Figure 1. The work
was carried out with a 400 MHz NMR spectrometer (Varian
Inova). The temperature was controlled with the air thermostat
unit of the NMR spectrometer; the temperature measurement
of the NMR spectrometer was calibrated prior to the experi-
ments. The overall uncertainty of the temperature is below
0.2 K.
Figure 2. Typical 1H NMR spectrum of a mixture of 1-butanol, acetic
acid, water, and 1-butyl acetate at 353 K.
Figure 2 shows a typical 1H NMR spectrum of a reacting
mixture of 1-butanol, acetic acid, 1-butyl acetate, and water.
The composition of a sample is calculated from the initial
composition and the signals D and d which are caused by
protons in 1-butyl acetate and 1-butanol, respectively. These
are the only two signals which are caused by protons in single
components. The area below these signals is directly propor-
tional to the number of corresponding molecules. As the
proportionality constant is the same for both signals, no
calibration is necessary. The signal of the OH groups shifts
strongly with varying composition of the mixture and may
overlap with one of the signals D or d, so that the corresponding
spectrum cannot be evaluated.
For the quantitative evaluation of the NMR spectra, it was
sufficient to use the standard Varian software for integrating
the signals as no overlaps occurred. The uncertainty of mole
fractions calculated from 1H NMR spectroscopic data in that
way is typically less than 5% (relative deviation). A more
detailed description of the experimental method and data
evaluation can be found elsewhere.22 Additional information is
also given by Grob and Hasse2 and in the Ph.D. dissertation of
Grob.23
Modeling
The reaction mechanism of the acid-catalyzed esterification
of an alcohol with a carbon acid is considered to consist of six
reaction steps.24 The first step is the protonation of the carbon
acid (here, acetic acid):
CH3COOH + H+ T CH3C(OH)2+ (II)
That step is relatively fast. Thus, it is considered to be always
in equilibrium.24 The second step is the reaction of the
protonated carbon acid with the alcohol (here, 1-butanol). This
reaction step is kinetically controlled. All subsequent reaction
steps are again very fast and are thus considered to be always
in equilibrium. Therefore, the second and all subsequent reaction
steps can be summarized into one kinetically controlled reaction
step:25
CH3C(OH)2+ + C4H9OH T CH3COOC4H9 + H2O + H+
(III)
The reaction equilibrium is modeled here using either activities
or fugacities so that the description is thermodynamically
consistent. To achieve consistency between the reaction equi-
librium model and the reaction kinetic model, the latter was
also formulated in activities or in fugacities, respectively.
 Ind. Eng. Chem. Res., Vol. 45, No. 6, 2006 1871

Applying a second-order kinetic approach in activities for

the pseudo-two-step reaction studied here yields the following
expression:

V 1 dnBuAc dxBuAc
ro ) ) )
n V dt dt

(
k oa (T)aH+ aBuaHAc -
1
a a
Ka(T) H2O BuAc)(1)

where ro is the overall reaction rate, V is the volume, n is the

total number of moles in the sample (n does not change due to
the reaction), ni is the number of moles of component i, xi is
the mole fraction of component i, t is the time, k oa is the
reaction rate coefficient based on activities, ai is the activity of
component i, and Ka is the reaction equilibrium constant based
on activities depending on the temperature T.
The product k oa (T)aH+ is called the reaction rate constant
here. It would be desirable that the reaction rate constants
determined from a fit to experimental data should depend only
on the temperature and the catalyst concentration but not on
the concentrations of the reacting components.
Analogously to eq 1, the following expression in fugacities
can be derived:

(
ro ) k of (T)fH+ fBufHAc -
1
f f
Kf(T) H2O BuAc ) (2)

In eq 2, k of is the reaction rate coefficient based on fugacities,

fi is the fugacity of component i, and Kf is the reaction
equilibrium constant based on fugacities. The reaction rate
coefficients k oa and k of are described by Arrhenius’ law using a
constant preexponential factor k o0 o0
a or k f , the universal gas
constant R, and the activation energy Eact:

k oa ) k o0 ( )
a exp -
Eact
RT
(3)

The activities and fugacities in the reacting mixture are

calculated from GE-models or equations of state, respectively.
In the present study, the GE-models NRTL26 and UNIQUAC27
and the PC-SAFT equation of state28 were used. The parameters
of these models as well as the reaction equilibrium constants
Ka and Kf were taken from a previous study on the reaction
equilibrium.2
Besides the activities or fugacities of the reacting components,
the activity or fugacity of the protons in the mixture has to be
specified; see eqs 1 and 2, respectively. As neither suitable Figure 3. Overview of the experimental program. The initial compositions
models nor equilibrium data for their parametrization is avail- of components i are plotted in transformed mole fractions xji for the
temperatures 353.15, 373.15, and 393.15 K. The mole fractions of the
able, an empirical expression was used for that term. The catalyst H2SO4 are marked as follows: (×) 0.5 mmol/mol; (+) 1.0 mmol/
approach is discussed below. mol; (2) 1.5 mmol/mol; (O) 2.0 mmol/mol.

which can be shown in a triangular diagram. The result of the

Experimental Reaction Kinetic Data
Figure 3 shows the initial compositions of the 42 reaction
kinetic experiments carried out in the present work. For the
representation, following a suggestion of Ung and Doherty,29
transformed composition coordinates are used. The transforma-
tion of the composition is based on the stoichiometry of reaction
I. The mole fractions of the educts, butanol, and acetic acid are
transformed by adding the smaller of the mole fractions of the
products, butyl acetate, and water. Analogously, the mole
fractions of the products are transformed by subtracting the
lower of the mole fractions of the products. Thus, the trans-
formed mole fraction of one of the products is zero, i.e., the
quaternary mixture is transformed to a pseudoternary mixture
transformation can be interpreted as concentrations in a mixture
that would be obtained if all products were reconverted to educts.
In Figure 3, both resulting triangular diagrams (the remaining
product is either butyl acetate or water) are joined at the common
axis of the educts butanol and acetic acid. Hence, the four pure
reacting components are found in the corners of the diagram.
The diagonal between 1-butanol and acetic acid represents
mixtures of these educts; the equimolar mixture is found in the
middle of the diagram. In the lower triangle, there is also the
product 1-butyl acetate in the initial mixture, whereas, in the
upper triangle, the third component in the feed mixture is not
1-butyl acetate but water. For a more detailed explanation, see
Grob and Hasse.2 As can be seen from Figure 3, the present
1872 Ind. Eng. Chem. Res., Vol. 45, No. 6, 2006

Table 1. Initial Compositions, Catalyst Concentrations, and

Temperatures of the Reaction Kinetic Experiments
xH2O xBuAc xBu xH2SO4
(mol/mol) (mol/mol) (mol/mol) (× 10-3 mol/mol)
T ) 353.15 K
0.1940 0.0040 0.1860 0.500
0.0042 0.6242 0.1859 0.497
0.0077 0.1977 0.1823 0.500
0.0109 0.1109 0.0891 1.000
0.0248 0.1248 0.4251 1.000
0.0026 0.4526 0.4474 0.997
0.0000 0.7996 0.1002 1.005
0.0076 0.4576 0.0924 0.994
0.0132 0.3464 0.3202 1.000
0.0043 0.6242 0.1858 0.994
0.0128 0.2032 0.6068 1.002
0.0172 0.2072 0.1728 1.001
0.1108 0.0104 0.0895 0.999 Figure 4. Influence of temperature on reaction kinetics. Experiments I
0.2035 0.013 0.1769 0.997 (]), II (4), and III (0) have practically the same initial composition and
0.4524 0.0021 0.0978 0.997 catalyst concentration but were carried out at different temperatures. The
0.0244 0.1245 0.0756 0.940 assignment of experiments to lines in Table 1 is as follows (Exp/Line):
0.1161 0.0159 0.4340 0.998 I/14, II/25, III/38.
0.0230 0.2234 0.3768 1.107
0.0071 0.627 0.1829 1.503
0.0228 0.2128 0.1672 1.496
0.0117 0.3105 0.0922 1.995
0.0190 0.6439 0.0811 2.056
0.0529 0.153 0.3971 2.177
T ) 373.15 K
0.0287 0.2187 0.1614 1.001
0.2151 0.0247 0.1652 0.997
0.0200 0.1200 0.0800 1.000
0.0203 0.1203 0.7796 1.000
0.0479 0.3810 0.2851 0.998
0.0039 0.8039 0.0961 1.003
0.1396 0.0367 0.3971 1.028
0.0398 0.3398 0.0603 2.004
0.1457 0.0458 0.0544 2.002
T ) 393.15 K
0.0329 0.1329 0.0671 1.000
0.0245 0.2145 0.1655 1.001
0.0168 0.1169 0.7830 1.000 Figure 5. Influence of sulfuric acid concentration on reaction kinetics.
0.0220 0.3553 0.3113 1.000 Experiments I (]), II (4), and III (0) have practically the same initial
0.1930 0.0928 0.3571 0.998 composition and were all carried out at 353.15 K, but different catalyst
0.2227 0.0322 0.1577 0.997 concentrations were used. The assignment of experiments to lines in Table
0.0441 0.3441 0.0559 2.004 1 is as follows (Exp/Line): I/2, II/10, III/19.
0.1637 0.0633 0.0367 2.001
0.4741 0.0242 0.0758 2.000
0.3808 0.0467 0.2863 2.000

study covers a large part of the composition space; only the

part of high water concentrations where a liquid-liquid phase
split occurs is excluded. Figure 3 was calculated using the initial
compositions, but due to the nature of the transformation, also
the complete trajectory of the reaction progress is represented
by the same point.
The initial compositions, catalyst concentrations, and the
temperatures of the experiments are summarized in Table 1.
The extensive numerical data collected in the kinetic runs are
available in the Ph.D. dissertation of Grob23 and are therefore
not reported here.
Figures 4 and 5 show examples for the influence of temper- Figure 6. Influence of initial composition of reaction kinetics. Experiments
ature and catalyst concentration on the reaction kinetics. The I (4) and II (]) were carried out at 353.15 K with the same catalyst
initial concentrations in the sets of experiments shown in Figures concentration. They differ only in the water/1-butyl acetate ratio in the initial
4 and 5, respectively, are practically the same. Differences in mixture (exp I 1-butyl acetate-rich; exp II water-rich). The assignment of
experiments to lines in Table 1 is as follows (Exp/Line): I/8, II/15.
the numerical values of the concentrations of the first data point
(cf. Table 1) stem from the fact that the reaction extent in the example is given in Figure 6 which shows two experiments at
period between the mixing and the acquisition of the first data the same temperature and catalyst concentration, with identical
point is different for different conditions. Besides the well- initial concentrations of acetic acid and 1-butanol, but different
known strong influence of these parameters on reaction kinetics, ratios of water and 1-butyl acetate, respectively. The reaction
there is also a smaller, but systematic and clearly discernible, obviously proceeds slower in the water-rich mixture than in the
influence of the initial composition on the reaction kinetics. An 1-butyl acetate-rich mixture. The reason for this behavior might
 Ind. Eng. Chem. Res., Vol. 45, No. 6, 2006 1873

Table 2. Model Parameters (cf. Equations 4-6)

model p1 p2 p3 p4 p5
NRTL 3.993 × -5007.0 8.490 ×
107 1.016 10- 4
116.6
UNIQUAC 3.989 × 107 -5012.0 8.502 × 10- 3 0.986 126.6
PC-SAFT 2.999 × 1012 -7477.0 3.000 × 10- 4 82.17 -1598.0

be that water hinders 1-butanol from approaching the protonated

acetic acid.

Modeling Results
Reaction kinetics is modeled with the activity-based approach
(eq 1, NRTL, UNIQUAC) or the fugacity-based approach (eq
2, PC-SAFT), respectively. The reaction rate constant k oa in eq
1 is described by eq 3 for which the following form was used
here:
Figure 7. Typical result of a comparison of the three reaction kinetic models
k oa ) p1 exp(p2/(T/K)) (4) to experimental results. The plot shows the reaction progress ∆ξ (eq 7) as
a function of time: (O) experimental (line 12 in Table 1); ()) NRTL; (---)
UNIQUAC; (s) PC-SAFT.
The same functional form was used for the correlation of k of .
Modeling the influence of the composition of the reacting
mixture on the reaction rate constants is a challenge. As
discussed below in more detail, the results obtained in the
present work show that it is not appropriate to simply use the
proton mole fraction for describing the influence of the catalyst
on the reaction kinetics. The activity of the protons is influenced
by a number of parameters, namely, the water concentration
plays an important role. As developing an appropriate physi-
cochemical model for this was out of the scope of the present
paper, it was decided to use an empirical approach. The
following expression for aH+ was the best compromise between
accuracy and simplicity:

( )( )
xH2O xH2SO4 R
xHAc
a H+ ) 1 - + p3 (5)
mol/mol mol/mol mol/mol
Figure 8. Comparison of different models in describing the influence of

( )
p5
R ) p4 exp
T/K
All statements made above for proton activities hold also for
fugacities. For describing the fugacity of the protons fH+ in eq
2, expressions analogous to es 5 and 6 were used.
For each of the three thermodynamic models (NRTL,
UNIQUAC, PC-SAFT), the parameters p1 to p5 were fitted to
the whole data set (global fit to 42 experiments, many hundred
data points). The overall sum of the relative deviations between
the experimental and calculated numbers of the reaction progress
∆ξ was minimized, where
xBuAc(t) - xBuAc(t ) 0)
∆ξ(t) )
xBuAc(t f ∞) - xBuAc(t ) 0)
The results for the parameters p1 to p5 obtained in that global
fit for the three models are presented in Table 2. All models
allow correlations of similar quality. The average relative
deviation between the experimental and calculated numbers for
the reaction progress is about 4% for all models. As an example,
Figure 7 shows the reaction progress of a typical experiment
as a function of time. The results from the correlations with the
three models are compared to the experimental data. There are
only small differences between the correlations with the three
different models. Note that the correlation is a global correlation
that holds for all reaction kinetic runs and not only for the
individual run shown in Figure 7. For a few experiments, larger
systematic deviations between the correlations and the experi-
the initial composition on reaction kinetics. The plot shows the reaction
(6) progress ∆ξ (eq 7) as a function of time. Experiments I (4) and II (])
differ only in the water/1-butyl acetate ratio in the initial mixture (exp I
1-butyl acetate-rich; exp II water-rich; the experiments are the same as those
shown in Figure 6). The dashed lines correspond to the simplified model,
and the full lines, to the full model. Only the full model predicts the
decreasing reaction rate with increasing water concentration.
mental data were observed. Also in these cases, there is no
distinct advantage for one of the models.
One can criticize the complicated form of eq 5 that was
chosen for the global fit of the entire data set. We only discuss
one alternative here. The most straightforward and simplest
assumption that could replace the expression for aH+ in eq 5 is:
aH+ ) xH+. The reaction kinetic model based on that assumption
will be called the simplified model in the following. Figure 8
(7)
shows, using NRTL as an example, that the simplified model
does not work and yields qualitatively wrong results, despite
the fact that activities are still used for describing the reactive
components. The two experiments shown in Figure 8 are the
same as those already shown in Figure 6, but now, the results
are presented in terms of the reaction progress. The experiments
differ practically only in the water/1-butyl acetate ratio of the
initial mixture (experiment I 1-butyl acetate-rich; experiment
II water-rich). The simplified model erroneously predicts that
the reaction in the water-rich mixture should be faster, while
the experiments show that it is the other way around. In contrast,
the model based on the correlation of eq 5 reasonably, though
not perfectly, describes the experiments. (Note that it is an
incident that prediction of experiment II with the simplified
model perfectly fits the experimental data for experiment I).
1874 Ind. Eng. Chem. Res., Vol. 45, No. 6, 2006
The findings discussed above show that introducing activities
of the reacting components alone is not sufficient for predicting
the concentration dependence of the reaction rate constants. The
composition of the reacting mixture has a strong influence on
the activity of the catalyst itself. Unfortunately, at present, this
effect can only be accounted for empirically in engineering
reaction kinetic models.
Conclusions
On the basis of a comprehensive experimental investigation
of the esterification of acetic acid with 1-butanol with 1H NMR
spectroscopy, thermodynamically consistent reaction kinetic
models were developed and tested. A second-order approach
in activities or fugacities, respectively, is used. Three thermo-
dynamic models are compared: NRTL, UNIQUAC, and PC-
SAFT. All three models yield similar results in describing the
reaction kinetics. The study shows that it is necessary to take
into account the influence of the mixture composition on the
activity of the catalyst. The resulting reaction kinetic models
compare favorably to the experimental data.
Acknowledgment
Thanks are due to H. H. Fischer, Y.-K. Kim, and M. Maiwald,
University of Stuttgart, who supported the NMR experiments
and to G. Sadowski and F. Tumakaka, University of Dortmund,
for supplying the PC-SAFT source code. Financial support of
Deutsche Forschungsgemeinschaft is gratefully acknowledged.
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ReceiVed for reView July 4, 2005
ReVised manuscript receiVed December 15, 2005
Accepted December 19, 2005
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