Development of Kinetic

Models for Acid-Catalyzed

Methyl Acetate Formation
Reaction: Effect of Catalyst
Concentration and Water
Inhibition
B. GANESH, K. YAMUNA RANI, B. SATYAVATHI, CH. VENKATESWARLU
Chemical Engineering Sciences, Indian Institute of Chemical Technology, Hyderabad 500 007, India
Received 24 September 2010; revised 19 January 2011; accepted 22 January 2011
DOI 10.1002/kin.20555
Published online 31 March 2011 in Wiley Online Library (wileyonlinelibrary.com).

ABSTRACT: The reaction kinetics of reversible liquid-phase esterification of acetic acid with
methanol is investigated in the temperature range 26–50◦ C using sulfuric acid catalyst. The main
goal of this work is to study the effect of catalyst concentration and sensitivity to the presence of
water on the rate expression of this industrially important reaction. Experiments are conducted
in an isothermal batch reactor and a second-order kinetic model is used to correlate the
experimental data, which are found to fit well with the assumed kinetic model in terms of the
concentrations of reactants and products. Furthermore, an activity-based kinetic model is also
developed employing the UNIQUAC (universal quasi-chemical equation) model to compute
the activities. It is observed that the rate constant is influenced by the concentration of catalyst,
and the reaction rate increased with an increase in the catalyst concentration. It is also observed
that the catalyst activity is slightly inhibited by the water present in the reaction mixture. The
performance of the proposed models is compared with that of other models reported in the
literature, and it is found that the proposed models outperformed all the other models reported
in the literature.  C 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 263–277, 2011

INTRODUCTION ticizers, and medicinal and surface-active agents. It is

Methyl acetate is widely used in various industrial
products including fragrances, flavors, solvents, plas-
Correspondence to: K. Yamuna Rani; e-mail: kyrani@iict.res.in,
k y rani@yahoo.com.
Contract grant sponsor: DST, New Delhi, India.
c 2011 Wiley Periodicals, Inc.
produced via esterification of methanol with acetic acid
according to the following scheme:
k1
CH3 COOH + CH3 OH ↔ CH3 COOCH3 + H2 O
k−1
The reaction is a reversible homogeneous liquid-phase
process, where the limiting conversion of the reactants
264 GANESH ET AL.
is determined by equilibrium. The reaction rate is very
slow; hence addition of a catalyst is necessary to in-
crease the rate of reaction.
The kinetics of the esterification reaction between
acetic acid and methanol was investigated as early as
1934 by Rolfe and Hinsshelwood [1], who based their
theory on molecular statistics of the reaction in al-
coholic and nonhydroxylic media by considering hy-
drochloric acid as the catalyst. Hilton and Smith [2]
summarized that the kinetics of the catalyzed ester-
ification reaction of normal aliphatic acid in methyl
alcohol is influenced by the length of carbon chain
while considering different buffer solutions such as
anisol and ammonium acetate. The kinetic model for
this esterification reaction using a homogeneous hy-
drogen iodide catalyst has been reported by Ronnback
et al. [3], where it is also stated that the rate-initiating
step in the reaction mechanism is the protonation of
carboxylic acid. Popken and Gmehling [4] investi-
gated the reaction kinetics and chemical equilibrium of
homogeneously and heterogeneously catalyzed acetic
acid esterification with methanol and methyl acetate
hydrolysis and developed a rate expression for non-
catalytic homogeneous reaction that suggests catalysis
by molecular acetic acid instead of solvated protons
and also indicates that the noncatalytic reaction is ex-
tremely slow and takes days to reach equilibrium.
Sulfuric acid has been reported as a preferred cat-
alyst for this esterification reaction due to its greater
density of acid sites per gram [5] and also because it is
found to be more active than some heterogeneous cata-
lysts. Process intensification by reactive distillation has
been adopted for many industrially important chemi-
cals including methyl acetate. Investigations have been
carried out by Agreda et al. [6], who proposed a rate
expression for this reaction using sulfuric acid (homo-
geneous) catalyst while carrying out the reaction in a
reactive distillation unit. The proposed rate expression
incorporates nonlinear dependence on the catalyst con-
centration; however, kinetic parameters have not been
reported. Engell and Fernholz [7] and Kreul et al. [8]
have modified the model proposed by Agreda et al. [6]
for application using a heterogeneous sulfonic acid ion
exchange resin as the catalyst. More recently, Liu et al.
[9] developed a rate expression for this reaction us-
ing homogeneous sulfuric acid catalyst by considering
linear dependence of the catalyst concentration on the
reaction kinetics, and Elgue et al. [10] have proposed
a similar dependence and applied it for intensification
of ester production in a continuous reactor.
Another important issue that needs to be addressed
while describing the kinetics for this esterification reac-
tion is the effect of water produced during the reaction.
Studies by Aafaqi et al. [11] and Kusdiana and Saka
[12] on other esterification and trans-esterification re-
actions reveal that the presence of water deactivates the
catalyst activity, which decreases the reaction rate. Liu
et al. [9] investigated the impact of water on the liquid-
phase sulfuric acid-catalyzed esterification of acetic
acid with methanol, by adding water initially to ap-
proximate different levels of conversion. The catalytic
activity of sulfuric acid has been found to be strongly
inhibited by water; the catalyst lost its activity up to
90% as the amount of water increased. Liu et al. [9]
reported that the diminished catalytic activity observed
as the concentration of water increases is likely to be
a consequence of acid strength decline due to strong
solvation of protons by water molecules.
Although a large number of researchers have stud-
ied the esterification reaction, some uncertainties still
appear with regard to the kinetic models reported. The
present investigation aims to develop a kinetic model
of the esterification reaction in a homogeneous liquid
phase using sulfuric acid as the catalyst by incorporat-
ing the effect of the catalyst concentration and the effect
of water formation during the reaction on the reaction
kinetics by carrying out experimental studies at differ-
ent temperatures and catalyst concentrations without
adding water initially. Experimental studies are con-
ducted in an isothermal batch reactor at atmospheric
pressure. Kinetic models, based the concentration and
activity, are developed, and the model predictions are
compared with the experimental data. A comparison
of different kinetic models from the literature with the
newly developed models is also presented.
EXPERIMENTAL
Materials
Methyl acetate (purity >99.436%), methanol (purity
>99.811%), acetic acid (purity >99.746), and sulfu-
ric acid (purity >98%) were purchased from SD Fine
Chemicals Ltd. (Mumbai, India) and used as such.
Apparatus
The experiments to study the effect of the temperature
and catalyst concentration on the acid-catalyzed ester-
ification of acetic acid with methanol are performed
in an isothermal batch reactor. A pictorial representa-
tion of the experimental setup is shown in Fig. 1. The
reactor is a 1-L glass-jacketed vessel equipped with
a digital overhead stirrer (a direct controlled model)
with a motor rating of 83/75 W, maximum torque of
85 N-cm, and a speed range of 200–3000 rpm. The im-
peller used is a propeller made of Teflon. The dimen-
sions of the impeller are 5-cm diameter, blade length
International Journal of Chemical Kinetics DOI 10.1002/kin
 KINETIC MODELS FOR ACID-CATALYZED METHYL ACETATE FORMATION REACTION
Figure 1 Schematic representation of the reactor assembly (R, jacketed reactor; TI, thermo well and temperature indicator;
SW, sample withdrawal provision; C, condenser; S, stirrer; TS, thermostat for coolant circulation; TIC, temperature indicator
and controller).
1.25 cm, blade width 1 cm, and 0.1-cm shaft diameter.
The agitator is located at 3.17 cm from the bottom of
the vessel (one third of the reactor diameter). The reac-
tor assembly is provided with a four-necked glass lid
with provision for the liquid-phase temperature mea-
surement in the reactor and periodic withdrawal of liq-
uid samples during the course of the reaction. To one
of the outlets, a condenser is connected wherein cold
water is circulated to minimize losses. Temperature is
measured using a Chromel Alumel type thermocou-
ple. A Polyscience refrigerating and heating circulator
thermostat model 9702 with a digital temperature con-
troller is used to maintain the temperature (±0.01◦ C
accuracy) in the jacketed reactor.
Procedure
In a typical experiment, equimolar quantities of
methanol (224 g) and acetic acid (420 g) are mixed
and taken in the reactor. The desired amount of sulfu-
ric acid (as a percentage with respect to the weight of
acetic acid) is added to initiate the reaction. Samples
are drawn after the temperature is stabilized at close
intervals of time and are analyzed for the acetic acid
concentration. The reaction is continued for 4 h. Af-
ter the reaction is completed, the reactor contents are
cooled, weighed, and analyzed.
The first set of experiments was performed at dif-
ferent temperatures 26, 40, and 50◦ C, with 2% catalyst
concentration to determine the kinetic parameters. The
next set of experiments was conducted at 40◦ C with
International Journal of Chemical Kinetics DOI 10.1002/kin
265
varying catalyst concentrations of 1%, 2%, and 5% to
find the effect of the catalyst concentration on the ki-
netics. The final set of experiments was conducted at
different temperatures with different catalyst concen-
trations (50◦ C: 1%, 40◦ C: 5% and 35◦ C: 4%) and is
used to validate the kinetic models developed and to
compare their performance with the literature-reported
models. During the last experiment (35◦ C: 4%), the ini-
tial reaction mixture consists of water also in addition
to methanol and acetic acid so that it can serve to com-
pare with the model incorporating inhibition effect of
water through initial addition of water.
Analysis
The acetic acid concentration was determined by titra-
tion with standard solution of NaOH using phenolph-
thalein as the indicator.
RESULTS AND DISCUSSION
Prior to the development of a new model, the mod-
els reported in the literature were explored to check
whether the experimental data generated in the present
study match with any of the model predictions. How-
ever, it is found that none of the reported models is
found to represent the kinetics of this reaction with suf-
ficient accuracy. Therefore, we attempted to develop a
new model based on the experimental data generated.
A comparison of the performance of other models is
reported at the end of this section.
266 GANESH ET AL.
Effect of Different Factors on Reaction
Kinetics
To develop a kinetic model of the present reacting sys-
tem, a second-order kinetic approach is adopted and
the kinetic model is obtained for a fixed catalyst con-
centration in a manner similar to that employed for a
noncatalytic elementary reaction. Later, the approach
is extended to develop the rate equation for the cat-
alyzed reaction by considering factors including ef-
fects of temperature, catalyst concentration, and water
sensitivity. Each of these effects is discussed in detail
below.
Reaction Temperature
The experimental results obtained at different tempera-
tures with the fixed catalyst concentration are depicted
in Fig. 2. As is evident from the plot, conversion of
acetic acid increases almost linearly at all tempera-
tures with an increase in the temperature initially and
is asymptotic later.
Catalyst Concentration
Experiments with varying concentrations of catalyst
show that the increase in the catalyst concentration en-
hances the reaction rate. The experimental results ob-
tained with different catalyst concentrations at a fixed
temperature are shown in Fig. 3. As is evident from
the plot that an increase in the catalyst concentration
increased the conversion of acetic acid and the equi-
librium conversion is attained earlier. The amount of
Figure 2 Effect of temperature on reaction kinetics at 2% catalyst concentration.
catalyst influences the reaction rate because more H+
ions are available when the amount of catalyst in the
reaction mixture increases.
Water Sensitivity
It is observed from the results that the formation of
water as a by-product inhibits the catalytic activity.
Similar results have been observed by Liu et al. [9] for
the acid-catalyzed esterification reaction with varying
amounts of water added initially to the reaction mix-
ture.
Development of the Concentration-Based
Kinetic Model
From thermochemistry, the equilibrium conversion ob-
tained is 69% at 25◦ C for the conventional methyl ac-
etate process as per the following reaction:
k1
A + B↔C + D
k−1
The reaction is carried out at 1:1 molar ratio of acetic
acid to methanol; hence a second-order elementary ki-
netic expression is assumed. The reaction rate expres-
sion (−rA ) of the homogeneous reaction is
−rA = (k1 CA CB − k−1 CC CD ) (1)
where CA is the acetic acid concentration, CB is the
methanol concentration, CC is the methyl acetate con-
centration, and CD is the water concentration. k1 is the
International Journal of Chemical Kinetics DOI 10.1002/kin
 KINETIC MODELS FOR ACID-CATALYZED METHYL ACETATE FORMATION REACTION
Figure 3 Effect of catalyst concentration on reaction kinetics at 40◦ C.
rate constant of the forward reaction, and k−1 the rate
constant of the backward reaction. It is also assumed
that water and ester are not present at the beginning of
the reaction. The etherification of alcohol is negligible,
and the reaction volume during the reaction is consid-
ered to be constant. The temperature dependency of
both the rate constants is expressed by the Arrhenius
equation.
k = k 0 exp(−Ea /RT ) (2)
where k 0 is the preexponential factor, Ea is the ac-
tivation energy, R is the gas constant, and T is the
temperature.
The standard procedure for second-order kinetic
model development [13] for elementary reactions is
followed to determine the specific reaction rates k1
and k−1 at each temperature and catalyst concentra-
tion based on the first two sets of experiments. The
procedure followed to determine the specific reac-
tion rate k1 is as follows: (a) plot ln((XAe − (2XAe −
1)XA )/(XAe − XA )) versus time, where XAe is the
equilibrium conversion; (b) find the slope of the straight
line obtained; and (c) calculate k1 according to
   
1 weight of acetic acid in the initial reaction mixture.
k1 = Slope 2 − 1 CAo .
XAe
Calculation of k−1 is straightforward using equi-
librium constant and k1 . The influence of temperature
on the specific reaction rate is determined by fitting
International Journal of Chemical Kinetics DOI 10.1002/kin
267
k1 and k−1 to the Arrhenius equation. The activation
energies for both the forward and backward reactions
are obtained from Figs. 4 and 5 as 63,062 and 63,012
J/mol, respectively. The activation energy for forward
and backward reactions are nearly equal, and therefore
the equilibrium constant (Ke ) for this reaction is nearly
temperature independent (similar to the approach con-
sidered earlier by Agreda [6]) and is approximately
equal to 5 for equimolar quantities of initial reactants.
To quantify the effect of the catalyst concentration
on the reaction kinetics, the preexponential factor at
each of the three catalyst concentrations considered
in the second set of experiments for a fixed tempera-
ture is determined after eliminating the temperature-
dependent term by using the activation energy deter-
mined earlier. The preexponential factor (k10 ) is plotted
as a function of the catalyst concentration as shown
in Fig. 6. It is found that this dependency can be ap-
proximated as a quadratic function passing through the
origin, and the equation is expressed as
k10 = −9.405338 × 106 (wc )2 + 1.344269 × 108 (wc )
(3)
where wc is the weight% of catalyst with respect to the
The model incorporating the temperature and cat-
alyst concentration dependence is employed to pre-
dict the conversion of acetic acid for both the first
and second sets of experiments mentioned above, and
the predicted conversion profiles are plotted along
268 GANESH ET AL.

Figure 4 Logarithm of the forward reaction rate constant (k1 ) for esterification of acetic acid with methanol as a function of
reciprocal of temperature.

Figure 5 Logarithm of the backward reaction rate constant (k−1 ) for esterification of acetic acid with methanol as a function
of reciprocal of temperature.

with the experimental data in Figs. 7 and 8, respec-
tively. The figures clearly indicate that there is a
considerable deviation between the predicted and ex-
perimental values during the initial region, whereas in
the later part, the match is reasonably good. The mis-
match can be attributed to the inhibition effect of water
formed during the reaction until equilibrium is reached.
Furthermore, it can be observed from Fig. 7 that as the
temperature is increasing, the mismatch is decreas-
ing, indicating an inverse dependence. Similarly in
Fig. 8, as the catalyst concentration is increasing, the
mismatch is found to decrease. As observed earlier,
with an increase in the catalyst concentration, the reac-
tion rate increases, indicating formation of more water
(being one of the products) at an early stage. There-
fore, a decrease in mismatch with an increase in the
catalyst concentration implies that although the pres-
ence of water inhibits the reaction, as the water con-
centration increases its impact on the reaction rate de-
creases, further implying an inverse dependence on the
water concentration. Keeping in view these two ef-
fects, a correction term is included in the reaction rate

International Journal of Chemical Kinetics DOI 10.1002/kin

 KINETIC MODELS FOR ACID-CATALYZED METHYL ACETATE FORMATION REACTION 269

Figure 6 Dependence of preexponential factor on the catalyst concentration.

Figure 7 Comparison of experimental profiles of acetic acid conversion at different temperatures with predictions of the
concentration-based kinetic model without water effect.

expression including temperature dependence in the sidered. The conversion profiles are predicted using the
form of specific reaction rate and water concentration proposed rate expression for both sets of experiments
dependence explicitly. After exploring different forms and are plotted along with the experimental data in
of dependence, the following expression is found to Fig. 9. This figure clearly indicates that the proposed
match the experimental results accurately: rate expression is able to represent the reaction kinetics
accurately.
  
k1 CC CD
−rA = √ CA CB −
(12.5k1 + CD ) Ke Development of the Activity-Based
(4) Kinetic Model
Equation (4) together with Eqs. (2) and (3) constitute When modeling the reaction for a liquid-phase sys-
the reaction kinetics for the esterification reaction con- tem where the mixture is nonideal, a correction must

International Journal of Chemical Kinetics DOI 10.1002/kin

270 GANESH ET AL.

Figure 8 Comparison of experimental profiles of acetic acid conversion at 40◦ C at different catalyst concentrations with
predictions of the concentration-based kinetic model without water effect.

be made to the concentration to indicate the departure
from ideal case. Nonideality exists from the difference
in the interaction between the molecules as well as
size and shape difference in the molecules participat-
ing in the liquid mixture. Usually phase models such as
the UNIFAC (universal functional activity coefficient),
UNIQUAC (universal quasi-chemical equation), and
NRTL (nonrandom two liquid) phase equilibrium mod-
els are used to predict this nonideality factor. The ac-
tivity coefficient (γi ) is determined from the excess
Gibbs energy (GE ); this excess energy originates from
the difference between Gibbs energy of mixing for the
real-liquid mixture by subtracting the Gibbs energy of
mixing of an ideal mixture at the same temperature,
pressure, and mole fraction.
The nonideality of the mixture then needs to be
incorporated in the rate equation. Generally, the rate
equation is then written in terms of the activity of
each component (ai ) present in the reaction mixture.
The activity coefficients of the components of the
main reaction (CH3 COOH, CH3 OH, CH3 COOCH3 ,
and H2 O) are estimated using the UNIQUAC activity

Figure 9 Comparison of experimental profiles of acetic acid conversion at different temperatures at varying catalyst concen-
trations with predictions of the concentration-based kinetic model with water effect.

International Journal of Chemical Kinetics DOI 10.1002/kin

 KINETIC MODELS FOR ACID-CATALYZED METHYL ACETATE FORMATION REACTION 271

Table I UNIQUAC r i and q i Values in terms of the activities is expressed as follows:

Component ri qi    act 
−rA,act = k1,act aA aB − aC aD Keq (6)
Acetic acid 2.2024 2.0720
Methanol 1.4311 1.4320 where ai = xi γi ; Keq
act
is the activity-based reaction
Methyl acetate 2.8042 2.5760 equilibrium constant defined as
Water 0.9200 1.4000 eq eq eq eq
xC γC xD γD
act
Keq = eq eq eq eq (7)
xA γA xB γB
Based on an equilibrium conversion of 69%, the mole
model:
fractions and activities at equilibrium point are com-
φi z θi puted and substituted in Eq. (7) to obtain the value
ln γi = ln + qi ln + li of Keqact
. The model development procedure adopted
xi 2 φi
⎡ ⎛ ⎞ for the concentration-based model is extended to the
φi   case of the activity-based model also, and the preex-
nc nc
− xj lj + qi ⎣1 − ln ⎝ θj τij ⎠ ponential factor for the forward reaction is computed
xi j =1 j =1 according to
⎤  eq eq 

nc
θj τij CA CB
− nc ⎦ (5)
0
k1,act = k10 eq eq (8)
 γA γB
j =1 k=1 θk τkj

where k10 is defined according to Eq. (3), and “eq”

where refers to the equilibrium concentrations and activity
coefficients at the corresponding compositions, which
ri xi qi xi
φi = nc , θi = nc , are determined from the equilibrium conversion. The
k=1 rk xk k=1 qk xk final rate expression incorporating inhibition effect of
q  xi water activity is given as
θi = nc i  ,
k=1 qk xk  
  k1,act aA aB − aC aD /Keq
act

τij = exp aij +

bij
+ cij T , −rA,act = (9)
T 5(0.9 + aD )
z The predicted conversion profiles of the reaction based
li = (ri − qi ) − (ri − 1) , z = 10 and nc = 4 on the activity-based kinetic model at 26, 40, and 50◦ C
2
with 2% catalyst concentration and at 40◦ C with 1%
The parameters ri and qi values of pure components and 5% catalyst concentration along with experimen-
are reported in Table I, and the interaction coefficients tal values without a correction term for water activity
are reported in Table II [4]. The basic rate expression are shown in Figs. 10 and 11, respectively, whereas the

Table II UNIQUAC Interaction Parameters

i j aij (K) bij cij (K−1 )
Acetic acid Methanol 390.26 0.97039 −3.0613 × 10−3
Methanol Acetic acid 65.245 −2.0346 3.1570 × 10−3
Acetic acid Methyl acetate −62.186 −0.43637 2.7235 × 10−4
Methyl acetate Acetic acid 81.848 1.1162 −1.3309 × 10−3
Acetic acid Water 422.38 −0.051007 −2.4019 × 10−4
Water Acetic acid −98.120 −0.29355 −7.6741 × 10−5
Methanol Methyl acetate 62.972 −0.71011 1.1670 × 10−3
Methyl acetate Methanol 326.60 0.72476 −2.354 × 10−3
Methanol Water −575.68 3.1453 −6.0713 × 10−3
Water Methanol 219.04 −2.0585 7.0149 × 10−3
Methyl acetate Water 593.70 0.010143 −2.1609 × 10−3
Water Methyl acetate −265.83 0.96295 2.0113 × 10−4

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272 GANESH ET AL.

Figure 10 Comparison of experimental profiles of acetic acid conversion at different temperatures with predictions of the
activity-based kinetic model without water effect.

predicted conversion profiles incorporating the correc-
tion term for both the sets are shown in Fig. 12. The
results clearly indicate that the activity-based model
with the correction term also represents the experi-
mental data very well.
Comparative Validation of Models
The data generated during the third set of experiments
at different temperatures with varying catalyst concen-
trations, that is, 50◦ C: 1%, 40◦ C: 5%, and 35◦ C: 4%
in addition to the data for the experiment at 40◦ C with
2% catalyst concentration are employed to validate the
concentration and activity-based models and compare
them with the models cited in the literature, as shown
in Figs. 13–16. The models reported in the literature
considered for comparison are listed in Table III along
with the parameters reported. In some cases, although
the models have been reported, the parameters have
not been reported and in such cases, we attempted in
the present study to refit the parameters and employ
the models for comparison. The parameters computed
in the present study for such models are also reported
in Table III.

Figure 11 Comparison of experimental profiles of acetic acid conversion at 40◦ C at different catalyst concentrations with
predictions of the activity-based kinetic model without water effect.

International Journal of Chemical Kinetics DOI 10.1002/kin

 Table III Kinetic Models Considered in the Present Study (Units as Per Notation)
Literature Model Model Structure Reported Parametersa Estimated Parameters
Agreda et al. −rA = k0 exp(−Ea /RT ).(CA CB − CC CD /Ke ), where Ke = 5.2 k3 = 2.0 × 1012
k0 = k1 (Xcat )2 + k2 (Xcat ) for Xcat ≤ 0.004 and k4 = 1.99543 × 1012

International Journal of Chemical Kinetics

k0 = k3 − k4 exp(k5 /(Xcat − 0.004)) for Xcat > 0.004 k5 = 2.457182 × 10−7
  Ea = 63, 062.4
Liu et al. −rA = Ccat 0.38
CD
(CA CB − CC CD /Ke ) Ke = 6.22 at 60◦ C –
  1  2 
−E −E
Elgue et al. −rA = Ccat k01 exp RTa CA CB − k02 exp RTa CC CD k01 = 4.21
k02 = 0.322

DOI 10.1002/kin
Ea1 = 53,800
  1  2  Ea2 = 52,580 –
−E −E
Bonnaillie et al. −rA = Ccat k01 exp RTa CA CB − k02 exp RTa CC CD k01 = 0.0055 –
k02 = 0.011
Ea1 = 41800
   Ea2 = 41800
√ k1 CC CD
Present work −rA = (12.5k1 +CD )
CA CB − Ke Ea = 63062.4
Concentration-based model   Ke = 5
−Ea
k1 = k10 exp RT , k10 = −9.405338 × 106 (wc )2 + 1.344269 × 108 (wc )
 
act
k1,act aA aB −aC aD /Keq
Activity-based model −rA,act = 5(0.9+a , Ea = 63062.4
   eqD ) eq  eq eq eq eq
0 −Ea 0 C CB act xC γC xD γD
k1,act = k1,act exp , k1,act , Keq = eq eq eq eq
RT = k10 γ Aeq γ eq
A B xA γA xB γB
a
Units for k01 and k02 are lit mol−1 min−1 mL−1 L H2 SO4 .
KINETIC MODELS FOR ACID-CATALYZED METHYL ACETATE FORMATION REACTION
273
274 GANESH ET AL.

Figure 12 Comparison of experimental profiles of acetic acid conversion at different temperatures at varying catalyst concen-
trations with predictions of the activity-based kinetic model with water effect.

Figures 13–16 clearly illustrate that the proposed
new models based on the concentration as well as
activity are able to predict the conversion achieved
comparable with experimental data with reasonable
accuracy throughout the reaction. The model reported
by Agreda et al. [6] with parameters as determined in
the present study is found to predict the conversion rea-
sonably well during the initial 10–15 min after which
it exhibits mismatch until equilibrium is attained in
all cases except for 50◦ C: 1% catalyst concentration,
where the deviation is drastic throughout the reaction.
The reason for the drastic deviation in this case is that
the catalyst concentration falls in another region of the
preexponential factor dependency on the catalyst con-
centration for which parameters are not available. The
model reported by Elgue et al. [10] is found to deviate
considerably both with respect to the equilibrium con-
version as well as the rate at which it is approached. In
all the cases except for 35◦ C: 4% catalyst concentra-
tion and initial water presence, the response is found to

Figure 13 Comparison of different kinetic models at 40◦ C at 2% catalyst concentration.

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 KINETIC MODELS FOR ACID-CATALYZED METHYL ACETATE FORMATION REACTION 275

Figure 14 Comparison of different kinetic models at 40◦ C at 5% catalyst concentration.

Figure 15 Comparison of different kinetic models at 50◦ C at 1% catalyst concentration.

be very slow compared to the experimental data. Only
in the latter case is the predicted conversion profile in
the initial region found to match the experimental data
to some extent. However, the latter part of the profile
is found to deviate considerably in this case also. The
model reported by Bonnaillie et al. [14] (as cited by
Elgue et al. [10]) is found to be slightly faster than
that reported by Elgue et al. [10] but is still unable
to match the speed of response of the conversion of
the experimental data. However, the equilibrium con-
version in this case is found to match reasonably well
with the experimental data. The only case where a com-
parison could be made with the model reported by Liu
et al. [9] is the reaction at 35◦ C: 4% catalyst concentra-
tion with some initial quantity of water because in all
other cases, the initial water concentration is zero and
therefore the rate expression as reported by them be-
comes undefined at time = 0, and hence the conversion

International Journal of Chemical Kinetics DOI 10.1002/kin

276 GANESH ET AL.

Figure 16 Comparison of different kinetic models at 35◦ C at 4% catalyst concentration.

cannot be determined. Figure 16 clearly illustrates that
the model reported by Liu et al. [9] is unable to pre-
dict the conversions to match the experimental data.
This could be because of the linear catalyst concen-
tration dependence and water inhibition dependence to
the power of −0.83 in contrast to the model proposed
in the present study, which has a quadratic catalytic
concentration dependence and water inhibition depen-
dence approximately to the power of −0.5.
Furthermore, it can be observed that at high cata-
lyst concentration (in the absence of water initially),
the reaction rate is very fast and all the models ex-
hibit a closer match with the experimental data (as
in Fig. 14), whereas both the models proposed in this
study have exhibited predicted conversion profiles con-
sistently matching with the experimental data in all
the cases studied. Based on the data from seven ex-
periments, the overall absolute mean deviation, over-
all% absolute deviation, and correlation coefficient of
fractional conversion prediction in comparison with
the experimental values for six models (including two
models proposed in the present study) are reported in
Table IV. This table, together with Figs. 13–16, clearly
illustrates the accuracy of the kinetic models devel-
oped in the present study. Although the performance
of both the proposed models is equally good, the use of
concentration-based model is recommended because
of its simplicity.
CONCLUSIONS
On the basis of comprehensive experimental investiga-
tion of the esterification of acetic acid with methanol
using sulfuric acid as the catalyst, a second-order ap-
proach in terms of the concentration and activities is

Table IV Comparison of Prediction Accuracy of Different Models for Fractional Conversion

Overall Absolute Overall % Absolute Correlation
Model Average Deviation Deviation Coefficient (R 2 )
Agreda et al. 0.086 20.9 0.7671
Liu et al. 0.124 32.2 0.5015
Elgue et al. 0.104 23.9 0.8114
Bonnaillie et al. 0.076 18.3 0.8313
Present work
Concentration-based model 0.025 5.8 0.9646
Activity-based model 0.027 6.7 0.9582

International Journal of Chemical Kinetics DOI 10.1002/kin

 KINETIC MODELS FOR ACID-CATALYZED METHYL ACETATE FORMATION REACTION 277

used to develop a model describing the reaction ki- Greek Symbols

netics. Concentration-based and activity-based kinetic
γi activity coefficient of component i
models are developed incorporating the effects of tem-  
θi , i , θi , i Uniquac model parameters of
perature, catalyst concentration, and water inhibition
component I
and are validated and compared with the literature-
cited models. Both the newly developed models predict
the experimental data very well when compared with Subscripts
the literature-cited models. The study shows that it is
A acetic acid
necessary to take into account the quadratic influence
B methanol
of the catalyst on the rate constants along with the in-
C methyl acetate
corporation of a correction term considering inhibitory
D water
effect of water formed.
cat catalyst

NOTATION BIBLIOGRAPHY
ai activity of ith component
1. Rolfe, C.; Hinsshelwood, C. N. Trans Faraday Soc 1934,
Ci concentration of ith component
30, 935.
Ea activation energy (J mol−1 )
2. Hilton, S.; Smith, H. A. J Am Chem Soc 1939, 61, 254.
k10 , k−1
0
preexponential factors (lit mol−1 3. Ronnback, R.; Sami, T.; Vuori, A.; Haario, H.; Lehtonen,
min−1 ) J.; Sundqvist, A.; Tirronen, E. Chem Eng Sci 1997, 52,
k1 esterification reaction rate constant 3369.
(lit mol−1 min−1 ) 4. Popken, T.; Gmehling, G. J. Ind Eng Chem Res 2000,
k−1 hydrolysis reaction rate constant(lit 39, 2601–2611.
mol−1 min−1 ) 5. Liu, Y.; Lotero, E.; Goodwin Jr. G. J. J Catal 2006, 242,
Ke equilibrium constant 278–286.
Keq act
equilibrium constant in 6. Agreda, V. H.; Partin, L. R.; Heise, W. H. Chem Eng
activity-based model Prog 1990, 86 (2), 40–46.
7. Engell, S.; Fernholz, G. Chem Eng Process 2003, 42,
R gas constant (J mol−1 K−1 )
201–210.
rA rate of reaction based on 8. Kreul, L. U.; Górak, A.; Dittrich, C.; Barton, P. I. Com-
concentration (mol lit−1 min−1 ) put Chem Eng 1998, 22, S371-S378.
rA,act rate of reaction based on activity 9. Liu, Y.; Lotero, E.; Goodwin Jr. G. J. J Mol Catal A:
(mol lit−1 min−1 ) Chem. 2006, 245, 132–140.

ri, qi , qi , li UNIQUAC model parameters 10. Elgue, S.; Devatine, A.; Prat, L.; Cognet, P.; Cabassud,
aij , bij , cij , τij Binary interaction parameters M.; Gourdon, C.; Chopard, F. Int J Chem React Eng
T temperature (K) 2009, 7, Article A24.
xi liquid-phase mole fraction of 11. Aafaqi, R.; Mohamed, A. R.; Bhatia, S. J Chem Technol
component i Biotechnol 2004, 79, 1127.
XA ,XAe conversion and equilibrium 12. Kusdiana, D.; Saka, S. Bioresource Technol 2004, 91,
289–295.
conversion
13. Levenspiel, O. Chemical Reaction Engineering, 3rd ed;
yi vapor-phase mole fraction of Wiley: New York, 1999.
component i 14. Bonnaillie, L.; Meyer, X. M.; Wilhelm, A. M. Proceed-
wc weight% of catalyst with respect to ings of IMSR2, Nuremberg: Germany, 2001 (as cited by
weight of acetic acid Elgue et al., 2009).

International Journal of Chemical Kinetics DOI 10.1002/kin