Homogeneous and

Heterogeneous Catalyzed
Esterification of Acrylic Acid
with Ethanol: Reaction
Kinetics and Modeling
GHOSHNA JYOTI,1 AMIT KESHAV,1 J. ANANDKUMAR,1 STUTEE BHOI2
1
Department of Chemical Engineering, National Institute of Technology Raipur, Raipur, India
2
Department of Chemical Engineering, Indian Institute of Technology Kharagpur, Kharagpur, India

Received 23 August 2017; revised 22 February 2018; accepted 24 February 2018

DOI 10.1002/kin.21167
Published online 22 March 2018 in Wiley Online Library (wileyonlinelibrary.com).

ABSTRACT: Kinetics of esterification of acrylic acid with ethanol in the presence of homo-
geneous (H2 SO4 , HCl, p-TSA, HI) catalysts as well as heterogeneous catalysts (Dowex 50WX,
Amberlyst 15) was studied. The effects and performance of these catalysts on the conversion
of acrylic acid were evaluated. In the kinetics of homogeneous catalyzed reaction, both con-
centration and activity-based model were employed. Activity coefficients were predicted by
the Universal Functional group Contribution (UNIFAC) method to consider nonideal behavior
of the liquid phase. The heterogeneous catalyzed reaction mechanisms were developed using
Eley–Rideal theory. The model results were compared with the experimental results and were
in good agreement. The temperature dependency of the constants, reaction enthalpy, and
entropy, and activation energy were determined. The conversion of acrylic acid was obtained
as 63.2%, 61.02%, 53.3%, 21.4%, 34.96%, and 14.84% for H2 SO4 , p-TSA, HCl, HI, Dowex 50WX,
and Amberlyst 15, respectively, under process temperature of 70°C, reactant molar ratio of 1:1,
and catalyst concentration of 2% (v/v) for homogeneous and 2.17 g for heterogeneous catalyst.
These outcomes provide an approach to understand the significant effect of each catalyst on
the esterification kinetics of acrylic acid and ethanol. 
C 2018 Wiley Periodicals, Inc. Int J Chem

Kinet 50: 370–380, 2018

INTRODUCTION widely employed in the application of solvents, plas-

ticizers, sealants, medicinal agents, flavors, and fra-
Esterification is an essential reaction-producing es- grances [1,2]. These reactions are reversible and hav-
ters in chemical industries. Desired product esters are ing low reaction rate, which shows limited conversion.
Owing to low and slow reaction rate, suitable catalyst
are employed in this reversible reaction. It takes a lot of
Correspondence to: Amit Keshav; e-mail: dr.amitkeshav@
gmail.com. energy to remove the –OH from the carboxylic acid, so

C 2018 Wiley Periodicals, Inc. appropriate catalyst and heat are needed to produce the
 KINETICS AND MODELING OF ESTERIFICATION OF ACRYLIC ACID WITH ETHANOL 371

necessary energy. Once the –OH has been removed, part in the reaction [14,17–19]. Finally, the E–R model
the hydrogen on the alcohol can be removed and that is applied when the reaction between one adsorbed
oxygen can be connected to the carbon. Because the species and one nonadsorbed reactant from the bulk
oxygen was already connected to a carbon, it is now liquid phase is assumed to occur [7,16,20].
connected to a carbon on both sides, and an ester is The present work investigates the kinetics of esteri-
formed. fication of acrylic acid and ethanol catalyzed by various
Both homogeneous and heterogeneous catalysts are homogeneous and heterogeneous catalysts. The effect
used to increase the reaction rate. A homogeneous of reaction temperature on kinetics of reaction was
catalyst such as sulfuric acid (H2 SO4 ), hydrochloric described. For comparative study of catalysts, four ho-
acid (HCl), and para-toluene sulfonic acid (p-TSA) mogeneous catalysts, namely H2 SO4 , HCl, p-TSA, HI,
acts as a protonating catalyst during the esterifica- and two heterogeneous catalysts, i.e., Dowex 50WX
tion reaction [3,4]. Drawbacks of homogeneous cat- and Amberlyst 15, are employed. The kinetic studies
alyst such as corrosion of equipment, side reactions, of both homogeneous and heterogeneous catalyzed es-
and difficult to separation from the product mixture terification reactions were performed. Nowadays, it is
can be resolved by the employment of heterogeneous essential to study the kinetics and reaction equilibrium
catalysts. Many researchers have done comparative of reaction to understand and describe chemical reac-
study of homogeneous and heterogeneous catalysts tions in a better way. Both concentration and activity-
[4–7]. These literature reports suggest that the homo- based model were considered for homogeneous as
geneous catalyst favors more conversion of acid or well as heterogeneous catalysts. The E–R model was
yield of product than a heterogeneous catalyst. But employed to correlate the experimental data of ion-
heterogeneous catalysts lead easy recovery of cata- exchange catalysts.
lyst and more purity of product than the homogeneous
catalyst.
Compared to the homogeneous catalyst, the reac-
EXPERIMENTAL
tion rate in the heterogeneous catalyst will proceed at
a slower rate. This is due to the fact that the homoge-
Material and Method
neous catalyst and reactants have a similar phase and
hence the reaction rate is faster [1]. This finding has All reactants acrylic acid (99% pure; Loba Chemie,
already been reported by several researchers. Aafaqi Mumbai, India), ethanol (99% pure; Hayman, Pune,
et al. [8] reported that the homogeneous catalyst gives India) and catalysts sulfuric acid (98% pure; Loba
better conversion than the heterogeneous catalyst for Chemie, Mumbai, India), hydrochloric acid (98% pure;
esterification of palmitic acid with isopropanol. Yal- Loba Chemie, Mumbai, India), and p-toluene sulfonic
cinyuva et al. [9] reported similar comparative results acid (99% pure; Fisher Scientific) were of analytical
for esterification of myristic acid with isopropyl alco- grade. Heterogeneous catalysts Amberlyst 15 hydro-
hol. They concluded that heterogeneous catalysts gave gen form and Dowex 50WX hydrogen form were ob-
poor conversions due to the diffusion problem of fatty tained from Sigma-Aldrich. No more purification was
acid into the pores of the catalyst. Henceforth, a lot performed for the experiments. Millipore ultrawater
of reports [2,10,11] suggested that the homogeneous was used for the preparation of aqueous solutions re-
catalyst induces more conversion compared to hetero- quired for product analysis.
geneous catalyst. The esterification reaction was carried out in a
Generally, for performing the kinetics of the ho- 1000-mL three-necked ball glass flask equipped with a
mogeneous catalytic esterification reaction, the power magnetic stirrer (Remi1 RML). The setup is shown in
law model is employed [1,12]. To describe the kinetic Fig. 1. One of the measured reactant was fed to the
behavior of heterogeneous catalytic esterification reac- reactor and heated up to a desired temperature. An-
tions, several kinetic models have been reported. The other reactant was heated in a separate flask and trans-
simplest one is the pseudo-homogeneous (P-H) model, ferred to the reactor followed by addition of cata-
which is similar to the power law model for homo- lyst. This time was taken as the initial (starting) time
geneous reactions [13–16]. The other widely adopted of the reaction. In this study, the experiments were
models are Langmuir–Hinshelwood (L–H) and Eley– performed at 50, 60, and 70°C reaction temperature
Rideal (E–R) models. The P-H model assumes that and the catalyst concentration of 2% (v/v) of reac-
the surface reaction is the controlling step, and adsorp- tion mixture with a molar ratio of 1:1 (acrylic acid
tion is negligible for all components. The L–H model to ethyl alcohol) of reactants. Samples were collected
is applicable for correlating the kinetic data whenever at regular intervals for 6–7 h and analyzed by a gas
their occurs the adsorption of the molecules is taking chromatograph (GC).

International Journal of Chemical Kinetics DOI 10.1002/kin.21167

372 JYOTI ET AL.

Figure 2 Effect of different catalysts on conversion of

acrylic acid at different temperatures (t = 420 min).

ditions were kept same for all experiment with same

temperature and the molar ratio acrylic acid/ethanol of
1:1. An amount of catalyst of 2% v/v of reaction mix-
ture was considered in case of homogeneous, and the
amount of catalyst corresponding to equivalent w/w%
of H2 SO4 was considered in case of the heterogeneous
Figure 1 Experimental setup for the esterification process. catalyst. Hence the resulted amount of heterogeneous
catalyst of 2.17 g was taken.
As evident from Fig. 2, the conversion of acrylic
acid increases with an increase in the temperature be-
GC Analysis cause of acceleration of the forward reaction. It is due
The samples collected from the reactor and the per- to the fact that high temperature gives rise to more
meate were analyzed by a NUCON series 5700 gas frequent and successful collision having sufficient en-
chromatograph equipped with a thermal conductivity ergy (activation energy) to break the bonds, and hence
detector, a cool glass lined injector, and a pressure pro- leads to higher conversion of reactants to ester prod-
grammable software. Separation was carried out on a ucts [1,21,22]. However, the reaction at too high tem-
porapak column (id 2mm, od 1/8”, length 2 m). Hy- perature leads to vaporization of reactants, which in
drogen gas taken as a carrier gas with a flow rate of turn decreases the efficiency of the system. Hence,
60 mL/min. The GC was calibrated using a known sam- there exists a trade-off between the high reaction rate
ple of acrylic acid, ethanol, ethyl acrylate, and water. due to the increased temperature and the decrease of the
One microliter of sample was injected into the chro- reaction rate, resulting from the vaporization of reac-
matograph. From the obtained peak area and retention tants. It is therefore essential to determine the optimal
time, the concentration of reactants, products, and per- reaction temperature or temperature profile for efficient
meates were found. The analysis was carried out with operation of the system considering the production rate
the injection chamber temperature at 150°C; the oven as well as the vaporizing rate of reactants [23].
and detection chamber temperatures were set at 180°C. Figures 3–5 show the effect of different homoge-
neous and heterogeneous catalysts on conversion of
acrylic acid at 50, 60, and 70°C, respectively. From the
figures, the obtained conversion of acrylic acid with
RESULTS AND DISCUSSION
different catalysts is in the following order: H2 SO4 >
p-TSA > HCl > Dowex 50W > HI > Amberlyst
Effect of Different Homogeneous and
15. This trend is maintained at all temperature except
Heterogeneous Catalyst
60°C where the conversion is nearly same for p-TSA
The effect of different types of catalysts on the perfor- and HCl. At 70°C, the final conversion is 63.2% for
mance of the esterification reaction was studied by us- H2 SO4 , 61.02% for p-TSA, 53.3% for HCl, 21.4%
ing four homogeneous catalysts, e.g., H2 SO4 , HCl, p- for HI, 34.96% for Dowex 50WX, and 14.84 for Am-
TSA, and HI, and two heterogeneous catalysts Dowex, berlyst 15. As expected, the conversion of acrylic acid
e.g., 50WX and Amberlyst 15. The operational con- is higher for the homogeneous catalyst as compared to

International Journal of Chemical Kinetics DOI 10.1002/kin.21167

 KINETICS AND MODELING OF ESTERIFICATION OF ACRYLIC ACID WITH ETHANOL 373

Figure 5 Effects of different catalysts on conversion of

Figure 3 Effects of different catalysts on conversion of acrylic acid for the esterification of acrylic acid and ethanol at
acrylic acid for the esterification of acrylic acid and ethanol 70°C, 1:1 acid/alcohol molar ratio, and catalyst concentration
at 50°C, 1:1 acid/alcohol molar ratio, and catalyst concen- of 2% (v/v) for homogeneous and 2. 17 gm for heterogeneous
tration of 2% (v/v) for homogeneous and 2.17 g for the catalysts.
heterogeneous catalysts.

reactions [12]. On the other hand, HCl is a gas and

needs to be dissolved in water to use in the liquid state.
The problem with this is that water is a product of
the esterification reaction, and more water increases
the rate of the reverse reaction thereby decreasing the
yield of the product ester. Besides, we have also used
p-TSA, which shows good catalytic activity due to
the presence of sulfonic acid groups, and subsequently
causes less acidity and less side reactions. Lastly, we
have considered the HI catalyst. HI shows very less
conversion as compared to other homogeneous cata-
lysts. It may be because of occurrence of side reaction,
which leads to formation of ethyl iodide. Ronnback
et al. [24] also revealed that in the esterification of
acetic acid with methanol in the presence of HI, a side
Figure 4 Effects of different catalysts on conversion of
acrylic acid for the esterification of acrylic acid and ethanol at
reaction appeared in which HI reacted with methanol
60°C, 1:1 acid/alcohol molar ratio, and catalyst concentration forms methyl iodide. The reaction was assumed to be
of 2% (v/v) for homogeneous and 2. 17 gm for heterogeneous the nucleophilic, whereas the rate-determining step in
catalysts. the hydrogen iodide esterification was supposed to be
the substitution of the iodide to protonated methanol.
Hydrogen iodide and acetic acid act as proton donors
the heterogeneous one. Overall, H2 SO4 was found to in the mechanism.
be the best among the all providing higher conversion There are some drawbacks of homogeneous cata-
in the studied conditions. The conversion of acrylic lyst such as corrosive nature and existence of possible
acid changes from 44.92% to 63.2% when tempera- side reactions. The use of heterogeneous catalyst such
ture is increased from 50 to 70°C. The sulfuric acid is as Dowex 50W and Amberlyst 15 may improve the
the most efficient homogeneous catalyst for the ester- conversion, but due to the diffusion problem of acid
ification reaction as it can lend two H+ ions for each into the pores of the catalyst heterogeneous catalysts
molecule of the acid present. Additionally, H2 SO4 is provided poor conversions [25]. Besides, the poor con-
stable and liquid in (nearly) the pure form. Moreover, version may be due to unavailability of some acid sites
concentrated sulfuric acid is a great dehydrating agent; on the catalyst for reaction or reduced activity because
hence, it will even seize some of the water produced of resin swelling or hydrophilicity. Moreover, restricted
in the reaction. Finally, sulfuric acid is neither a strong conformation of intermediate complexes adsorbed on
oxidant (nitric acid) nor a strong reductant (hydroiodic acid sites of the heterogeneous catalyst (as opposed
acid), thus reducing the possibilities for undesired side to unrestricted movement in solution in the presence

International Journal of Chemical Kinetics DOI 10.1002/kin.21167

374 JYOTI ET AL.

of the homogeneous catalyst) can also be a factor (equimolar concentration), which is given as
for reduced conversion [26]. It can be observed from
Figs. 3–5 that the performance of Dowex 50Wx8–100 2
k1 CEA CW XAe
is better than Amberlyst 15 for promoting the reac- Keq = = = (6)
k−1 CAA CEOH (1 − XAe )2
tion. Ali et al. [1] and Sert et al. [27] have also shown
higher conversions in the presence of Dowex compared Equation (6) can be rearranged in terms of conver-
to Amberlyst for propionic acid with 1-propanol and sion of acrylic acid
acrylic acid with n-butanol, respectively. In industries,
generally the concentrated H2 SO4 catalyst is used for  
dxA XA2
the esterification reaction due to the reason that it is CAA0 = k1 CC CAA0 (1 − XA ) −
2 2
(7)
dt Keq
more efficient and economical than other catalysts.

 xA
Kinetics of the Homogeneous Esterification dXA
= k1 CC CAA0 t (8)
Reaction 0 (1 − XA )2 −
XA2
Keq
The kinetic model of esterification of acrylic acid (AA)
with ethyl alcohol (EOH) to produce ethyl acrylate where
(EA) and water (W) can be presented as an elemen-
tary second-order reversible reaction, first-order with CAA
XA = 1 − (9)
respect to each reagent [28,29] and is represented as: CAA0

AA + EOH  EA + W (without catalyst) (1) XA and CAA0 are the conversion and initial con-
centration of acrylic acid. Equation (9) was solved in
MATLAB by applying the experimental data in the
AA + EOH + C  EA + W + C (with catalyst) temperature range of 50–70°C. A plot of the left-hand
side of Eq. (9) against reaction time, t along with the
(2)
fitted linear curve is given in Fig. 6. The reaction tem-
perature was varied from 50 to 70°C. The forward
The rate expression for the second-order reversible reaction rate constant, k1 , was obtained from the slope
reaction is written as of straight lines shown in Fig. 6, and the values of the
backward reaction rate constant, k−1 , was calculated
− ri = k1 CAA CEOH − k−1 CEA CW (3) from the Keq relation.
The temperature dependency of the rate constants,
Equation (3) can be rewritten as considering a con- k1 and k−1 , was determined from the Arrhenius expres-
centration term of catalyst, CC : sion and is given as
 
E1
−dCi k1 = k0 exp (10)
− ri = = k1 CAA CEOH CC − k−1 CEAc CW CC RT
dt
(4)
 
E−1
where CAA , CEOH , CEA , CW , and CC represent the con- k−1 = k−0 exp (11)
RT
centration (mol/L) of acrylic acid, ethanol, ethyl acry-
late, water, and catalyst, respectively. k1 and k−1 are
where R is a gas constant (8.31 J/mol·K). Table I
the forward and backward reaction rate constants, and
presents the activation energies of forward and back-
t is the reaction time.
ward reactions for different catalysts used in the present
Equation (4) can be written as
system. The obtained values of E1 from the litera-
  ture are 52.3 ± 1.9 kJ/mol for acrylic acid with 2-
−dCi CEA CW ethylhexan-1-ol, 40.7 kJ/mol for palmitic acid with
− ri = = k1 CC CAA CEOH − (5)
dt Keq isopropanol, and 42.07 kJ/mol for propionic acid with
benzyl alcohol [8,30,31]. The difference in results
The equilibrium constant, Keq , can be calculated could be because of the different system and catalyst
from the equilibrium conversion (XAe ) of the mixture employed in the present study.

International Journal of Chemical Kinetics DOI 10.1002/kin.21167

 KINETICS AND MODELING OF ESTERIFICATION OF ACRYLIC ACID WITH ETHANOL 375

Figure 6 Plot of the left-hand side of Eq. (9) against reaction time t (catalyst used: H2 SO4 ).

Table I Kinetic Parameters of Present System (Acrylic phase models such as Universal Functional group
Acid + Ethanol) for Different Catalysts Contribution (UNIFAC), Universal QUAsi Chemi-
H S cal (UNIQUAC), and non random two liquid model
Catalyst E1 (kJ/mol) E–1 (kJ/mol) (kJ/mol) (kJ/mol·K) (NRTL) models are used to describe a nonideal factor.
The activity model accounts for the nonideal ther-
H2 SO4 35.04 36.89 71.94 0.22
modynamic behavior of the reaction mixtures. It can
p-TSA 42.92 36.18 79.11 0.24
HCl 36.87 38.25 75.12 0.224
be developed from the concentration-based model by
HI 23.75 12.28 36.03 0.884 defining the activity as

ai = γi xi = γi Ci /Ct (13)
The Van’t Hoff equation is employed for the predic-
tion of the nature of reaction endothermic or exother-
where, γ i , Ci , and xi represent the activity coefficient,
mic by using experimentally determined equilibrium
concentration, and mole fraction of each component.
constant (Keq ):
The activity coefficients in the reaction mixture were
calculated by using the UNIFAC method.
H S
ln keq = − + (12) The chemical activities instead of concentrations
RT R can be used in the reaction rate equation:
Reaction enthalpys for H and entropy S were
obtained for various catalyzed reactions and are shown − ri = k1 aAA aEOH − k−1 aEA aW (14)
in Table I. The positive value of reaction enthalpy
shows that the reaction is endothermic. These values Keq is an equilibrium constant, which can be cal-
are in a good agreement with the literature findings of culated from the equilibrium molar concentration of
70.1–74.6 kJ/mol for acrylic acid with 2-ethylhexan- components (Ci )eq as given in the equation below
1-ol, 69.03 kJ/mol for acrylic acid with n-butanol, and
69–75 kJ/mol for acrylic acid with 2-ethylhexyl alco-
hol [30,32,33]. k1 (aEA )eq (aW )eq
Keq = =
To study the nonideality associated with the reaction k−1 (aAA )eq (aEOH )eq
mixture, we need to consider the activity coefficients (CEA )eq (CW )eq γEA γW
along with the molar concentration or mole fractions = = Kc Kγ (15)
to show the departure from the ideal case [34]. Real (CAA )eq (CEOH )eq γAA γEOH
mixtures involve the activity term of the component in-
stead of their concentration term for the calculation of Based on the equilibrium conversion or concentra-
thermodynamic equilibrium constant [30]. Commonly tion, the activities are computed and using Eq. (16) into

International Journal of Chemical Kinetics DOI 10.1002/kin.21167

376 JYOTI ET AL.

Table II Activity Coefficients of Components

in the Equilibrium State of the Reaction
at Different Temperatures
Component 50°C 60°C 70°C
Ethanol 1.275 1.269 1.264
Acrylic acid 0.794 0.802 0.810
Ethyl acrylate 1.480 1.476 1.471
Water 2.247 2.229 2.212

Eq. (15), the kinetic rate equation becomes

γAA γEOH Figure 7 Comparison of acrylic acid conversion be-
− ri = k1 CAA CEOH tween experimental data and simulation results using the
Ct2
concentration-based model with estimated parameters at 2%
γEA γW
− k−1 CEA CW (16) H2 SO4 catalyst and 1:1 acrylic acid to the ethanol molar
Ct2 ratio (symbols represent experimental data, and solid lines
represent concentration-based model results).
In this work, it is assumed that the reaction volume
is constant and also observed that the product between
the activity coefficients of both reactants and both prod-
ucts do not vary significantly, so the rate constants of
forward and backward of Eq. (17) can be grouped as

− ri = k1,act CAA CEOH − k−1,act CEA CW (17)

where

k1,act
Keq =
k−1,act

The forward rate parameter k1,act is related to the

Figure 8 Comparison of acrylic acid conversion between
temperature through an Arrhenius relation
experimental data and simulation results using the activity-
  based UNIFAC model with estimated parameters at 2%
E
K1,act = k0,act exp − (18) H2 SO4 catalyst and 1:1 acrylic acid to the ethanol molar
RT ratio (symbols represent experimental data, and dotted lines
represent the activity-based model results).
In present work, the UNIFAC model was consid-
ered to determine the activity coefficients. The coeffi-
cients are directly determined from Aspen Plus soft- ODE solver, ode15s implemented in the MATLAB.
ware. Truong et al. [35] also used same interface (As- The simulated values of conversion of acrylic acid
pen Plus) for the determination of activity coefficient mentioned in the kinetic modeling section were com-
by the NRTL model for the same reaction system. pared to that obtained experimentally. Figure 7 shows
The obtained activity coefficients and experimental a plot between simulated and experimental values of
equilibrium mole fractions of components in the se- conversion. It can be seen from the figure that the model
lected temperature range of 50–70°C are presented in (Eq. (9) predicted and experimental values are in good
Table II. agreement.
The experimental results and the activity-based
model predicted values were plotted for acrylic acid
Comparison of Experimental and Model
conversion at different reaction temperatures as shown
Predicted Results
in Fig. 8. The model values match reasonably well with
The numerical integration of Eq. (9) for each compo- experimental values. It can be observed that beyond
nent namely acrylic acid, ethanol, ethyl acetate, and 200 min, the activity-based model prediction matches
water, which was required during each iterative step well with the experimental data. The sum of squared
in the nonlinear regression, was accomplished by the error is 0.033 for the concentration-based model

International Journal of Chemical Kinetics DOI 10.1002/kin.21167

 KINETICS AND MODELING OF ESTERIFICATION OF ACRYLIC ACID WITH ETHANOL 377

and 0.030 for the activity-based model. Hence, the where k1 is the forward reaction rate constant, m is the
UNIFAC model predicts the experimental data slightly quantity of dry resin, V the volume of the reaction mix-
better than the concentration-based model. In the ture, Ke the equilibrium constant of the reaction, KEOH
present system, the obtained value of error is less, and KW the adsorption equilibrium constants. Consid-
which proves the accuracy of the UNIFAC model for ering chemical activities instead of concentrations, the
estimating the activity coefficients of the components. reaction rate equation for a nonideal mixture can be
written as

Kinetics of the Heterogeneous dai k1 (m/V ) (aAA aEOH − (aEA aW/Ke ))

− ri = − =
Esterification Reaction dt 1 + KEOH aEOH + KW aW
The heterogeneous reaction mechanism experimen- (21)
tally performed can be modeled by the E–R model,
The model equations described for all the compo-
which is the reaction on the basis of the assumption
nents consists of nonlinear differential equations and
that one of the adsorbed reactants is reacting with an-
are solved by an ODE solver, ode45 in MATLAB, to
other in the bulk fluid [1]. In this work, it was assumed
obtain the concentration profile of reactants and prod-
the reaction between adsorbed ethyl alcohol on acid
uct. The set of kinetic parameters were estimated by a
sites of the catalyst and acrylic acid in the bulk so-
nonlinear optimization subroutine fmincon from MAT-
lution, as proposed by Santos et al. [36]. However,
LAB. The objective function of the optimization prob-
ethyl acrylate molecules adsorbed were neglected and
lem is
adsorption of water by resin has an inhibiting effect
on the reaction mechanism [28]. Thus in the present 
NC
 cal 2
work the adsorption/desorption of water on this ion- φ= Ci − Ciexp (22)
exchange resin (solid) was considered. i=1
The esterification reaction of acrylic acid (AA) with
ethyl alcohol (EOH) for producing ethyl acrylate (EA) For a nonideal mixture
and water (W) in the presence of ion-exchange resin 
Na
 cal 2
(Dowex 50WX and Amberlyst 15) catalyst is given as φ= ai − aiexp (23)
follows: i=1

exp
AA + EOH  EA + W (19) where Cical and Ci are calculated and experimental
values of acrylic acid concentration of each experimen-
tal point “i,” respectively. NC is the number of experi-
The reaction mechanism can be given as following
mental data points for the concentration of acrylic acid.
steps [36]: exp
Similarly, aical and ai are calculated and experimental
values of acrylic acid activities of each experimental
EOH + S ↔ EOH · S adsorption of ethanol point “i,” respectively. Na is the number of experi-
mental data points for activity of acrylic acid. The ki-
netic parameters are obtained by solving the model
EOH · S + AA ↔ EA · S + W surface reaction equation based on the successive guess values of the
kinetic parameters. The resulting values are given in
Table III.
EA · S ↔ EA + S desorption of ester As mentioned previously for the homogeneous sys-
tem, reaction enthalpy for Dowex and Amberlyst 15 is
evaluated as 38.85 and 45.70 kJ/mol, respectively. The
positive value of reaction enthalpy shows that the reac-
W + S ↔ W · S adsorption/desorption of water
tion is endothermic. Activation energy of the forward
reaction for Dowex and Amberlyst 15 was calculated
where S represents solid site of catalyst. Depending as 31.04 and 35.52 kJ/mol, respectively.
on this mechanism, the reaction rate expression can be
given by
Comparison of Experimental and
dCi k1 (m/V ) (CAA CEOH − (CEA CW /Ke )) Model-Predicted Results
− ri = − =
dt 1 + KEOH CEOH + KW CW A comparative plot between experimental and
(20) model values of conversion of acrylic acid using

International Journal of Chemical Kinetics DOI 10.1002/kin.21167

378 JYOTI ET AL.

Table III Values of Kinetic Parameters at Different Temperatures

KEOH KW
k1 (m3 mol−1 min−1 ) Ke ((m3 )2 mol−1 min−1 ) ((m3 )2 mol−1 min−1 )

Concentration Activity Concentration Activity Concentration Activity Concentration Activity

Catalyst T (°C) Model Model Model Model Model Model Model Model
Amberlyst 15 50 0.0040 0.0330 0.0700 0.0007 0.0060 0.0053 0.0258 0.0258
60 0.0079 0.0285 0.1110 0.0011 0.0010 0.0009 0.0301 0.0301
70 0.0086 0.0589 0.1890 0.0019 0.0020 0.0009 0.0502 0.0499
Dowrex 50WX 50 0.0264 0.0502 0.0900 0.0090 0.0007 0.0007 0.0266 0.0266
60 0.0374 0.0800 0.1155 0.0116 0.0009 0.0009 0.0557 0.0557
70 0.0518 0.1870 0.2100 0.0210 0.0036 0.0013 0.0564 0.5640
Rate constants of channels 29, 30, 36, 37, and 43 were calculated with VTST, otherwise with CTST.

Figure 10 Comparison of acrylic acid conversion between

Figure 9 Comparison of acrylic acid conversion be- experimental data and simulation results using the activity-
tween experimental data and simulation results using the based UNIFAC model with estimated parameters at 2.17 g
concentration-based model with estimated parameters at 2.17 of catalyst and 1:1 acrylic acid to the ethanol molar ratio
g of catalyst and 1:1 acrylic acid to the ethanol molar ratio (symbols represent experimental data, and solid lines repre-
(symbols represent experimental data, and solid lines repre- sent model results; the filled symbol represents Amberlyst
sent model results; the filled symbol represents Amberlyst 15, and the hollow symbol represents Dowex 50WX).
15, and the hollow symbol represents Dowex 50WX).

heterogeneous catalysts is presented in Figs. 9 and 10. values of the kinetic parameters (k1 , Ke , KEOH , KW ) was
Figures explain the precision of the model for predict- also performed. To perform the sensitivity analysis, we
ing conversion of acrylic acid and well agreed with the considered the kinetic parameters obtained for Dowex
conversion obtained experimentally for both catalysts 50WX case (reaction temperature = 60°C) using the
Dowex 50WX and Amberlyst 15. The sum of squared UNIFAC model. The values of the parameters were
error for Dowex 50WX and Amberlyst 15 is 0.017 and varied in the range of ±50% of the estimated value. One
0.00314, respectively, for the activity-based model and parameter was varied at a time to realize its effect on
0.021 and 0.005, respectively, for the concentration- system performance. The most sensitive parameter was
based model, respectively. In the present system, the found to be k1 , and comparatively the most insensitive
obtained value of error is less, which proves the accu- parameters were KEOH and KW . The final conversion
racy of the UNIFAC model for estimating the activity of the acrylic acid was changed by nearly 8.5% when
coefficients of the components. the value of k1 was changed by 10% of its base value,
The sensitivity of the model prediction (or more whereas even a 50% change of the Ke value changes
precisely final conversion of acrylic acid) to changes in the conversion by only 0.15%.

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 KINETICS AND MODELING OF ESTERIFICATION OF ACRYLIC ACID WITH ETHANOL 379

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International Journal of Chemical Kinetics DOI 10.1002/kin.21167