Applied Catalysis A: General 299 (2006) 185–192

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Esterification of alcohols with acetic acid over zeolites Hb,

HY and HZSM5
Sharath R. Kirumakki a, N. Nagaraju a,*, Komandur V.R. Chary b,*
a
Department of Chemistry, St. Joseph’s College P.G. Center, 46 Langford Road, Bangalore 560027, India
b
Catalysis Division, Indian Institute of Chemical Technology, Tarnaka, Hyderabad 500007, India
Received 1 June 2005; received in revised form 12 October 2005; accepted 13 October 2005
Available online 2 December 2005

Abstract
Kinetic studies on the liquid phase esterification of C3 and C4 alcohols on acetic acid were carried out over zeolites Hb, HY and HZSM5. The
aims of this study were to arrive at the reaction mechanism from the kinetic data and to investigate the effects of the type of alcohol and zeolite type
on the reaction mechanism. Zeolite Hb was found to be the most active for this reaction. The acidity of zeolite determines the extent of the
esterification reaction. The esterification reaction was found to follow the Eley–Rideal pathway. Acetic acid is activated by adsorption on the
zeolite acid site, which then reacts with the alcohol in the bulk to form the corresponding acetate.
# 2005 Published by Elsevier B.V.

Keywords: Esterification; Zeolites; Acetic acid; Reaction kinetics; Eley–Rideal mechanism

1. Introduction mechanism for esterification of acetic acid with butanol. From

Esterification reactions have been carried out extensively
using homogenous as well as heterogeneous catalysts. Though
homogenous catalysts are widely used in industries for
economical reasons, ecological factors favor the use of
heterogeneous catalysts. Solid acids such as zeolites and metal
oxides have been widely studied in esterification reactions [1–
9]. Although the mechanism of esterification catalysed by
homogenous catalysts is well established, the mechanism of the
reaction catalysed by heterogeneous catalysts is still debated.
Most of the researchers agree on a protonated carboxylic acid
intermediate. We have also proposed a similar intermediate in
the esterification reactions carried out over zeolites [7–9].
Literature data on whether the esterification follows a dual site
Langmuir–Hinshelwood (LH) mechanism or a single site Eley–
Rideal (ER) mechanism is contradictory.
Chu et al. studied gas-phase esterification of acetic acid with
butanol and ethanol over heteropolyacids supported on carbon
[10]. They proposed a Langmuir–Hinshelwood mechanism for
the esterification of acetic acid with ethanol, but an Eley–Rideal
* Corresponding authors.
E-mail addresses: nagarajun@yahoo.com (N. Nagaraju),
kvrchary@iict.res.in (Komandur V.R. Chary).
0926-860X/$ – see front matter # 2005 Published by Elsevier B.V.
doi:10.1016/j.apcata.2005.10.033
their studies on the gas-phase esterification of acetic acid with
ethanol over MCM-41, Koster et al. have concluded that it
proceeds via a protonated acetic acid intermediate and follows a
LH pathway [11]. Altiokka and Citak have studied the liquid
phase esterification of acetic acid with isobutanol in the
presence of a strongly acidic ion-exchange resin, Amberlite IR-
120, as catalyst [12]. They found that the reaction occurs
between an adsorbed alcohol molecule and a molecule of acid
in the bulk phase, i.e. an ER model. Teo and Saha have studied
the kinetics of esterification of acetic acid with isoamyl alcohol
over a cation-exchange resin catalyst, Purolite CT-175 [13].
They report that this reaction proceeds through a modified LH
model, where acetic acid adsorbed on one active site reacts with
isoamyl alcohol adsorbed on the adjacent active site to give
isoamyl acetate and water. Liu and Tan, from their studies on
liquid phase esterification of propionic acid with n-butanol have
concluded that this esterification proceeds via an ER pathway
over Amberlyst catalyst [14]. We have concluded from our
kinetic studies that the liquid phase esterification of benzyl
alcohol with acetic acid proceeds through an Eley–Rideal
mechanism [9]. The esterification reaction takes place between
acetic acid adsorbed on the zeolite surface, forming an electro-
phile and benzyl alcohol in the bulk.
From the above literature survey, it is clear that the
mechanism of esterification is ambiguous and that it is
186 S.R. Kirumakki et al. / Applied Catalysis A: General 299 (2006) 185–192

Table 1
Physico-chemical characteristics of zeolites
Zeolite Si/Al Area BET Acidity (mmol/g) NH3
(m2/g)
Weak (A) Medium (B) Strong (C)
Hb 8 434 1.03 2.30 4.50
HZSM5 25 400 1.89 1.16 3.05
HY 30 730 1.51 1.70 0.99
Desorption temperature: A = 423–523 K, B = 523–623 K, C = 623–723 K.

dependent on the catalysts and the reactants. It is also possible

that the mechanism varies for gas-phase and liquid phase
operations. Reports on mechanisms and kinetics of esterifica-
tion of C3–C4 alcohols with acetic acid over zeolites are scarce.
The aim of this study therefore was to investigate the effect of
different alcohols and zeolite type on the reaction pathway in Fig. 1. Esterification of alcohol with acetic acid, effect of the catalyst type—
the liquid phase esterification with acetic acid. acetic acid (AA):alcohol (Alc) = 1:1 (mol/mol), reaction time 1 h, catalyst
weight 0.5 g, reaction temperature 383 K.

2. Experimental
Protonated forms of Zeolites Y and ZSM5 used in the
esterification of alcohols with acetic acid were obtained from
Conteka, The Netherland. The sodium form of zeolite b was
obtained from United Catalysts India Limited and was
converted to its protonated form following the conventional
ion exchange procedure using aqueous 0.5 M NH4NO3
solution, followed by calcination at 823 K. BET surface areas
of the zeolite samples were measured on a Micromeritics Pulse
Chemisorb 2700 instrument, using N2 as the adsorbate. The
acidity of the zeolites was measured by stepwise temperature-
programmed desorption (STPD) of ammonia on the same
instrument using a TCD detector, and by bracketing the tem-
perature of desorption we could arrive at the relative strengths
of acidity [15]. The relevant physico-chemical properties of the
zeolites are given in Table 1.
The esterification reaction was carried out in a round bottom
glass flask (50 cm3) fitted with a water-cooled condenser in the
temperature region 383–403 K. The temperature was main-
tained using an oil bath connected to a thermostat. The
reactants, alcohol and acetic acid, were taken directly into the
flask along with the catalyst. The different alcohols used in this

Fig. 2. Esterification of alcohols with acetic acid, effect of Alc:AA molar ratio, reaction time 1 h, catalyst weight 0.5 g, reaction temperature 383 K. Hb (&), HY (&)
and HZSM5 ( ).
 S.R. Kirumakki et al. / Applied Catalysis A: General 299 (2006) 185–192
investigation are n-propyl alcohol, iso-propyl alcohol (2-
propanol), n-butyl alcohol and iso-butyl alcohol (2-butanol).
The total volume of the reactants was kept constant at 12 cm3.
The reaction mixture was continuously stirred during the
reaction using a magnetic stirrer. The reaction was carried out
for a definite period of time after which the catalyst was
separated from the reaction mixture by filtration and washed
with acetone. The reaction products were analyzed by GC–MS
(column: HP-1MS 15 m
0.25 mm
0.25 mm). Blank reac-
tions were also carried out in the absence of a catalyst. The only
product formed was the corresponding acetate. Experiments
were designed by varying the amount of the catalyst, the molar
ratio of the reactants, the reaction temperature and the reaction
period to obtain various kinetic parameters.
The conversion was calculated based on the GC analyses
using the following expression:
conversion of alcohol ð%Þ
 
½alcohol
¼ 1
100
½alcohol þ ½acetate
Fig. 3. Esterification of alcohols with acetic acid, effect of catalyst weight—Alc:AA = 1:1 (mol/mol), reaction time 1 h, reaction temperature 383 K. Hb (&), HY
(*) and HZSM5 (~).
187
3. Results and discussion
3.1. Preliminary results
Initial investigations have been carried out on the effect of the
catalyst type on the esterification; the results are presented in
Fig. 1. The only product formed is the corresponding acetate, i.e.
selectivity towards the ester is 100%. Conversion of alcohol
depends on the type of catalyst as well as on the alcohol used.
Even in the absence of a catalyst, the ester was formed, although
to a much smaller extent. Protonated forms of zeolites b, Y and
ZSM5, being acidic in nature, increase the conversion levels
when used as acid catalysts. The conversion of alcohols was
found to be the highest for Hb, followed by HZSM5 and HY. This
implies that the difference in conversion levels can be attributed
to the difference in acidity of zeolites. For a given catalyst, the
conversion was highest for n-propyl alcohol and least for iso-
butyl alcohol. The conversion was found to decrease in the order
n-propyl > n-butyl > iso-propyl > iso-butylalcohol
188 S.R. Kirumakki et al. / Applied Catalysis A: General 299 (2006) 185–192
Straight chain alcohols are more active than their branched
counterparts in the esterification reaction.
3.2. Influence of molar ratio of the reactants
The reaction was carried out over zeolites Hb, HY and
HZSM5 using different molar ratios of acetic acid to alcohol
(Fig. 2). The conversion of alcohol was found to decrease with
increase in concentration of alcohol in the reaction mixture. In
the case of Hb, the conversion of n-propyl alcohol decreased
from 94 to 70% as the ratio of alcohol:acid was increased from
0.2 to 5. Similarly, in the case of HY the conversion decreased
from 83 to 59.6% and for HZSM5 the decrease in conversion
was 88 to 62% when n-propyl alcohol was used in the
esterification. The same trend was also observed over the other
alcohols. This implies that an increase in the alcohol
concentration hinders the esterification reaction, probably by
blocking the active sites on the catalyst.
3.3. Influence of catalyst concentration
The amount of the catalyst was varied from 0 to 1.0 g while
keeping the molar ratio of acid:alcohol at 1:1. The reaction was
carried out at 383 K for 1 h. The conversion of the alcohol
increased linearly on increasing the weight of zeolite (Fig. 3).
For example, n-butyl alcohol conversion increased from 48 to
Fig. 4. Esterification of alcohols with acetic acid, effect of reaction temperature—Alc:AA = 1:1 (mol/mol), reaction time 1 h, catalyst weight 0.5 g. Hb (&), HY (*)
and HZSM5 (~).
89% on increasing the Hb weight from 0.25 to 1.0 g. In the case
of HY the increase in conversion was from 41 to 68% and for
HZSM5 the increase was from 62 to 88%. In the absence of a
catalyst the reaction yielded 29% of the ester. A similar linear
increase in conversion was observed for the other alcohols on
increasing the catalyst weight.
3.4. Influence of reaction temperature
The esterification reaction was carried out in the temperature
region 383–403 K while keeping the acid:alcohol molar ratio at
1:1 and the catalyst weight at 0.5 g (Fig. 4). In general, it has
been found that the conversion of the alcohol increases with
increase in reaction temperature. The conversion of n-propyl
alcohol over Hb increases from 83 to 93% on increasing the
reaction temperature from 383 to 403 K, this increase, when
iso-propyl alcohol was used, is from 52 to 70%.
3.5. Influence of reaction time
The esterification reaction was carried out for up to 2 h
keeping the acid:alcohol molar ratio at 1:1 and the catalyst
weight at 0.5 g (Fig. 5). Esterification, being a reversible
reaction, reached equilibrium in about 1 h, indicated by the
leveling of the conversion after about 60 min of the reaction time.
In case of reactions carried out in the absence of a catalyst, the
 S.R. Kirumakki et al. / Applied Catalysis A: General 299 (2006) 185–192 189

Fig. 5. Esterification of alcohol with acetic acid, effect of the catalyst type—acetic acid (AA):alcohol (Alc) = 1:1 (mol/mol), catalyst weight 0.5 g, reaction
temperature 383 K. Hb (&), HY (*), HZSM5, (~) and blank (
).

equilibrium was not achieved within this time. The time required zeolites Hb, HY, and HZSM5 are given in Fig. 7. The plots are
to achieve equilibrium depends on the alcohol used. The reactive nearly linear in all cases, indicating the esterification reaction to
alcohols reach equilibrium faster than the less reactive ones. be a first order reaction.
From the above discussion and the results presented it is
clear that the conversion variation pattern is the same for all the 3.7. Mechanism
alcohols used in this study. This implies that the reaction
mechanism for this esterification involving the above alcohols The reaction mechanism over zeolites can be described by
is the same. Therefore, a kinetic study on any one of the either a Langmuir–Hinshelwood pathway or an Eley–Rideal
alcohols would be sufficient to gain insight into the mechanism
of this esterification reaction. n-Propyl alcohol was chosen to
carry out the comprehensive kinetic study on the zeolite
catalysed esterification with acetic acid.

3.6. Kinetics of esterification of n-propyl alcohol with

acetic acid

Prior to the kinetic studies, experiments were conducted to

establish the effect of mass transfer limitations during the
reaction. The mass transfer limitations can be evaluated using the
Madon–Boudart test [16,17]. Such a test utilizes the fact that in
the absence of all transport limitations, the rate of a reaction is
proportional to the number of active sites, which in turn is
proportional to the weight of the zeolite. A plot of rate as a
function of the weight of catalyst is linear and the rate increased
proportionally with the weight of zeolite (Fig. 6), indicating the
absence of any mass transfer limitations during the reaction. Fig. 6. Esterification of n-propyl alcohol with acetic acid, effect of catalyst
Plots of ln (1  conversion) versus reaction time for the weight on the rate of conversion of n-propyl alcohol—Alc:AA = 1:1 (mol/mol),
esterification reactions carried out at 383 and 403 K over reaction temperature 383 K. Hb (&), HY (*) and HZSM5 (~).
190 S.R. Kirumakki et al. / Applied Catalysis A: General 299 (2006) 185–192
Fig. 7. Plot of the first order rate equation for the esterification of n-propyl
alcohol with acetic acid over zeolites; acetic acid (AA):alcohol (Alc) = 1:1
(mol/mol), catalyst weight 0.5 g. Hb(&), HY (*), HZSM5 (~) and blank (
)
at (a) 383 K and (b) 403 K.
pathway or by one of their modified forms. Derouane [18,19]
has argued that a Eley–Rideal model cannot be used to describe
accurately the behavior of zeolite catalysts used in the synthesis
of fine chemicals in liquid phase because both the reactants are
confined within the zeolite pores and there is a competitive
Fig. 8. Esterification of n-propyl alcohol with acetic acid, effect of n-propyl
alcohol on the initial reaction rate. Concentration of acetic acid 9.1
103 mol,
reaction temperature 383 K, catalyst weight 0.5 g. Hb (&), HY (*) and
HZSM5 (~).
adsorption of the reactant molecules on the zeolite surface.
Some authors have also stated that a pure Eley–Rideal model
cannot fully represent a chemical process occurring over
zeolites [20,21]. As mentioned in Section 1, both these models
have been successfully employed to describe various transfor-
mations over zeolites. In this study, we have tried to fit the data
in both the kinetic models and to arrive at the mechanism based
on the best fit.
Let KA and KB be the equilibrium adsorption constants for
acetic acid and n-propyl alcohol, let CA and CB be the initial
concentrations of acetic acid and n-propyl alcohol, respectively.
The rate of reaction for LH mechanism is given by the
following equation (Eq. (1)):
ks0 KN KA CA
rA ¼ (1)
ð1 þ KA CA þ KB CB Þ2
The initial rate equation for ER is given by Eqs. (2) and (3):
(a) without competitive adsorption of n-propyl alcohol
ks0 KA CA
rE ¼ (2)
1 þ KA CA
(b) with competitive adsorption of n-propyl alcohol
ks0 KA CA
rE ¼ (3)
1 þ KA CA þ KB CB
where ks0 ¼ ks (rate constant) if the adsorption of n-propyl
alcohol is the controlling step, and ks0 ¼ ks CB if the che-
mical reaction is the rate limiting step [22,23]. As already
mentioned, there is no mass transfer limitation on the
zeolite surface, i.e. the chemical step is the rate determining
step. If the esterification reaction proceeds through a LH
mechanism, then a plot of rate versus concentration must
pass through a maximum according to Eq. (1), if it follows
an ER mechanism, then no such maximum is encountered.
Fig. 8 indicates that the initial reaction rate increases
linearly with alcohol concentration. This would suggest
that the esterification of alcohol with acetic acid follows ER
Fig. 9. Plot of CB/rE vs. CB/CA for the esterification reaction of n-propyl
alcohol with acetic acid. Reaction temperature 383 K, catalyst weight 0.5 g. Hb
(&), HY (*) and HZSM5 (~).
 S.R. Kirumakki et al. / Applied Catalysis A: General 299 (2006) 185–192 191

Scheme 1. Plausible reaction mechanism for the esterification of alcohol with acetic acid over zeolites.

mechanism. A decrease in the rate observed with an increase found to the highest for Hb, followed by HZSM5 and HY. The
in the alcohol concentration can be explained by the satura- KB/KA was also found to follow the same order. The efficiency
tion of the catalyst surface with the alcohol thereby blocking of the catalyst in this reaction depends therefore on its acid
the acid adsorption. Thus, we can say that acid adsorption is a character as well as on its ability to adsorb the alcohol, which
must for the esterification to proceed and that there is a would hinder the reaction. The esterification reaction takes
competitive adsorption of alcohol. Then the initial rate place between acetic acid adsorbed on the zeolite surface,
equation can be given by Eq. (4): forming a protonated acetic acid intermediate, which is an
electrophile, and the alcohol in the bulk (Scheme 1). There is
ks CB KA CA
rE ¼ (4) competitive adsorption of the alcohol on the acid sites, which
1 þ KA CA þ KB CB
reduces the efficiency of the catalyst. This effect is more pr-
After one linearises Eq. (4), a plot of CB/rE against CB/CA onounced in reactions carried out at high alcohol concentration.
(Fig. 9) yields a slope = KB/KAks and an intercept = 1/ks. From
this the adsorption coefficient KB/KA can be obtained. The fit 4. Conclusions
was found to be good and the reaction rate constants and the KB/
KA value obtained are given in Table 2. The rate constant was Liquid phase esterification of acetic acid with different C3
and C4 alcohols was carried out over zeolite catalysts. The
degree of esterification depends on the type of alcohol and the
Table 2
Rate constants and adsorption constants for the esterification of n-propyl
acidity of the zeolite, as seen by the differences in conversion
alcohol with acetic acid over different zeolites. The order of activity of alcohols is n-
propyl > n-butyl > iso-propyl > iso-butyl alcohol and the
Zeolite ks (
103 min1) KB/KA
order of activity of zeolites is Hb > HZSM5 > HY. The
Hb 51.34 0.2602 mechanism of this reaction is the same for all alcohols and
HY 33.42 0.1073
zeolites studied. It follows a Eley–Rideal mechanism where the
HZSM5 40.31 0.1541
acid is first adsorbed on the zeolite to form an electrophile and
192 S.R. Kirumakki et al. / Applied Catalysis A: General 299 (2006) 185–192
this reacts with alcohol in the bulk to form the corresponding
acetate and water.
Acknowledgement
We thank the DST, New Delhi, for funding this research.
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