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Enhancement of Esterification Reaction

between Ethanol and Sulphuric Acid Using
Ionic Liquids
a a
Sarvani Kuchibhotla & P.S.T. Sai
a
Department of Chemical Engineering, Indian Institute of Technology
Madras, Chennai – 600 036, India
Published online: 02 Sep 2013.

To cite this article: Sarvani Kuchibhotla & P.S.T. Sai (2013) Enhancement of Esterification Reaction
between Ethanol and Sulphuric Acid Using Ionic Liquids, Indian Chemical Engineer, 55:3, 143-152, DOI:
10.1080/00194506.2013.829260

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 INDIAN CHEMICAL ENGINEER – 2013 Indian Institute of Chemical Engineers
Vol. 55 No. 3 September 2013, pp. 143
152
Print ISSN: 0019-4506, Online ISSN: 0975-007X, http://dx.doi.org/10.1080/00194506.2013.829260

Enhancement of Esterification Reaction between

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Ethanol and Sulphuric Acid Using Ionic Liquids

Sarvani Kuchibhotla & P.S.T. Sai*

Department of Chemical Engineering, Indian Institute of Technology Madras, Chennai
600 036, India

Abstract: Experiments were conducted in a batch reactor under isothermal conditions to study the enhancement
of the esterification reaction between ethanol and sulphuric acid with ionic liquid as catalyst. The three catalysts
used for the study were 1-butyl 3-methylimidazolium octyl sulphate, 1-ethyl 3-methylimidazolium octyl sulphate
and 1-butyl 3-methylimidazolium methyl sulphate. The effect of reaction temperature, catalyst concentration and
type of catalyst on conversion of the reactant was studied to obtain the kinetics of the reaction. The conversion
levels increased with increasing catalyst concentration and decreased with increasing reaction temperature in the
temperature range investigated. The rate data fitted first-order kinetics at high concentrations of the reactant and
zero-order kinetics at low concentrations of the reactant, thus exhibiting shifting order-type kinetics. The
proposed reaction mechanism suggested the possibility of splitting of the ionic liquid before participating in the
reaction.

Keywords: Ionic liquids, Esterification, Diethyl sulphate, Shifting order kinetics

Introduction
The demand for chemicals with vital applications is constantly increasing. One such chemical that has
industrial importance is diethyl sulphate (DES). DES finds many applications, for example as a
catalyst in the conversion of acetals to vinyl esters, as an alkylating agent for converting metal halides
to alkyl halides, in the preparation of detergents and in the refining of fats. Smaller quantities are used
in household products, cosmetics, agricultural chemicals and pharmaceuticals.
The two existing industrial processes for the manufacture of DES are (a) the action of ethanol
with chlorosulphonic acid [1] and (b) absorption of ethylene in concentrated sulphuric acid [2]. One of
the principle drawbacks of the above processes is the difficulty in maintaining extreme operating
conditions. In the ethylene absorption process, it is essential that the pressure be kept high (20
30 atm)
to obtain a good yield of DES. In contrast, the ethanol
chlorosulphonic acid process requires a very

*Author for Correspondence: E-mail: psts@iitm.ac.in

 144 S. KUCHIBHOTLA AND P.S.T. SAI

low temperature (0
58C) for the esterification step. These conditions deviate widely from the normal
pressure and temperature. This requires vigorous control procedures and careful monitoring. Another
drawback is the high cost of chemicals used in both processes. The ethanol
chlorosulphonic acid
process produces large amounts of hydrogen chloride which should be recovered as hydrochloric
acid [3].
To overcome the drawbacks of these processes, Theodore and Sai [3] employed a reactive
adsorption technique, in which the water formed during the reaction was removed with anhydrous
sodium sulphate as an adsorbent. This method requires normal conditions, viz., room temperature and
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atmospheric pressure. The conversion obtained at optimum conditions was 97%. Even though the
reactive adsorption method yielded good conversion, regeneration and recirculation of solid
adsorbent on continuous scale would be a problem. Hence, an efficient homogeneous catalyst is
necessary in order to overcome this drawback.
The use of ionic liquids as good catalysts for the esterification reactions between aliphatic acids
and alcohols has been studied under mild reaction conditions and it was reported that the esters
formed are not soluble in ionic liquids, hence, they can be separated easily [4]. The esterification of
carboxylic acids with alkyl halides catalysed by fluoride ions in ionic liquids was investigated and a
yield of 95% was reported under mild and safe conditions [5]. Bronsted acidic ionic liquids
derived from alkyl amines were used as catalysts and media for the esterification of octanol with
acetic acid. The study concluded that the higher acidity of the anion in ionic liquid resulted in higher
yield of ester and that the yield of ester decreased with increase in the size of the cation [6].
Esterification of carboxylic acids with alkyl halides using the ionic liquid as solvent in the presence
of triethylamine was studied and conversions of up to 99% were reported [7]. It was suggested that
the ionic liquid can be recycled and reused [7].
An analysis of the literature indicates that there is no reported information on the use of ionic
liquids as catalysts to enhance the esterification reaction between ethanol and sulphuric acid. Being
a homogeneous catalyst, ionic liquid eliminates the drawbacks of the reactive adsorption technique.

Experimental
Experiments were conducted in a stirred batch reactor under isothermal conditions with a mole ratio
of ethanol to sulphuric acid of 1. Known amounts of ethanol and ionic liquid were taken in one
conical flask and a calculated amount of sulphuric acid taken in a separate flask was cooled; both
were transferred to the reaction vessel. Since the reaction is exothermic, the reactants were pre-
cooled before they were mixed in order to limit the temperature rise following mixing so that a
constant temperature could be maintained in the reactor throughout the experiment. Samples of 0.1
ml were drawn from the reaction vessel at regular time intervals for analysis using a Karl Fischer
titrator. The reaction temperature was varied from 293 to 303 K and the catalyst concentration was
varied between 0.25 and 1 vol%. The three catalysts used were 1-butyl 3-methylimidazolium octyl
sulphate (BMOS), 1-ethyl 3-methylimidazolium octyl sulphate (EMOS) and 1-Butyl 3-methylimi-
dazolium methyl sulphate (BMMS).

Results and Discussion

The aspects considered here are: (a) effect of operating variables on the yield of ethyl hydrogen
sulphate (EHS); (b) kinetics of the reaction; and (c) mechanism of the reaction. Since conversion

INDIAN CHEMICAL ENGINEER Vol. 55 No. 3 September 2013

 Esterification Reaction between Ethanol and Sulphuric Acid 145

Ethanol + Sulfuric acid

Ethanol + Sulfuric acid + Anh. Sodium sulfate
Ethanol + Sulfuric acid + ionic liquid
1

0.8
Fractional conversion

0.6
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0.4

0.2

0
0 5 10 15 20 25 30 35 40
Time, min

Fig. 1. Comparison of fractional conversion obtained using ionic liquid with conventional methods.

levels are high even with mole ratio of 1, experiments were not conducted at higher mole ratios of
reactants. The chemical reactions involved in this process are as follows:

C2 H5 OHð1Þ þ H2 SO4 ð1ÞXC2 H5 HSO4 ð1Þ þ H2 Oð1Þ (1)

2C2 H5 HSO4 ð1ÞX ðC2 H5 Þ2 SO4 ð1Þ þ H2 SO4 ð1Þ (2)

Since the distillation of EHS to produce DES is a well established step, the esterification
reaction between ethanol and sulphuric acid to produce EHS was chosen for the present study. The
progress of the reaction was followed by monitoring the concentration of water in the sample with a
Karl Fischer titrator. The concentration of the reactants and products were obtained from the
measured concentration of water by stoichiometry.
Effect of Operating Variables
In order to check the applicability of ionic liquids as catalysts for the ethanol
sulphuric acid system,
as literature is available only for organic esters with ionic liquids as catalysts, preliminary
experiments were conducted with BMOS as the catalyst. The fractional conversion vs time data
obtained with 1% (by volume) of catalyst was compared with the two conventional methods,
namely, the reaction between ethanol and sulphuric acid with no catalyst, and the reaction between
ethanol
sulphuric acid and a stoichiometric amount of anhydrous sodium sulphate as adsorbent.
These experiments were conducted at a reaction temperature of 303 K and a mole ratio of reactants
of 1. The results are shown in Fig. 1.
These results indicate that ionic liquid gives better fractional conversion compared with the
other methods. The fractional conversion obtained with anhydrous sodium sulphate as adsorbent is
more or less the same as that obtained with no adsorbent. This is because of the use of a low mole
ratio of reactants. It was reported [3] that higher fractional conversions can be obtained with
anhydrous sodium sulphate as adsorbent, but at a high mole ratio of reactants. Ionic liquid gives

INDIAN CHEMICAL ENGINEER Vol. 55 No. 3 September 2013

 146 S. KUCHIBHOTLA AND P.S.T. SAI

0.8
* 283 K
Fractional conversion
1

0.8
293 K
0.6
303 K
0.6 313 K
0.4
0.4
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0.2

0
0.2 0 0.2 0.4 0.6 0.8 1

0
0 5 10 15 20 25 30 35

Fig. 2. Variation of fractional conversion with time for different temperatures.

higher fractional conversion even at lower mole ratios, and thus eliminates the process of separation
of unreacted reactants from the products as required in the reactive adsorption method.
Experiments were conducted to screen the reaction temperature range for better fractional
conversion using 1% (by volume) of BMOS as catalyst and the results are shown in Fig. 2. It can be
observed from the figure that the fractional conversion was less when the reaction was conducted at
283 and 313 K compared with 293 and 303 K, respectively. This indicates that the higher fractional
conversion can be obtained when the reaction is conducted between 293 K and 303 K.
A set of 27 experiments was performed covering the range shown in Table 1. All of the
experiments were conducted with mole ratio of reactants of 1. Since conversion levels are high even
with the mole ratio of reactants of 1, experiments were not conducted at higher mole ratios of
reactants. This is in contrast to the mole of ratio of reactants of 6 used in the literature [3] to achieve
similar conversion levels.
Figure 3 shows the effect of reaction temperature on variation of concentration of the reactant
with time for the three catalysts at fixed catalyst concentration. The concentration variation with
time during 1 min of reaction time is shown in the inset. From the figure, it can be observed that the

Table 1. Details of experiments performed

Variable Range

Mole ratio of reactants 1

Type of catalyst 1-Butyl 3-methylimidazolium octyl sulphat (BMOS)
1-Ethyl-3-methylimidazolium octyl sulphate (EMOS)
1-Butyl-3-methylimidazolium methyl sulphate (BMMS)
Temperature, K 293, 298, 303
Catalyst concentration (vol%) 1.00, 0.50, 0.25

INDIAN CHEMICAL ENGINEER Vol. 55 No. 3 September 2013

 Esterification Reaction between Ethanol and Sulphuric Acid 147

-3
x 10

8 x 10 -3
303 K
7 8
298 K
6
CA, mol/cc 6 293 K
4
5 2
4 0 0.2 0.4 0.6 0.8 1
3
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0
0 5 10 15 20 25 30 35

Time, min

Fig. 3. Concentration of reactant vs time plot for 1% by volume of BMOS.

fractional conversion decreases with an increase in reaction temperature for any catalyst and for any
catalyst concentration. This behaviour is true for reversible exothermic reactions as equilibrium
conversion decreases with an increase in temperature. Since conversion levels are high, the reaction
may not be reversible. However, this is to be confirmed by the rate data analysis.

Effect of Catalyst Concentration

Figure 4 depicts the effect of catalyst concentration on variation of reactant concentration with time
at fixed temperature for the three catalysts used in the present study. From the figure, it can be
observed that the fractional conversion increases with the increase in catalyst concentration at any
reaction temperature.

-3
x 10

9 x 10 -3
8 8
1.0 vol. %
6
CA, mol/cc

7 0.5 vol. %
4
6 0.25 vol. %
2
5
0 0.2 0.4 0.6 0.8 1
4

1
0 5 10 15 20 25 30 35
Time, min

Fig. 4. Concentration of reactant vs time plot for 298 K of EMOS.

INDIAN CHEMICAL ENGINEER Vol. 55 No. 3 September 2013

 148 S. KUCHIBHOTLA AND P.S.T. SAI

Effect of Type of Catalyst

Figure 5 shows the effect of the type of catalyst on variation of reactant concentration with time at
fixed temperature and catalyst concentration. Unlike the previous variables, a common trend in
concentration variation with time is not observed with the variation of type of catalyst. For example,
at the reaction temperature of 303 K, the fractional conversion follows the sequence BMMS 
BMOS EMOS for catalyst concentrations of 1 and 0.5%. On the other hand, the fractional
conversion follows the sequence BMOS BMMS EMOS at a catalyst concentration of 0.25%.
While EMOS yields the lowest fractional conversion at all catalyst concentrations, the other two
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catalysts swap their sequence. Similarly, at the reaction temperature of 298 K, the fractional
conversion follows the sequence BMMS BMOS EMOS for catalyst concentrations of 0.5 and
0.25%, respectively. On the other hand, at a catalyst concentration of 1%, the sequence is BMOS 
BMMS EMOS, which is the same as obtained at the lowest concentration at a reaction
temperature of 303 K. At the reaction temperature of 283 K, when the catalyst concentrations are
0.5 and 0.25% respectively, the fractional conversion follows the sequence EMOS BMMS 
BMOS. However, where the catalyst concentration is changed 1%, the sequence changes to
EMOS BMOS BMMS. These observations indicate no trend with the type of catalyst, the
catalyst concentration or the reaction temperature.

Kinetics of the Reaction

Concentration vs time data obtained from the experiments conducted at different temperatures and
catalyst concentrations for the three different catalysts was subjected to both integral and differential
methods of analysis for deriving a suitable rate law. The rate laws considered were: irreversible first
order, irreversible second order, reversible first order, reversible second order and shifting order.
Since integral and differential methods did not yield a proper rate equation, shifting-order kinetics
was attempted. As the concentration vs time plots show a sudden drop in concentration until 1 min
of reaction time and a slow decrease beyond that, shifting order-type kinetics was attempted to fit
-3
x 10
9

8 x 10 -3

8
7
BMOS 6
CA, mol/cc

6 EMOS 4
BMMS
5 2

0 0.2 0.4 0.6 0.8 1

4

1
0 5 10 15 20 25 30 35
Time, min

Fig. 5. Concentration of reactant vs time plot for 293 K and catalyst concentration of 0.25 vol%.

INDIAN CHEMICAL ENGINEER Vol. 55 No. 3 September 2013

 Esterification Reaction between Ethanol and Sulphuric Acid 149

the rate data. There is published information on the use of shifting order-type kinetics [8
10] for
explaining the kinetics of a reaction.
In the present study, irreversible first order fitted the rate data for 0
1 min, as shown in Fig. 6,
and zero order beyond that, as shown in Fig. 7. Hence, the rate data follows irreversible first order
up to 1 min and zero order beyond that. In summary, the analysis of rate data indicates that the
following rate laws fit the experimental data satisfactorily: at high concentration of reactants,

rA ¼ k1 CH2 SO4 (3)

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and at low concentration of reactants

rA ¼ k0 (4)

The values of the rate constant obtained under various experimental conditions are presented in
Table 2. Following the Arrhenius equation, the frequency factor and activation energy values are
provided in Table 3 for the temperature range 293
303 K.
Reaction Mechanism
From the kinetics it was observed that the reaction followed first order at higher concentration of
reactants and zero order at lower concentrations. This indicates that the reaction is non-elementary;
hence, there is a necessity to determine the mechanism. The following assumptions are based partly

2.5

2
-ln(CA /C Ao)

1.5

0.5

0
0 0.2 0.4 0.6 0.8 1 1.2
Time, min

Fig. 6. Test for irreversible first-order kinetics by integral method.

0.002
0.0016
CA, mol/cc

0.0012
0.0008
0.0004
0
0 5 10 15 20 25 30 35 40
Time, min

Fig. 7. Test for zero-order kinetics by integral method.

INDIAN CHEMICAL ENGINEER Vol. 55 No. 3 September 2013

 150 S. KUCHIBHOTLA AND P.S.T. SAI

Table 2. Rate constant values for the three catalysts

n)
Rate constant k, 1/s (mol/m3)(1
BMOS EMOS BMMS

Catalyst concentration, Temperature, 0
1 1
35 min 0
1 1
35 min 0
1 1
35 min
vol% K min min min

303 0.0341 3.3310 7 0.0311 1.6710 7 0.0347 6.67 10 7

2.5010 7 1.3310 7 5.83 10 7
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1 298 0.0325 0.0254 0.0317

293 0.0294 1.6710 7 0.0228 1.0010 7 0.0306 5.00 10 7
303 0.0365 3.3310 7 0.0302 1.6710 7 0.0348 6.67 10 7
0.5 298 0.0304 2.5010 7 0.0293 1.3310 7 0.0300 5.83 10 7
293 0.0285 1.6710 7 0.0271 1.0010 7 0.0284 5.00 10 7
0.25 303 0.0352 3.3310 7 0.0310 1.6710 7 0.0348 6.67 10 7
298 0.0315 2.5010 7 0.0288 1.3310 7 0.0303 5.83 10 7
293 0.0287 1.6710 7 0.0276 1.0010 7 0.0298 5.00 10 7

Table 3. Values of activation energy and frequency factor for the three catalysts

0
1 min 1
35 min

Catalyst Activation energy (kJ/mol) Frequency factor Activation energy (kJ/mol) Frequency factor

BMOS 14.77 12.33 51.21 228.26

EMOS 13.03 5.41 37.73 0.5400
BMMS 11.85 3.78 21.24 0.0031

on experimental information and partly on accumulated knowledge about the characteristics of the
different species involved in the reaction.

(1) The ionic liquid used splits up as anion and cation.

(2) The anion and cation of the ionic liquid form intermediate complexes with ethanol and
sulphuric acid respectively.
(3) All of the steps are assumed to be elementary and irreversible.
(4) The final product formation step is considered to be the rate-determining step.

The mechanism proposed is as follows:

k1
IL ! Aþ þ B (5)
k1
C2 H5 OH þ B ! C2 H5 B þ OH (6)
k1
H2 SO4 ! HSO
4 þH
þ
(7)

INDIAN CHEMICAL ENGINEER Vol. 55 No. 3 September 2013

 Esterification Reaction between Ethanol and Sulphuric Acid 151

k1
HSO þ
4 þ A ! HSO4 A (8)
k1
C2 H5 B þ HSO4 A þ Hþ þOH ! C2 H5 SO4 þH2 O þ IL (9)
Employing pseudo-steady-state approximation to all the intermediates,
rEHS ¼k5 ½C2 H5 B½HSO4 A½Hþ ½OH  ¼ k4 ½HSO þ
4 ½A  ¼ k 3 ½H2 SO4  (10)
This is the final form of the rate equation for 0
1 min, that is, at high concentration of reactant,
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which is the same as was obtained from the analysis of rate data by both integral and differential
methods. Hence, the assumed reaction mechanism is consistent with the experimental observations.
At lower concentrations of reactant, Equation (10) reduces to
rA ¼ k0 (11)
This is same as that obtained from kinetic analysis.

Conclusions
A method for the manufacture of diethyl sulphate for better yield has been identified by employing
ionic liquid as catalyst. The lower the reaction temperature, the better the conversion levels were for
all three catalysts investigated. The fractional conversion decreased with increase in temperature of
the reaction mixture. While all the three catalysts yielded better conversion, the suitability of the
catalyst for better yield depended on the experimental conditions. The fractional conversion
increased with increase in catalyst concentration. The reaction followed first order during initial
stages and shifted to zero order at lower concentrations of the reactants. The mechanism suggests
that the ionic liquid splits before participating in the reaction. Ionic liquids yield higher conversion
than the reaction adsorption process in a shorter reaction time.

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