Devi et al. Int. J. Res. Chem. Environ. Vol.

3 Issue 4 October 2013(20-23)

International Journal of Research in Chemistry and Environment

Vol. 3 Issue 4 October 2013(20-23)
ISSN 2248-9649
Research Paper

Eco-friendly esterification of Oxalic acid with Ethanol using Mesoporous MgAlPO4

Catalyst
Murugan R Devi and *Chellapandian Kannan
Department of Chemistry, Manonmaniam Sundaranar University, Tirunelveli-627012, Tamilnadu, INDIA

(Received 06 August 2013, Accepted 16th September 2013)

Abstract: Esterification of oxalic acid with ethanol using novel mesoporous Mg substituted aluminophosphate
(MgAlPO4) as catalyst was carried out in liquid phase. The effect of certain reaction conditions like temperature,
time, catalyst dosage on ethanol conversion, molar ratio of reactants and selectivity of product was studied. The
substitution of magnesium in the AlPO4 framework generates high strength of bronsted acid sites. This
amendment makes the catalyst to be highly active towards esterification of oxalic acid with ethanol.
Keywords: Esterification, MgAlPO4, oxalic acid, ethanol.
catalyst for the synthesis of industrially useful esters of
oxalic acid.

Introduction
The esters of oxalic acid have ample applications
in the field of organic chemistry. In organic condensation
reactions, the dialkyl and alkyl oxalates are used as
efficient reagents [1,2]. These alkyl oxalates also undergo
reduction reactions [3,4] resulting in the products like alkyl
glycolates and ethylene glycol which are industrially
important [5].

Material and Methods

The MgAlPO4 was synthesized according to the previous
report [19] using a simple hydrothermal method with the gel
composition of 0.8Al2O3:1P2O5:0.2MgO:0.5SDS:300H2O.
Esterification reaction was carried out in a batch
reactor fitted with a reflux condenser and a thermometer.
The ethanol and oxalic acid mixture was added with
MgAlPO4 catalyst.

In the conventional method of synthesis of

oxalates, organic solvents, strong acids and precious metals
such as Pd, Pt, Rh etc. supported catalysts are used to
enhance the esterification [6-9]. These types of catalysts are
very costly, unrecyclable and also generates unhealthy
environment.

After the completion of the reaction, the reaction

products were separated from solid MgAlPO4 catalyst by
filtration and the product was analyzed by gas
chromatography (Chemito 1000). The effect of reaction
conditions like temperature, contact time, catalyst dosage
and molar ratio of the reactants were studied to optimise
the maximum ethanol conversion and product selectivity.

Several other heterogeneous catalysts used in the

esterification reactions comprised of heteropolyacids, ion
exchange resins, zeolites etc., [10-13]. Although these solid
acid catalysts are found active for the esterification
reactions, the low thermal stability and high degree of
formation of side products make the catalysts inefficient.
Hence, frequent efforts have been made in order to replace
these drawbacks by thermally stable, highly acidic, large
pore heterogeneous catalysts.

Results and Discussion

The synthesized MgAlPO4 [19] have more acidity,

thermal stability (1200oC) and large pore size (pore
dia=28.7nm). These properties make the catalyst more
active towards the esterification reaction.

Metal substituted mesoporous aluminophosphates

are the emerging heterogeneous catalysts used in the
number of synthetic organic reactions [14-18]. The high
thermal stability and acidic nature of these materials make
several acid catalysed organic reactions possible. Thus, in
this present investigation, magnesium substituted
aluminophosphate [19] has been employed as a solid acid

Effect of reaction temperature: The effect of reaction

temperature was investigated by varying the temperature
from 50 to 200oC at alcohol to acid mole ratio of 3:1 for
6h. The results in the table 1 clearly depicted the
conversion of ethanol increased with the increase of
temperature. At 50 and 100oC, a marginal increase in
conversion was observed and the selectivity of the ester
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Devi et al. Int. J. Res. Chem. Environ. Vol.3 Issue 4 October 2013(20-23)
was found to be very low. This implies that the reaction
was unfeasible at lower temperatures. With the raise in
temperature from 150 to 200oC, a massive increase of
conversion with respect to ethanol was observed.

selectivity with respect to temperature was due to the

increase of activity of the catalyst at higher temperatures.
The higher temperature promotes the mobility of the H+
sites in the catalyst. This makes the reactants to likely form
diethyl oxalates. The selectivity of diethyl oxalate versus
reaction temperature is given in Figure 1.

Moreover, the selectivity of diethyl oxalate also

increased. This tremendous increase in conversion and

Table 1: Effect of reaction temperature on esterification of oxalic acid over MgAlPO 4

Temperature (oC)

Conversion of ethanol (%)

Product selectivity (%)

Ethyl oxalate
Diethyl oxalate

50
25
47.3
100
27
39.2
150
88
9.1
200
90
8
Reaction conditions: acid: alcohol 3:1, Time 6h, Catalyst amount 0.5g

52
60.4
91.5
91.7

Table 2: Effect of reaction time on esterification of oxalic

acid over MgAlPO4
Time
(h)

Conversion of
ethanol
(%)

Product Selectivity (%)

85

Ethyl
oxalate
7.6

Diethyl
oxalate
90.8

89

7.8

91.3

90

91.7

92

8.8

91.1

Reaction conditions: acid:alcohol 3:1, Temperature 200oC,

Catalyst amount 0.5g
Figure 1: Effect of reaction temperature Vs selectivity of
diethyl oxalate (Table 1)
follows Eley-Rideal mechanism (Scheme 1) [10]. Although
the conversion of ester decreased, the selectivity of diethyl
oxalate remains high.

Effect of contact time

The influence of reaction time on the esterification
of oxalic acid with ethanol was studied on MgAlPO 4 at
200oC (Table 2). With the increase in the reaction period,
the ethanol conversion and the selectivity of diethyl oxalate
and mono ethyl oxalate remains almost similar. From the
table 2, it is clearly found that the conversion slowly
increases with the increase of contact time. This indicated
that the catalyst is highly active for this reaction. Hence, the
conversion is almost maximum at low contact time (2h).

The influence of catalyst in the esterification was

also studied by varying the catalyst amount from 0.1, 0.2,
0.3, 0.4 and 0.5g at 200oC for 6h in the acid to alcohol
mole ratio 3:1. The percentage of conversion and
selectivity of diethyl and monoethyl oxalate with the
increase in catalyst loading are clearly illustrated in Table
3. It is concluded that the conversion of ester increased
with increase in catalyst loading due to the multiplicity of
active sites. But, a controversy was observed in the case
of selectivity of monoethyl and diethyl oxalate. The
selectivity of monoethyl oxalate decreased whereas
diethyl oxalate increased with the raise in catalyst
loading. The lesser number of active sites has little
difficulty to generate diethyl oxalates because lesser
number of active sites produces lesser number of ethyl
carbo cations. Hence, ethyl oxalates are easily generated
at low catalyst dosage. This interprets that the low

Effect of molar ratio of the reactants and catalyst

loading
The acid to alcohol molar ratio for the esterification
of oxalic acid with ethanol was increased from 1:1 to 5:1. It
is found that there is increase in the percentage of
conversion up to 3:1 molar ratio and further increase in mole
ratio (acid:alcohol) diminished the percentage of conversion
(Figure 2). The decrease in the conversion is due to the
flooding of active sites by oxalic acid molecules [10] which
prevent the alcohol adsorption on the active sites. Hence, it
creates a barrier for the further reaction. This clearly
illustrated that the esterification of oxalic acid with ethanol
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Devi et al. Int. J. Res. Chem. Environ. Vol.3 Issue 4 October 2013(20-23)
amount of catalyst likely produce mono ethyl oxalates

whereas increase in acid sites devised diethyl oxalates.

Figure 2: Effect of molar ratio Vs percentage of conversion of ethanol over MgAlPO 4

Scheme 1: Schematic representation of formation of monoethyl and diethyl oxalate using MgAlPO4 catalyst
Table 3: Effect of catalyst loading on esterification of oxalic acid over MgAlPO 4
Catalyst amount (g)

Conversion of ethanol (%)

Product selectivity (%)

Ethyl oxalate

0.1
0.2
0.3
0.4
0.5

81
35.4
84.3
21
86
10.5
88.9
9.1
90
8
Reaction conditions: acid:alcohol 3:1, Temperature 200oC, Time 6h
[22]

Diethyl oxalate
64.2
78.6
89
90.8
91.7

Devi et al. Int. J. Res. Chem. Environ. Vol.3 Issue 4 October 2013(20-23)

Conclusion
10. Jermy B. R. and Pandurangan A., A highly efficient
catalyst for the esterification of acetic acid using n-butyl
alcohol. J. Mol. Catal. A: Chem., 237, 146-154 (2005).

The efficient organic reagents monoethyl and

diethyl oxalates were successfully synthesized in an ecofriendly method by using mesoporous MgAlPO4 solid acid
catalyst. The various experimental conditions like
temperature, time, molar ratio and catalyst loading are
examined in order to attain the maximum conversion of
ethanol and selectivity of the products. The results
confirmed that the diethyl oxalate is the major product but
at lower catalyst loading slightly enhances the selectivity
of monoethyl oxalate. Thus, a new green approach has
been established for the synthesis of alkyl oxalates.

11. Verhoef J. M., Kooyman J. P., Peters A. J. and Van

Bekkum H., A study on the stability of MCM-41-supported
heteropoly acids under liquid and gas-phase esterification
conditions. Micropor. Mesopor. Mater., 27, 365-371 (1999).
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esterification of acetic acid with ethanol catalyzed by a
macroporous sulfonated styrene-divinylbenzene (20 %) resin.
Ind. Eng. Chem., 26, 198-202 (1987).

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