Catalytic hydrolysis of sucrose in the presence of vanadium oxide nanoparticles on SiO2

Article abstract of DOI:10.1007/s11172-012-0251-y

The kinetics of heterogeneous catalytic hydrolysis of sucrose in the presence of the V₂O₅/SiO₂ catalyst was studied using polarimetry. The optimum conditions for the reaction were selected. The activation parameters were calculated from the Arrhenius and Eyring equations. The particle size of the catalyst was determined by X-ray diffraction analysis.

Full text of DOI:10.1007/s11172-012-0251-y

1822
Russian Chemical Bulletin, International Edition, Vol. 61, No. 9, pp. 1822—1824, September, 2012
Brief Communications
Catalytic hydrolysis of sucrose in the presence
of vanadium oxide nanoparticles on SiO2
N. S. Langeroodi, J. Asghari, and M. Ghaemi
Science Faculty, Chemistry Department, Golestan University,
Gorgan, Iran.
Eꢀmail: nsamadani@yahoo.com
The kinetics of heterogeneous catalytic hydrolysis of sucrose in the presence of the
V O /SiO catalyst was studied using polarimetry. The optimum conditions for the reaction
2
5
2
were selected. The activation parameters were calculated from the Arrhenius and Eyring equaꢀ
tions. The particle size of the catalyst was determined by Xꢀray diffraction analysis.
Key words: hydrolysis, sucrose, heterogeneous catalyst, Xꢀray diffraction analysis.
Sucrose plays an important role in food allowance:
dangerous, and the catalysts are more easily recovered
and recycled. In this work we attempted to prepare the
heterogeneous catalyst V O /SiO , to examine sucrose
sucrose itself is widely used in food industry and, in addiꢀ
tion, invert sugar is obtained from sucrose by partial or
2
5
2
1
complete hydrolysis. Examples are known when sucrose
hydrolysis in the presence of SiO and V O /SiO , and to
2 2 5 2
was used in nonꢀfood industry. For instance, sucrose serves
as a raw materials for synthesis of valuable furan derivaꢀ
tives (5ꢀhydroxymethylfurfurol).2 The development of
chemical kinetics was facilitated by the study of sucrose
hydrolysis in the presence of an acidic homogeneous cataꢀ
study the thermodynamic and kinetic parameters of the
reaction.
,3
Experimental
4
—7
lyst.
In the recent time researchers are interested in
Preparation of the catalyst and the choice of the catalytic
reaction conditions. Sucrose, SiO2, and NH4VO3 (analytical puꢀ
rity grade, Merck) were used as received, prior to use water was
distilled twice and degassed. The catalyst V O /SiO was preꢀ
sucrose hydrolysis in the presence of heterogeneous cataꢀ
lysts.8
—12
Enzymes are most frequently used as catalysts
for the hydrolysis of sucrose to invert sugar in industrial
scales.13 However, when enzymes are used in food indusꢀ
try, the reaction is carried out at conversions lower than
2
5
2
1
5
pared using a procedure described earlier. The method of imꢀ
pregnation of SiO with V O (10 wt.%) was also described.
1
6
2
2
5
Sucrose hydrolysis was studied in the temperature range from 50
to 80 С by continuous stirring a 0.3 М solution of sucrose
9
5%, because glucose and fructose formed in the reaction
14
inhibit hydrolysis. Insoluble heterogeneous catalysts have
many advantages over liquid acidic systems, since they
decrease the corrosion rate, operation with catalysts is less
(
250 mL) in the presence of 3, 5, and 7 g of the catalyst. After
centrifuging, samples of the solution were taken for analysis at
certain intervals, and the rotation angle of light polarization
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1806—1809, September, 2012.
066ꢀ5285/12/6109ꢀ1822 © 2012 Springer Science+Business Media, Inc.
1

Catalytic hydrolysis of sucrose
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 9, September, 2012
1823
(4)
plane was determined in these samples using a WXGꢀ4 disc poꢀ
larimeter.
Catalyst characterization. The Xꢀray patterns were detected
on a D&ADVANCE diffractometer using CuꢀК radiation
or
lnk´ = lnk + n lnmcat.
´
If the value of r is known, the value of k can be determined
(
 = 1.5406 Å, graphite monochromator). The samples were
t
scanned over the 10  2  50 range at a voltage of 40 kV and
a current strength of 80 mA. The calculation by the Scherrer
equation showed that the particle size of the synthesized catalyst
[
ln(r – r )/(r – r )] = –k´t.
(5)

i

0
The value r = 6.5 was calculated by the Guggenheim
method17,18 from the data obtained at 353 K for a catalyst
weight of 3 g. This method assumes a linear dependence

(
D) was close to 70 nm.
Results and Discussion
Invertion of sucrose. Hydrolysis of sucrose affording
glucose and fructose in the presence of an acidic catalyst
proceeds via the known equation
of [ln(r – r )/(r – r )] on t (min). Since this depenꢀ

t

0
dence was observed in the plots obtained in the work,
the value of the constant k´ can be calculated from the
slope of the corresponding curves. The results obtained at
3
53 K for a catalyst weight of 3 g are shown as an example
in Fig. 2. The linear dependence (see Fig. 2) confirms that
the reaction is described by the firstꢀorder rate equation
with respect to sucrose. The linear character is also seen in
the plots of lnk´ vs lnmcat. This allows one to determine
rate constant k and reaction order n at 323—353 K from
the section cut in the ordinate and from the slope angle.
The corresponding data are given in Table 1.
С12Н22О11 + Н О
С Н О + С Н О .
6 12 6 6 12 6
2
The reaction is irreversible and follows a firstꢀorder
rate law with respect to the sucrose concentration. No
sucrose hydrolysis is observed in the presence of the SiO2
catalyst. Evidently, the hydrolysis is prevented by the stronꢀ
ger hydrophilic properties of SiO . A sample of V O /SiO
10 wt.%) turned out to be more active. In order to deterꢀ
mine the activity of this catalyst during the hydrolysis of
sucrose, we measured the kinetics of changing rotation
2
2
5
2
(
As known, if experimental data are approximated by
the Arrhenius equation in the linear form
k = Aexp[–E /(RT)],
(6)
angles r in different sugar solutions at different temperaꢀ
a
t
tures. The typical results at 353 K are plotted in Fig. 1.
The reaction rate is described by the following firstꢀ
order rate equation:
the plot of k vs 1/T will be a straight line. Then the activaꢀ
tion energy (E ) and preꢀexponential factor (А) can be
a
calculated from the slope of the straight line and the secꢀ
tion cut in the ordinate. The results of calculation are
plotted in Fig. 3.
R = kCsucmcatn,
(1)
where k is the rate constant, C is the sucrose concentraꢀ
suc
The Eyring equation can be used for the calculation of
tion (mol L– ), mcat is the catalyst concentration (g L ),
and n is the reaction order with respect to the catalyst.
Since the catalyst weight is constant in each experiment,
the equation rate can be written as follows:
1
–1
19
the enthalpy and entropy of activation


k = [RT/(Nh)]exp(TS /–H )/(RT),
(7)
where k is the rate constant. This equation can be reduced
R = k´Csuc
,
(2)
to the following form:
where


ln(k/T) = ln[R/(Nh)] + S /R — H /(RT).
(8)
k´ = kmcatn,
(3)
ln[(r – r )/(r – r )]

t

0
rt/deg
7
6
5
4
3
2
5
5
5
5
5
5
–
–
–
0.05
0.25
0.45
1
2
3
–0.65
–0.85
3
0
60
90
120
150 t/min
3
0
60
90
120
150 t/min
Fig. 1. Rotation angle r of the products of sucrose hydrolysis in
t
the presence of 3 (1), 5 (2), and 7 g (3) of the catalysts vs reaction
Fig. 2. Dependence of [ln(r – r )/(r – r )] on the reaction time

i
0
time at 353 K.
at 353 K (catalyst weight 3 g).

1824
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 9, September, 2012
Langeroodi et al.
Table 1. Rate constants of sucrose hydrolysis (k) on V O /SiO
2
at different temperatures
ln(k/T)
12
2
5
–
–
–
T/K T–1•104 k•10 /s
4
–1
(k/T)•107 –lnk
–ln(k/T)
13
14
3
3
3
3
23
33
43
53
30.95
30.03
29.15
28.32
1.25
2.10
5.70
3.86
6.30
16.61
56.09
8.99
8.47
7.47
6.22
14.76
14.28
13.31
12.09
19.80
–15
2
.9
3.0
T–1•10 /K
3
–1
Thus, the plot of ln(k/T) vs 1/T should be a straight line,
whose slope and the section cut by the straight line in the
ordinate can be used for the calculation of the activation
Fig. 4. Dependence of lnk on T–1 in the coordinates of the
Eyring equation.


enthalpy (H ) and activation entropy (S ). The obꢀ
,
tained results are shown in Fig. 4. The calculated values of
level of catalytic activity. Other advantages are the simꢀ
plicity of preparation, a high activity in hydrolysis, and a
low cost of manufacturing of this catalytic system.
#
–1
#
–1 –1
–1

H (kJ mol ), S (kJ mol
K ), E (kJ mol ), and
a
A for sucrose hydrolysis in the presence of V O /SiO are
2
5
2
given below.
H
S
A•10–10
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
Ea
8
4.84
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3
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1
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1
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2
1
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2
V O /SiO system adsorbs water not very strongly, and
2
5
2
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1
1
1
1
1
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–
–
–
6.5
7.5
8.5
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2
2
T–1•10 /K
3
–1
2
.9
3.0
Fig. 3. Dependence of lnk on T–1 in the coordinates of the
Arrhenius equation.
Received December 21, 2010