Cent. Eur. J. Chem.

• 6(1) • 2008 • 99-105

DOI: 10.2478/s11532-007-0064-2

Central European Journal of Chemistry

Kinetic and anion degradation products study

on photocatalytic degradation of reactive
orange 5 solution with phosphotungstic acid

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Research article

Zhong Junbo1*, Zhao Hong2, Ma Di1, Lian An1, Li Minjiao1, Xie Bin1, Li Jianzhang1
1
Department of Chemistry, Sichuan University of Science and engineering,

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Zi gong, 643000, PR China

2
College of Environmental & Chemical Engineering,

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Dalian Jiaotong University, Dalian, 116026, PR China

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Received 12 September 2007; Accepted 22 November 2007

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Abstract: Increasing environmental pollution caused by toxic dyes is a matter of great concern due to their hazardous nature. So it is crucial
to develop processes which can destroy these dyes effectively. It has been generally agreed that reactive orange 5 (KGN) can be ef-
fectively degraded in aerated phosphotungstic acid (HPA) in a homogeneous reaction system using near-UV irradiation. In this paper,
photocatalytic degradation of reactive orange 5 solutions with phosphotungstic acid was investigated, especially more attention was
paid to the kinetic model and the anion degradation products. The results revealed that the photocatalytic degradation reaction of KGN
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with HPA in a homogenous solution can be described by Langmuir-Hinshelwood equation and Langmuir–Hinshewood kinetic model
described it well. The reaction manifested the first order with lower concentration(≤30 mg L-1) with the limiting rate constant and the
adsorption constant in this case being 0.8098 mg L−1 min−1 and 4.359 10−2 L mg−1, respectively. The degradation mechanism of KGN
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with HPA is different from that with TiO2, the anion products of the two reaction systems are the same. The difference in degradation
mechanism of KGN with HPA from that with TiO2 is caused by the nature of the photocatalyst.
Keywords: Phosphotungstic acid • Photocatalytic degradation • Reactive orange • Kinetics • Anion products

© Versita Warsaw and Springer-Verlag Berlin Heidelberg.

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1. Introduction effluents must be treated before being released into the

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aquatic and terrestrial environment [4].

There are several methods which are used to
Increasing environmental pollution caused by toxic dyes
decolorize textile wastewater, but they cannot be
is a matter of great concern due to their hazardous nature
effectively applied for all the dyes [5]. Activated carbon
[1]. Azo dyes, the largest class of synthetic dyes used
adsorption process for the removal of dyes is an accepted
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in food industries, are characterized by the presence

practice, but the cost of treatment is high. Ozone and
of one or more azo bonds (-N=N-) in association with
hypochlorite oxidations are effective decolorization
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one or more aromatic systems, which may also carry

methods, but they are not desirable because of the
sulfonic acid groups. Many studies indicate that these
high cost of the equipments, operating costs and the
dyes are toxic or carcinogenic. If these colorants come
secondary pollution arising from the residual chlorine
into contact with certain drugs in the human body they
[6].
can induce allergic and asthmatic reactions in sensitive
Therefore, there is currently a great deal of interest
people. An additional difficulty is that, when present,
in developing processes which can destroy these dyes
these dyes are not normally removed by conventional
effectively. Photocatalysis by solid polyoxometalate
wastewater treatment systems [2,3]. Therefore, the
(POM) is a new branch in the field of photocatalytic
employment of these dyes must be controlled and the

* E-mail: junbozhong@163.com
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 Kinetic and anion degradation products study
on photocatalytic degradation of reactive
orange 5 solution with phosphotungstic acid

chemistry, and has given rise to some attractive research
developments in recent years. POMs exhibit UV-light
photocatalytic activity in a homogeneous system [7]. In
fact, many of POMs share very similar photochemical
characteristics with the semiconductor photocatalysts.
POMs represent the analogues of semiconductor metal
oxides [8]. The photochemical behavior of POMs have
been extensively studied in homogeneous systems
[8-16]. However, kinetic studies on their photooxidative
behavior have received less attention compared to the
room. Then the mixture was put under UV illumination at
a distance of 15 cm while being agitated continuously to
keep it uniform. Samples were withdrawn at specific time
intervals and changes in the concentration of KGN were
measured using the spectrophotometer at 485 nm.
Chromatography spectrum of the KGN solution was
carried out on a waterTM 600E chromatogram.
35

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30 5
semiconductor photocatalysts.

Concentration of KGN[mg/L]
Reactive Orange 5 (KGN) is a water-soluble azo
25 4
dye, which is widely applied in the tanning and textile
industries. The toxic nature of the dye is still not

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20 3
quantified much, but its high content in living systems
can prove to be harmful. Thus, in the present paper, 15 2

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KGN was chosen as the model azo dye.
In this paper, we studied the kinetic and anion 10 1
degradation products obtained from the photocatalytic

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degradation of KGN with phosphotungstic acid (HPA), 5
wherein the initial reaction rate and its relating factors
were emphasized. Efforts were put to draw conclusions
on the apparent kinetic model and the effects of initial
concentration. It was noted here that besides the
A 0
0 10 20 30
Re action time [min]
40 50 60

understanding of the role of photo-catalyst, consideration
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must be paid to the nature of the photocatalyst. The
structure of reactive orange 5 is given in Fig. 1.
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Figure 2. Plot of photo-degradation of KGN vs. irradiation time (1)
10 mg L−1 (2) 15 mg L−1 (3) 20 mg L−1, (4) 25 mg L−1
(5) 30 mg L−1.

SO3Na 1. 8
H H 1
N N N SO3Na 1. 6
2
1. 4 3
N N
N N
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1. 2 4
SO3Na Cl OH SO3Na
ln(C0/Ct)

1 5
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Figure 1. Structure of Reactive Orange 5. 0. 8

0. 6
2. Experimental
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0. 4
0. 2
2.1. Materials and instruments
Analytical grade HPA was purchased from Chendu 0
0 10 20 30 40 50 60 70
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Kelong Chemical Reagents Factory and used as

Reaction time [min]
received. Reactive Orange 5 was donated by Dalian
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University of Technology.
A Shimadzu UV-120-02 spectrophotometer, an
HY-4 vibrator and a 20W medical violet lamp (Philips,
with maximum emission at 254 nm) were used in the
experiments. Water used in the experiments was
deionized and fully aerated with oxygen (DO is 8.8 mg L-1).
2.2. Procedures
A quartz tube (1.5 cm diameter, 100 cm length) was used
as the reactor. 100 mL KGN solution containing 60 mg
HPA was introduced into the reactor each time in the dark
Figure 3. ln(C0/Ct) vs. illumination time (1) 10 mg L−1 (2) 15 mg L−1
(3) 20 mg L−1 (4) 25 mg L−1 (5) 30 mg L−1.
3. Results and discussion
3.1. Blank experiments
The contrast experiments were carried out in two
conditions: one with HPA but no illumination, the other
with illumination but no catalyst. The results showed that
the concentration of KGN solution (10 mg L−1) remained
the same under the former condition, while in the latter

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Z. Junbo et al.

4.5 1.791
0.008
y = 28.06x + 1.2367
4 0.006
R2 = 0.9889

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0.004
3.5
0.002
1/r0[Lmin/mg ]

3 0.000

200.00 250.00 300.00 350.00 400.00 450.00 500.00 550.00 600.00

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nm
2.5
Figure 6. The UV-vis spectrum of KGN.

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1.5
0.02 0.04 0.06 0.08 0.1 0.12

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1/C0[L/mg]

Figure 4. The linear transformation of 1/r0 vs. 1/C0.

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0.007 2 .0 0 4 .0 0 6 .0 0 8 .0 0 1 0 .0 0
M in u t e s
0.006

0.005

0.004
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Figure 7. Chromatography spectrum of KGN after 2 h of irradiation
with H3PW12O40.
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0.003
of the normalized concentrations versus irradiation time
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0.002
for KGN at five low initial concentrations (≤30mgL-1). The
0.001
logarithmic transforms for these concentration curves
0.000
are shown in Fig. 3. The degradation rates fit a first-order
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1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00
Minutes
model well, that is, the integral equation of ln(C0/Ct) =
Figure 5. Chromatography spectrum of KGN. Kobst describes the tendency well, where C0 and Ct are
case it changed so little that it could be ignored (during the concentrations of KGN at time 0 and t, respectively,
90 min time period). The blank tests proved the stability and Kobs is the observed pseudo first-order rate constant.
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of KGN. Without illumination or photo-catalysts, KGN The slope of a liner plot of ln(C0/Ct) versus time gives
the apparent degradation rate constant. To make the
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is kinetically stable. It also suggested that the dark

adsorption for KGN from aqueous HPA was small, further mathematic inferences clear, all the related
therefore the adsorption equilibrium could be established kinetic parameters, such as the reaction rate constants
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quickly. (Kobs), half-life (t0.5), and interrelated coefficients (R)

of the lines in Fig. 2, are all presented in Table 1. It is
clear that the rate constant is inversely proportional to
3.2. Kinetics on the destruction of KGN the initial concentration of KGN to the lowest limit of 30
In general, for TiO2 heterogeneous reaction system, the
mgL−1. The decrease of Kobs with the increasing initial
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kinetics would follow the Langmuir-Hinshelwood (L-H)

KGN concentration indicates that there is a competition
model [17-20]. Mylonas [21] and Turchi [22] reported that
between the instantaneous intermediates and KGN for
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the kinetics also follow the L-H model for homogeneous

the oxidant [17]. During the process of degradation,
reaction system.
the higher the initial concentration is, the more the
dCt kKCt (1)
r=− = intermediates appear, and the stronger the negative
dt 1 + KCt
effects on the apparent reaction rate constant. With
Where r is the photocatalytic degradation rate; k is the
regard to the negative effect of initial concentration, it
L–H rate constant; K is the Langmuir adsorption constant
can be speculated to be caused by the limited dosage
of the KGN in the photocatalytic degradation reaction;
of oxidants which is fixed in our case because the
and Ct is the concentration of KGN under study.
intermediates would compete with KGN for the oxidant.
Fig. 2 and Fig. 3 show information on the
Considering the results above, the adsorption process
kinetics of photocatalytic degradation for five various
can be excluded from the rate-determining step; hence
concentrations under identical conditions. Fig. 2 is a plot

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 Kinetic and anion degradation products study
on photocatalytic degradation of reactive
orange 5 solution with phosphotungstic acid

Table 1. Parameter and reaction kinetic equation for different initial concentration.

C0/mgL-1 reaction kinetic equation rate constant t0.5(min) R

10 ln(C0/Ct)=0.0276t+0.0032 0.0276 min-1 25.00 0.9889
15 ln(C0/Ct=0.0244t+0.0077 0.0244 min-1 28.09 0.9998
20 ln(C0/Ct=0.0213t+0.0088 0.0213 min -1
32.13 0.9990
25 ln(C0/Ct=0.0194t+0.0120 0.0194 min-1 35.11 0.9997
30 ln(C0/Ct=0.0173t+0.0273 0.0173 min-1 38.49 0.9990

Table 2. Relating kinetic parameters on the photo-degradation of KGN.

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C0/mg L-1 1/C0(L mg-1) r0(mg L-1min-1) 1/r0(L minmg-1)
10 0.10 0.2451 4.0800
15 0.0667 0.3333 3.0000

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20 0.0500 0.3745 2.6702
25 0.0400 0.4081 2.4504

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30 0.0333 0.4717 2.1200

the oxidation reaction is probably the rate-determining were obtained using linear least squares analysis. The
step. value of k and K are 0.8098 mg L-1 min-1 and 4.359

Further information about r0 ( the initial rate) of the
five low initial concentrations (≤30 mg L-1) is shown in
Table 2.
Owing to the complex mechanism of reactions, it is
difficult to develop a model for the dependence of the
photocatalytic degradation rate on the experimental
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parameters for the whole treatment time. Thus, kinetic
modeling of the photocatalytic process is usually
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R
10-2 L mg-1 respectively. It is clear that a good fitting of
the model to the experimental data may be observed
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thus confirming the L-H nature of the photocatalytic
degradation reaction mechanism.
Actually, L–H kinetic model has successfully
described many similar homogeneous photocatalytic
systems [21-24].

restricted to the analysis of the initial rate of photocatalytic
degradation. This can be obtained from the initial
slope to the curves and the initial concentration in an
experiment in which the variation of the concentration
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3.3. Anion products investigation during
photocatalytic oxidation
The objective of Chromatogram experiments was to
identify the reaction intermediates and products during

is measured as a function of time. The extrapolation photocatalytic oxidation. In general, such information
of the photocatalytic degradation rate to time=0 avoids can provide a vital understanding of the mechanism. The
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the possible interference from by-products. The initial chemical chromatogram during photocatalytic oxidation
photocatalytic degradation rate (r0) is observed to be a was analyzed. As shown in Fig. 5, the residence time
function of the initial concentration (C0). A linear plot of
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(RT) of KGN solution is 1.791 min, wherein the initial

r0-1 vs. C0-1 is often obtained, and that gives k as the concentration of the solution is 10 mg L-1.The UV-
L–H rate constant and K as the Langmuir adsorption vis spectrum of KGN solution is shown in Fig. 6. The
constant of the KGN in the photocatalytic degradation chromatography spectrum of KGN after 2 hours of
reaction [18]. kKc0 irradiation with H3PW12O40 is shown in Fig. 7. As shown
r0 =
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1 + Kc0 (2) in Fig. 7, the RT is 1.919 min, which indicates that KGN
The equation is further expressed in a linear form: has been degraded. This result can be further confirmed
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1 1 1 by the UV-vis spectrum of KGN after 2 h of irradiation

=
+ (3)
r0 kKc0 k
In order to find the effect of initial concentration
on the photocatalytic degradation and half life, more
detailed analyses were done based on the kinetics of
the photocatalytic degradation. Fig. 4 shows the plot of
the reciprocal of the initial rate r0-1 versus the reciprocal
of the initial concentration C0-1 for photocatalytic
degradation of KGN. The kinetic parameters k and K
with H3PW12O40, as shown in Fig. 8. Compared with
Fig. 6, the peaks from 350 nm to 550 nm disappeared,
which suggests that the N=N has been destroyed,
however, there is still a peak from 250 nm to 300 nm.
This result clearly shows that the KGN has not been
degraded totally, and that some intermediates are
present in the reaction system. The fact that no benzene
was detected (RT is 2.8-2.9 min) suggests that ring
of benzene in the KGN molecule has been attracted.

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Z. Junbo et al.

0.25
1.919

0.20

0.15
AU

0.10

0.05

0.00 2 .0 0 4 .0 0 6 .0 0 8 .0 0 1 0 .0 0
200.00 250.00 300.00 350.00 400.00 450.00 500.00 550.00 600.00
M in u t e s
nm

Figure 9. Chromatography spectrum of KGN after 2 h of irradiation

Figure 8. The UV-Vis spectrum of KGN after 2 h of irradiation with with TiO2.
H3PW12O40.

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is unclear and so further attention should be focused
To further investigate the photocatalytic oxidation
on the mechanisms of HPA in photocatalytic reaction.
mechanism of KGN as to whether or not it is the same
More information will be needed to understand the
as the photocatalytic oxidation mechanism of KGN with
photocatalytic process better. In fact, all these results

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TiO2 reaction system, the investigation of intermediate
are attributed to the nature of the photocatalyst itself,
products during photocatalytic oxidation with TiO2 reaction
thus the photocatalytic degradation of KGN manifests a

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system was carried out, and the results are shown in
different photocatalytic degradation mechanism using a
Fig. 9, Fig. 10 and Fig. 11 (initial KGN concentration
different photocatalyst in our case.
is 10mg L-1,TiO2 is 600mg L-1). It is clear that the
However, the difference in the photocatalytic

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chromatogram and the spectrum results are greatly
degradation mechanism of the two photocatalysts does
different from the results of the reaction system with
not mean that the anion products would be different. The
HPA, which indicates that the photocatalytic oxidation
mechanism with HPA is different from the mechanism
with TiO2. Based on all these results, it is clear that in
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anion products of the two reaction systems are shown
in Table 3.
Shown in Table 3, NH4+, NO3- and Cl- were detected
our case the degradation mechanisms of KGN in the two
soon after the photocatalytic reaction. Cl- comes from –Cl,
reaction systems are different. Some researchers have
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NH4+ may form by attacking -NH- in the KGN molecule,
reported that the degradation products are the same for
then NH4+ can be further oxidized into NO3-. Sheng and
a pollutant using POM,TiO2 and H2O2 as photocatalysts
Feng [33] have reported that –N=N- would form N2. As
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[21,25-27], but in our case, the degradation mechanism

shown in Table 3, after 10 hours of irradiation, the anion
of KGN with HPA is different from that of with TiO2.
products in the two reaction system have an obvious
This suggests that for the degradation mechanism of
difference. In the H3PW12O40 reaction system SO42- was
KGN with HPA, there may exist another degradation
not detected, while in the TiO2 reaction system SO42-
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mechanism besides the mechanism wherein OH

was detected. To exclude the effect of reaction time,
radicals attack. Some studies have reported that HPA
the anion products were investigated after 12h and
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can directly photocatalytically degrade the pollutants

15h. After 12 hours of irradiation, SO42- was detected
by abstracting H atom from the pollutants [28-32].
in H3PW12O40 reaction system, while after 15 hours of
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Based on the above results, it is plausible that there

irradiation (the removal of Total Organic Carbon in both
is a synergistic effect between the oxidation of •OH
reaction system is 100%), SO42- was detected in both
and the direct photocatalysis of KGN with H3PW12O40.
reaction systems. SO42- comes from –SO3Na.
However, the role of HPA in the photocatalytic reaction
In fact, some results are speculated based on the
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Table 3. Anion products of photocatalytic degradation of KGN.

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catalyst time/h 0 0.5 1 1.5 2 4 6 8 10 12 15

HPA Cl- × √ √ √ √ √ √ √ √ √ √
SO42- × × × × × × × × × √ √
NH4+ × √ √ √ √ √ √ √ √ √ √
NO3 -
× √ √ √ √ √ √ √ √ √ √
TiO2 Cl- × √ √ √ √ √ √ √ √ √ √
SO42- × × × × × × × × √ √ √
NH4+ × √ √ √ √ √ √ √ √ √ √
NO3 -
× √ √ √ √ √ √ √ √ √ √
√: the product was detected; ×: the product was not detected

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 Kinetic and anion degradation products study
on photocatalytic degradation of reactive
orange 5 solution with phosphotungstic acid

1.888 2.222
0.000
0.08
-0.002
0.06
-0.004
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AU
-0.006 0.04

-0.008
0.02
-0.010
0.00
200.00 250.00 300.00 350.00 400.00 450. 00 500.00 550.00 600.00 200.00 250.00 300.00 350.00 400.00 450.00 500.00 550.00 600.00
nm nm

Figure 10. The UV-Vis spectrum of KGN at 1.888 after 2 h of ir- Figure 11. The UV-Vis spectrum of KGN at 2.222 after 2 h of ir-
radiation with TiO2. radiation with TiO2.

experimental phenomena, however further study will
be needed. More considerations should be focused on
the mechanisms of HPA in the photocatalytic reaction.
Knowledge about the mechanism of the system
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Mathematical inference showed that the limiting rate
constant and the adsorption constant in this case were
0.8098 mg L−1 min−1 and 4.359 10−2 L mg−1, respectively.
The photocatalysis degradation mechanism of KGN with

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possesses both practical and theoretical values. H3PW12O40 was illustrated, where special attention was
paid to the nature of the photocatalyst itself. The anion

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products of the two reaction systems are the same.
4. Conclusions

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This paper revealed that the photocatalytic degradation
of KGN was a pseudo first-order reaction when the
concentration of KGN is below 30mgL-1 and the
Langmuir–Hinshewood kinetic model describes it well.
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