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457-469, 2014
Available online at http://www.ijsrpub.com/ijsres
ISSN: 2322-4983; 2014; Author(s) retain the copyright of this article
http://dx.doi.org/10.12983/ijsres-2014-p0457-0469
Abstract. Congo Red in aquatic system has been recognized as a serious problem in living organism because of its toxic nature
and therefore, its degradation is highly essential. In the present work, the efficacy of thermally activated ZnO was studied for
photo-catalytic degradation of Congo red (CR) dye. The batch operation was carried out by irradiating the aqueous solution of
dye in the presence of semiconductor. The effect of various parameters such as catalyst loading, pH, oxidant dose, intensity
variations and initial concentration of the dye on degradation was investigated. The maximum degradation capacity of ZnO for
CR was found to be 11.8 mg g-1 at optimized condition [303 K, 60 min, pH (8), dose (0.05g)]. The pseudo-second-order kinetic
model described the CR degradation process with a good fitting. Thermodynamic parameters such as H, S, and G were
calculated, which indicated that the process was spontaneous and exothermic in nature, that was evident by increasing the
randomness of the dye at the solid and liquid interface. The high CR degradation ability and regeneration efficiency of this
photocatalyst suggest its applicability in industrial systems and data generated would help in further upscaling of the
degradation process.
Keywords: Congo Red; Kinetic model; Photo-catalytic degradation; Thermodynamic study; Zinc Oxide
1. INTRODUCTION
Environmental problems associated with organic
pollutants promote the development of fundamental
and applied research in the area of environment
(Ahmad et al., 2011). Several of these chemicals such
as azo dyes, herbicides and pesticides are actually
present in rivers and lakes, and are in part suspected of
being endocrine-disrupting chemicals (Ohko et al.,
2001; Coleman et al., 2000; Wang and Hong, 2000;
Hong et al., 1998). Synthetic dyes are the major
industrial pollutants and water contaminants
(Modirshahla et al., 2007). These dyes are used
extensively in the textile industry for dying nylon,
cotton, wool, and silk, as well as for colouring oils,
fats, waxes, varnishes, and plastics. The paper, food,
cosmetic, and leather industries are also major
consumers of these dyes (Chen, 2007).
The discharge of dye-coloured wastewaters into
the aquatic ecosystem represents both environmental
and public health risks because of the negative
ecotoxicological effects and bioaccumulation in
wildlife. Most importantly, many dyes contained in
wastewaters can decompose into carcinogenic
aromatic amines under aerobic conditions which can
cause serious health problems to humans and animals
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International Journal of Scientific Research in Environmental Sciences, 2(12), pp. 457-469, 2014
(2)
where Co is the initial dye concentration (mg/L), Ct
is the concentration of the dye at any time t, V is the
volume of solution (L) and m is the mass (g) of zinc
oxide powder (ZnO).
(1)
The dye removal efficiency i.e., % of degradation
was calculated as
Parameter
Only UV(Without ZnO)
Only ZnO(without UV)
Both ZnO & UV
Removal (%)
0.00
47.95
96.45
Kinetic model
Pseudo
first
Equation
)
Constants
qexp (mgg-1)
qcal(mgg-1)
R2 = 0.995
order
KL = 0.0819 min-1
11.50
12.03
R2 = 0.9999
K2 = 0.0586 g.mg1
min-1
Pseudo second
order
11.8 mg.g-1
qt and qe are the amount of dye adsorbed (mg g-1) at time t and at equilibrium and KL (min-1) is the Lagergren rate constant of rst-order degradation and K2 (g
mg-1 min-1) is the second-order degradation rate constant.
Table 3: Thermodynamic parameters for adsorption of Congo Red onto ZnO particles
Temperature(K)
303
323
343
373
-10.0680
-9.6690
-10.1138
-10.8370
-6.335
11.45
2.5. Photocatalysis
Photocatalysis may be termed as a photoinduced
reaction which is accelerated by the presence of a
catalyst (Mills et al., 1997). These types of reaction
are activated by absorption of a photon with sufficient
energy (equal or higher than the band gap energy of
the catalyst (Carp et al., 2004). The absorption leads
to a charge separation due to promotion of an electron
(e-) from valence band of the semiconductor catalyst
to the conduction band, thus generating a hole (h+) in
the valence band (Gaya et al., 2008).
The
recombination of the electron and the hole must be
prevented as much as possible if a photocatalyst
459
100
18
80
Removal(%)
16
B
C
14
70
12
60
50
10
Degradation Capasity(mg/g)
90
40
8
0.02
0.03
0.04
0.05
0.06
Catalyst Dose(g)
Fig. 1: Effect of catalyst dose on photodegradation of CR dye (6 ppm), pH (8.0), Temp. (303K),
11.60
96
11.55
11.50
Removal(%)
11.45
11.40
11.35
11.30
94
11.25
Degradation Capasity(mg/g)
B
C
11.20
11.15
4
10
pH
3.2. Effect of pH
The effect of initial solution pH on the degradation
capacity at equilibrium conditions is shown in Figure
2. The results indicate that the dye degradation
capacity increased from 11.2 mg/g to 11.8 mg/g with
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International Journal of Scientific Research in Environmental Sciences, 2(12), pp. 457-469, 2014
100
Removal(%)
80
10
70
60
8
Degradation Capasity(mg/g)
12
90
50
10
Concentration(ppm)
Fig. 3: Effect of concentration on photodegradation of CR dye pH (8.0), ZnO (0.5mg/L), Temp. (303K),
min)
461
B
C
12
98
96
92
90
Removal(%)
88
86
84
10
82
80
78
76
74
Degradation Capasity(mg/g)
94
72
70
240
8
260
280
300
320
340
360
Wave Length(nm)
Fig. 4: Effect of wave length on photodegradation of CR dye, (6 ppm), pH (8.0), ZnO (0.5mg/L), Temp. (303K), Time (60
min)
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International Journal of Scientific Research in Environmental Sciences, 2(12), pp. 457-469, 2014
11.60
B
C
96
Removal(%)
11.50
11.45
11.40
Degradation Capasity
11.55
11.35
11.30
94
20
30
40
50
60
70
80
90
100
110
Temperature(C)
98
Degradation capasity
96
Removal(%)
94
B
C
92
90
88
86
84
0
20
40
60
80
10
100
Contact Time(min)
Fig. 6: Effect of contact time on photodegradation of CR dye (6 ppm), pH (8.0), ZnO (0.05mg), Temp. (303K),
(254 nm)
463
Fig. 7: Pseudo-first-order kinetics for degradation of Congo Red by photocatalytic agent ZnO
Fig. 8: Pseudo-second-order kinetics for degradation of Congo Red by photocatalytic agent ZnO
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International Journal of Scientific Research in Environmental Sciences, 2(12), pp. 457-469, 2014
4. CONCLUSION
The active species generated in the degradation of CR
under uv light irradiation were studied using thermally
heated ZnO as model systems. The present
investigation shows that zinc oxide can be utilized for
the removal of hazardous dye from aqueous solution.
The removal process is a function of shaking time,
465
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International Journal of Scientific Research in Environmental Sciences, 2(12), pp. 457-469, 2014
Mr T. K. Roy received his M.Sc. degree in Chemistry (Organic Chemistry) from the faculty
of Science, Visva-Bharati Unviersity, Santiniketan.
Dr Naba Kumar Mondal presently holding the position as Assistant professor in the
department of Environmental Science, The University of Burdwan, India. Dr Mondal has
experience more than 16 years of teaching and research in both Education and
Environmental Science (masters degree). His research interest includes: Pure
Science:Adsorption Chemistry, Nutrient dynamics, indoor pollution, soil Chemistry, Plant
Physiology, Social Science: corporal punishment, development of teaching methodology,
noise and its impact on school children etc. Dr Mondal also published more than 130
research papers in reputed International and National Journals and four (04) Ph.D. scholars
(upto May 2014) and has been serving as an guest Editor and reviewer in many prestigious
International Journals.
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