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Applied Surface Science xxx (2013) xxxxxx
a r t i c l e
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Article history:
Received 13 February 2013
Received in revised form 12 April 2013
Accepted 21 April 2013
Available online xxx
Keywords:
Adsorption
Malachite green
Dye
Organoclay
Modied clay
a b s t r a c t
The adsorption of toxic dye malachite green from aqueous efuents by organically modied clay was
studied in a batch system. The organoclay (OC) used was prepared by the intercalation of cationic surfactant hexadecyltrimethylammonium bromide in a Mexican montmorillonite. The effects of initial dye
concentration, temperature, pH, and contact time were investigated. The OC showed a high dye removal
(99.6%) from an initial dye concentration of 60 mg L1 at pH 6 and 25 C. The adsorption capacity was
independent of pH and increased with the temperature. Equilibrium data were well tted by Langmuir
adsorption model. The rate of sorption was adjusted to a pseudo second-order kinetic model.
2013 Elsevier B.V. All rights reserved.
1. Introduction
Malachite green (MG) is a synthetic dye (Fig. 1) which is widely
used as biocide in the aquaculture as well as a dye in textile industry.
It is also applied as a food coloring agent, food additive, medical disinfectant and anthelminthic [1,2]. However, despite its wide
use, MG represents a risk to the consumers of treated sh because
its adverse effects on the immune and reproductive systems, carcinogenic, genotoxic, mutagenic and teratogenic properties. For
these reasons and because that this colorant is highly accumulative
within edible sh tissues, a zero tolerance has been established. The
United States and the European Council have imposed a strict ban
on the use of malachite green in all categories of food-producing
sh [3]. In addition to this, discharge of MG into the hydrosphere
can cause environmental degradation as it gives undesirable color
to water and reduces sunlight penetration [14]. Therefore, it
is important to remove MG from aqueous efuents before they
are discharged into bodies of water. Many methods have been
developed for color removal such as electrocoagulation, otation,
chemical oxidation, ltration, ion-exchange, ozonation, membrane
separation and microbial degradation [5]. Adsorption processes are
0169-4332/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.apsusc.2013.04.097
Please cite this article in press as: S. Arellano-Crdenas, et al., Study of malachite green adsorption by organically modied clay using a batch
method, Appl. Surf. Sci. (2013), http://dx.doi.org/10.1016/j.apsusc.2013.04.097
G Model
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V
W
(1)
Please cite this article in press as: S. Arellano-Crdenas, et al., Study of malachite green adsorption by organically modied clay using a batch
method, Appl. Surf. Sci. (2013), http://dx.doi.org/10.1016/j.apsusc.2013.04.097
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Table 1
Freundlich and Langmuir parameters obtained for the adsorption of malachite green
on the organoclay at various temperatures.
Model
Constants
25 C
40 C
60 C
Freundlich
KF
1/n
R2
22.49
0.14
0.913
35.37
0.08
0.923
27.99
0.25
0.995
Langmuir
Q (mg g1 )
b (L mg1 )
R2
40.48
1.36
0.999
51.81
2.09
0.995
56.82
2.75
0.998
1
log Ce
n
(2)
(3)
99.6% in the pH interval 410. It is reported that MG color is stable in the pH range 37 and color reduction increases from pH 7
to 11 [26]. Furthermore, the MG molecules (pka = 10.3) get protonated in the acidic medium and deprotonated at higher pHs [5]. Also
surface groups of the OC (pHzpc = 8.0) are protonated below pH 8.
Consequently, there was no electrostatic attraction between MG
molecules and the OC. Therefore, the hydrophobic and chemical
interactions could be the major forces for adsorption. These mechanisms have been reported to explain the adsorption of Reactive
Red 141 [18], Direct Red 2 [21], Reactive Blue 19 [18], and tannins
[14] by OCs.
3.4. Effect of time
Fig. 4 shows the effect of time on the MG adsorption by the OC,
conducted at different temperatures ranging between 25 and 60 C.
All curves show that adsorption capacity increases with time. The
initial rate was rapid and thereafter it was gradual until the equilibrium was reached. The initial stage indicates rapid attachment
of MG molecules to the external surface of the OC. The second stage
is due to diffusion of solute molecules into pores of the adsorbent
or other surface reactions. The third step is the nal equilibrium
stage where MG diffusion is very slow due its low concentration.
The uptake of MG at the equilibrium was of 7.5 mg g1 (99.6% of
removal). As temperature increased, the time to reach equilibrium was lower. Specically, at 25, 40, and 60 C, the equilibrium
was reached in 240, 180 and 30 min, respectively. This implies
an increased surface activity and the kinetic energy of the solute
molecules, resulting in fast interactions between MG and the OC at
high temperatures.
3.4.1. Kinetic model
In order to investigate the sorption processes of MG onto the
OC, pseudo second-order kinetic model of adsorption was used.
This model was developed by Ho and Mckay [27], and is based on
the assumption that the chemical sorption is the rate-limiting step.
Its linear expression is:
t
1
1
=
+
t
qt
qe
k2 q2e
(4)
Please cite this article in press as: S. Arellano-Crdenas, et al., Study of malachite green adsorption by organically modied clay using a batch
method, Appl. Surf. Sci. (2013), http://dx.doi.org/10.1016/j.apsusc.2013.04.097
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Table 2
Pseudo-second order kinetic parameters obtained for the adsorption of malachite
green on the organoclay at various temperatures.
Model
Pseudo-second order kinetic
Constants
1
k2 (g mg min
qe (mg g1 )
R2
25 C
40 C
60 C
0.006
7.6
0.995
0.027
7.4
0.995
0.597
7.5
0.998
Fig. 5. Plot of ln b (b is the Langmuir constant) vs. 1/T for malachite green adsorption
on the organoclay.
S
H
R
RT
G = RT lnb
(5)
(6)
where b is the Langmuir constant (L mol1 ), R is the ideal gas constant (1.987 cal mol1 K1 ) and T is the absolute temperature (K).
The plot of ln b vs. 1/T was found to be linear (Fig. 5). The positive
H value obtained (3.9 kcal mol1 ) indicates that the adsorption
was endothermic. The S value obtained (26 cal mol1 ) reects
the afnity of the solid for MG [14].
The negative G value decreased with increased temperature.
Specically, at 25, 40 and 60 C the values obtained were 2.9,
4.15, and 4.6, respectively, indicating that the spontaneity of
adsorption is directly proportional to the temperature.
4. Conclusion
The organoclay prepared showed a 99.6% of aqueous malachite
green removal at initial concentrations of 60 mg L1 and a complete
removal at lower concentrations, according to the zero tolerance
imposed by several international legislations.
The Langmuir model predicted well the adsorption in the temperature interval of 2560 C. The adsorption was independent of
pH and increased with the temperature. The adsorption kinetic data
were well described using the pseudo-second order kinetic model,
implying that chemisorption could be the rate-controlling step.
Please cite this article in press as: S. Arellano-Crdenas, et al., Study of malachite green adsorption by organically modied clay using a batch
method, Appl. Surf. Sci. (2013), http://dx.doi.org/10.1016/j.apsusc.2013.04.097
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[23] C.H. Giles, T.H. Mac Ewan, S.N. Nakwa, D. Smith, Studies in adsorption. Part.
XI. A system of classication of solution adsorption isotherms, and its use in
diagnosis of adsorption mechanisms and in measurement of specic surface
areas of solids, Journal of the Chemical Society 3 (1960) 39733993.
[24] H.B. Senturk, D. Ozdes, A. Gundogdu, C. Duran, M. Soylak, Removal of phenol
from aqueous solutions by adsorption onto organomodied Tirebolu bentonite:
equilibrium, kinetic and thermodynamic study, Journal of Hazardous Materials
172 (2009) 353362.
[25] L. Juang, C. Wang, C. Lee, T. Hsu, Dyes adsorption onto organoclay and MCM-41,
Journal of Environmental Engineering and Management 17 (2007) 2938.
[26] I.D. Mall, V.C. Srivastava, G.V.A. Kumar, I.M. Mishra, Characterization and utilization of mesoporous fertilizer plant waste carbon for adsorptive removal
of dyes from aqueous solution, Colloids and Surfaces A: Physicochemical and
Engineering Aspects 278 (2006) 175187.
[27] H.S. Ho, G. McKay, The kinetics of sorption of divalent metal ions onto Sphagnum moss peat, Water Research 34 (2000) 735742.
[28] Y.L.L. Shu, Q. Zhang, H. Wu, Equilibrium, kinetics and thermodynamic studies
for sorption of chlorobenzenes on CTMAB modied bentonite and kaolinite,
Journal of Hazardous Materials 173 (2010) 4753.
Please cite this article in press as: S. Arellano-Crdenas, et al., Study of malachite green adsorption by organically modied clay using a batch
method, Appl. Surf. Sci. (2013), http://dx.doi.org/10.1016/j.apsusc.2013.04.097