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prepared and systematically studied for its adsorption behavior as an efcient adsorbent
for the removal of basic dyes such as methylene blue (MB), crystal violet (CV) and Rho-
February 2015
damine B (RB) from aqueous phase. Organo modied clay shows better capacity for the
removal of three dyes. The adsorption process was found to be dependent on pH and initial
dye concentration. The maximum dye sorption was found to be at a pH of 9.0 (99.99% for
MB, 95.0% for CV and 83.0% for RB). The adsorption capacity for the dyes was found to be
Keywords:
399.74, 365.11 and 324.36 mol/g for MB, CV and RB, respectively at 30 C. The equilibrium
Bentonite
uptake was attained within 240 min. The kinetic studies were revealed that sorption follows
Organoclay
Adsorption isotherm
Adsorption kinetics
which t with Freundlich isotherm model. The tness of kinetics and isotherm models was
evaluated by using HYBRID error analysis function. Competitive adsorptions of dyes were
Basic dyes
1.
Introduction
216
2.
2.1.
Materials
The basic dyes used in this study were methylene blue (MB),
Rhodamine B (Rh-B) and crystal violet (CV). The dyes were
used as such without any further purication and were purchased from Fluka, Switzerland. The structures of these dyes
are shown in Fig. 1. The aqueous solutions of dyes were
prepared by dissolving denite amount of dyes in distilled
water within the concentration range 2001000 mol/L. The
surfactant hexadecyltrimenthylammonium chloride was purchased from Aldrich Chemicals (USA). Commercially available
bentonite clay was purchased from SigmaAldrich Chemie
(Germany). The cation exchange capacity (CEC) of the bentonite clay was found to be 0.52 mmol/g.
2.2.
Preparation of organoclay
2.3.
Instrumental studies
217
H 3C
CH3
N
Cl-
N
C
H3C
CH3
Cl-
CH3
CH3
N
H 3C
H 3C
CH3
(A)
CH3
(B)
COOH
CH 3
CH 3
O
CH 3
ClN
CH 3
(C)
Fig. 1 Structures of basic dyes: (A) Methylene Blue, (B) Crystal violet and (C) Rhodamine B.
2.4.
0 =
(1)
218
Parameters
Surface area (m2 /g)
Zeropoint charge
Density (g/cm3 )
Porosity (mL/g)
Particle size (mm)
CEC (meq/g)
Na-bentonite
36.5
4.5
1.25
0.28
0.096
0.52
Organoclay
27.9
7.8
1.48
0.40
0.096
0.71
2.5.
Volume of N2 adsorbed
[mL(STP)/g]
40
30
20
organo clay
10
Na-bentonite
0
0
P/Po
Fig. 2 Adsorption isotherms of N2 /77 K of Na-bentonite
and organoclay.
Adsorption experiments
The concentration of dyes in samples was determined during adsorption experiments (single-component system) by
using UV-Visible spectrophotometer (model Jasco model V530) at maximum wavelength absorption for each dye. The
max for each dye was 662, 591 and 554 nm for MB, CV and
RB respectively. Adsorption equilibrium studies were done by
treating 0.1 g of organoclay with 50 mL of various dye solutions
(2001000 mol/L) in a stoppered bottle and they were placed
in a temperature controlled water bath shaker (Labline, India).
The pH of the solution was calibrated by using NaOH and HCl
with a -362 pH meter (systronics). After the completion of
the reaction period (4 h), the asks were taken out and the dye
concentrations were determined.
Adsorption studies were also performed to determine the
competition among various binary solution mixtures (MB-RB,
MB-CV and RB-CV). Batch experiments were performed using
50 mL binary mixture solutions containing varied concentration of dyes with 0.1 g of the adsorbent in 100 mL stoppered
asks. The contents were shaken over a water bath shaker
with a constant speed of 200 rpm at pH 9.0 and 30 C. Then, the
equilibrium samples were withdrawn and centrifuged, and
supernatants were analyzed for dye concentrations by using
the following equations.
CA =
KB2 d1 KB1 d2
KA1 KB2 KA2 KB1
(2)
CB =
KA1 d2 KA2 d1
KA1 KB2 KA2 KB1
(3)
3.
3.1.
Characterization of organoclay
219
Counts
Organoclay
Transmitance (%)
RB - Organoclay
Na-B
CV - Organoclay
10
15
20
25
30
35
40
45
0
50
2Theta
MB- Organoclay
O rga noclay
Na-Bentonite
400
-1
220
120
120
100
100
Na-bentonite
80
MB
CV
RB
80
organoclay
60
60
MB
40
20
40
Adsorption(%)
Adsorption (%)
20
100
80
Na-benton ite
60
organoclay
Initial concentration : 40 0 mol/L
pH
: 9.0
: 6h
Equilibrium time
40
20
MB
CV
RB
100
80
CV
60
Initial concentration :400 mol/L
T emperature : 30 0 C
40
20
100
0
80
Na-benton ite
60
organoclay
Initial con centration : 40 0 mol/L
pH
: 9.0
Equilibrium time
: 6h
40
20
10 0
20 0
30 0
RB
40 0
10
12
50 0
3.2.
Effect of surface modication on the adsorption of
dyes onto organoclay
Batch experiments were carried out in order to evaluate the
effect of surface modication on the efciency of dye removal.
Fig. 6 shows the percentage removal of dye from aqueous
solutions as a function of adsorbent dose at a dye concentration of 400 mol/L. As expected the adsorption efciency
increased with the increase in the amount of adsorbent, however this did not occur in a steady progression. From the results
obtained it was observed that organoclay is 1.6, 1.7 and 1.75
times effective than Na-bentonite for the removal of MB, CV
and RB respectively. This is due to the fact that after modication, the surface area of the clay increases and its porosity
also increases. Increasing dose increases the partitioning of
per gram of adsorbent, which leads to an increase in adsorption. As a result more adsorbate molecules can be bound to
adsorbent surface through chemical bonding.
3.3.
pH
0
0
Effect of pH
50 mL of each of dye solutions was treated with 0.1 g of adsorbent at different pH (2.011.0) in 100 mL stoppered bottles.
The results are shown in Fig. 7. From the results it was
observed that increase in pH increases the adsorption. As the
pH of the solution increases, the positive charge on the surface decreases and the number of negatively charged sites
increases (Baskaralingam, 2006). A negative charged surface
site on the clay favors the adsorption of cationic dye due to
electrostatic attraction. Earlier works reported that cationic
dye sorption increases with increase in pH (Gupta et al., 2004;
Singh et al., 2003). From Fig. 7, it was found that the adsorption
capacity of the organoclay for dyes at initial concentrations
of 200 and 400 mol/L was 99.0 and 97.0 mol/g for MB, 95.0
and 184.0 mol/g for CV and 90.0 and 174.0 mol/g for RB,
respectively at pH 9.0. The order of afnity based on the
amount of dye uptake is as follows: MB > CV > RB. The order
of afnity is due to the fact that different dyes will experience
different physical and electrostatic forces according to their
structure, molecular size and functional groups (Allen et al.,
1989). Basically, methylene blue and other cationic dyes produce molecular cations (C+ ) and reduced ions (CH+ ) (Kavitha
and Namasivayam, 2007). At lower pH range the decrease in
adsorption is due to the electrostatic repulsion between the
cationic dye species and the protonated adsorbent surface.
However, after the surface modication the adsorbent surface
becomes more positive and the pHzpc is found to be 7.8. But
the optimum removal was observed at pH 9.0. Above the pHzpc
surface is negative and adsorption occurring by electrostatic
attraction between negative surface of adsorbent and cationic
dye species (Janos et al., 2003).
The mechanism of this adsorption process is also
explained on the basis of adsorption/partition model (Zhu and
Chen, 2000). On the basis of this model, they have pointed
out that the organic fraction of the surfactant modied clays
221
with long alkyl chains behaves mechanistically as a partition medium (Zhu and Su, 2002; Rawajh and Nsour, 2006),
where clay mineral acts as the conventional adsorbent in the
uptake of organic compounds (Jang and Kamens, 1999; Grate
et al., 1995; Burg et al., 2000, 2002). Adsorption of organics onto
clay minerals may occur through ion exchange, protonation,
hydrogen bonding and iondipole reactions. Partition occurs
through the interaction of the organic solutes with organic
fraction of the organoclay. For organoclay, the HDTMA surfactant evidently modies interlayer spaces by close packing of
the alkyl chains to create hydrophobic regions. Partition of the
dyes into hydrophobic regions plays an important role in dye
uptake. Moreover, in clay-aqueous systems the potential of the
surface is determined by the activity of ions (e.g., H+ or pH),
which react with the mineral surface. For clay minerals the
potential determining ions are H+ and OH and complex ions
formed by bonding with H+ and OH .
At high pH the reaction is:
SiOH + OH SiO + H2 O
(4)
200
150
MB
100
CV
50
RB
0
50
100
150
200
250
300
Time (min)
Fig. 8 Effect of contact time on the adsorption of MB, CV
and RB onto organoclay.
3.5.
Adsorption kinetics
250
(5)
k2 q2e t
1 + k2 qe t
(6)
400
3.4.
350
Equilibrium Time : 4 h
300
Temperature
pH
250
: 30 C
: 9.0
200
150
MB
100
CV
50
RB
0
0
20 0
40 0
60 0
800
100 0
120 0
C0 (mol/L)
Fig. 9 Effect of initial concentration on the adsorption of
dyes onto organoclay.
222
250
500
A
200
150
T heoretical
Initial concentration : 400 mol/L
pH
: 9.0
: 30 0 C
T emperature
50
Langmuir
MB
CV
RB
200
B
150
Exp erimental
MB
CV
RB
T heoretical
Initial concentration : 400 mol/L
pH
: 9.0
T emperature
: 30 0 C
50
Freundlich
Redlich peterson
Equilibrium T ime : 4 h
T emperature
: 30 0 C
pH
: 9.0
100
200
100
Exp erimental
300
Exp erimental
100
MB
400
CV
350
300
250
Experimental
Langmuir
Freundlich
Redlich peterson
200
150
100
Equilibrium T ime : 4 h
T emperature
: 30 0 C
pH
: 9.0
50
0
0
50
100
150
200
250
RB
300
300
250
Time (min)
200
Fig. 10 Plots for (A) pseudo-rst-order, (B)
pseudo-second-order model for the adsorption of MB, CV
and RB onto organoclay.
Experimental
150
Langmuir
100
50
0
0
MB
CV
RB
1.46 101
19.11
6.19
2.69 102
44.23
7.06
2.49 102
48.17
4.57
Pseudo-second-order
1.43 102
k2
2
0.37
0.37
HYBRID
2.99 104
3.32
1.49
4.96 104
0.75
1.12
200
300
400
500
Peterson isotherms (Fig. 11). The non-linear forms of equations are given as,
Adsorption isotherm
100
Ce (mol/L)
qe =
3.6.
Freundlich
Redlich peterson
Equilibrium T ime : 4 h
: 30 0 C
T emperature
: 9.0
pH
Q 0 bCe
1 + bCe
(7)
1/n
qe = KF Ce
qe =
(8)
KR Ce
1 + aR Ce
(9)
3.6.1.
Error analysis
In order to check the best t isotherm model to the experimental data, the hybrid fractional error analysis (HYBRID) was
chosen.
223
400
Isotherm constants
MB
CV
CV adsorbed (mol/g)
Langmuir
Q0 (mol/g)
b (L/mol)
2
HYBRID
399.74
0.04
8.75
0.86
365.11
0.02
7.68
5.72
324.36
0.01
1.08
1.31
Freundlich
KF
1/n
2
HYBRID
81.76
0.28
0.44
0.29
35.59
0.39
0.73
0.63
18.64
0.46
0.48
1.20
350
Initial CV concentration
300
200
800
250
200
150
100
0.98
0.04
0.84
0.47
0.99
0.023
0.94
1.34
MB adsorbed (mol/g)
50
RedlichPeterson
b
aR
2
HYBRID
0.86
0.02
2.4
1.43
i=1
600
1000
600
500
400
300
Initial CV concentration
0
600
1000
200
100
200
800
(10)
100
200
300
400
500
600
3.7.
Comparison of adsorption capacity with other
available adsorbents
Adsorption capacity of organoclay correlates with other available adsorbents along with equilibrium time and is listed in
Table 4. From the comparison it was clear that the adsorbent
developed is much more effective for the removal of basic dyes
from aqueous phase.
3.8.
aij Cej
[(1/ni )1]
[(1/ni )1]
(12)
Bi
Cej
Bj
Cei
aij
(13)
aji
(14)
n /(n 1)
3.9.
The extended Freundlich isotherm for binary
components and competitive coefcients
(11)
224
Adsorption capacity
Banana peel
Fe(III)/Cr(III) hydroxide
Clay
Fly ash (treated with H2 SO4 )
Sugarcane dust
Activated sludge
Coir pith carbonized
Blast furnace sludge
Carbonaceous adsorbent
Surfactant modied bentonite
20.8 mg/g
22.8 mg/g
6.3 mg/g
0.0021 mmol/g
3.798 mg/g
113.2 mg/g
2.56 mg/g
25 mg/g
161 mg/g
399.4 mol/g
1h
72 h
30 min
6h
10 min
120 min
120 min
4h
Reference
Annadurai et al. (2002)
Namasivayam and Sumithra (2005)
Gurses et al. (2004)
Lin et al. (2008)
Khattri and Singh (1999)
Chu and Chen (2002)
Namasivayam et al. (2001)
Jain et al. (2003)
Jain et al. (2003a)
Present study
Competitive coefcients
aij
aji
MB + CV
n
R2
0.103
64
0.985
0.036
64
0.988
RB + CV
n
R2
0.253
64
0.992
0.534
64
0.985
MB + RB
n
R2
0.047
64
0.992
1.101
64
0.995
3.10.
C (RB/MB)
12
10
4.
8
6
4
2
0
-2 0
10
B (RB/MB)
5
C (MB/RB)
4
3
2
1
0
-1
0.5
1.5
Conclusions
B (M B/RB)
Acknowledgement
The authors are grateful to the Professor and Head, Department of Chemistry, University of Kerala, Trivandrum, for
providing laboratory facilities for this work.
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