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Adsorption of dye from aqueous solution by cashew nut shell: Studies on equilibrium
isotherm, kinetics and thermodynamics of interactions
P. Senthil Kumar a,, S. Ramalingam b, C. Senthamarai a, M. Niranjanaa a, P. Vijayalakshmi c, S. Sivanesan c
a
b
c
Department of Chemical Engineering, SSN College of Engineering, Chennai, 603 110, India
Department of Chemical Engineering, University of Louisiana at Lafayette, LA 70504, United States
Environmental Management Laboratory, AC Tech, Anna University-Chennai, 600 025, India
a r t i c l e
i n f o
Article history:
Received 27 March 2010
Received in revised form 13 May 2010
Accepted 17 May 2010
Available online 9 June 2010
Keywords:
Adsorption
Cashew nut shell
Congo red dye
Isotherm
Kinetics
Thermodynamic
a b s t r a c t
Cashew nut shell (CNS) a novel, low cost adsorbent prepared from agricultural waste has been utilized as
the adsorbent for the removal of Congo red (CR) dye from an aqueous solution. The effect of pH, adsorbent
dose, initial dye concentration, time and temperature on adsorption was studied. The results indicate that
CNS can be employed as a low cost alternative compared to other commercial adsorbents in the removal of
dyes from wastewater. The experimental data were analyzed by Langmuir, Freundlich, RedlichPeterson,
KobleCorrigan, Sips, Toth, Temkin and DubininRadushkevich adsorption isotherms. The characteristic
parameters for each isotherm and related correlation coefcients have been determined using MATLAB 7.1.
Thermodynamic parameters such as Go, Ho and So have also been evaluated and it has been found that
the sorption process was feasible, spontaneous and exothermic in nature. Pseudo-rst-order, pseudosecond-order and intraparticle diffusion models were used to t the experimental data. Kinetic parameters,
rate constants, equilibrium sorption capacities and related correlation coefcients, for each kinetic model
were calculated and discussed. It was shown that the adsorption of CR could be described by the pseudosecond-order equation, suggesting that the adsorption process is a presumably chemisorption.
2010 Elsevier B.V. All rights reserved.
1. Introduction
Wastewater efuents from different industries such as textiles,
leather, rubber, paper and plastics, contain several kinds of synthetic
dye stuffs [1]. A very small amount of dye in water is highly visible.
Further, discharging even a small amount of dye into water can
affect aquatic life and food webs due to the carcinogenic and
mutagenic effects of synthetic dyes [2]. Synthetic dyes are difcult
to biodegrade due to their complex aromatic structures, which
provide them physico-chemical, thermal and optical stability [3],
thus bringing some difculties for the treatment of these dyes.
Hence, it is imperative that a suitable treatment method should be
devised.
In recent years, many methods including coagulation and
occulation [4], reverse osmosis [5], chemical oxidation [6],
biological treatments [7], photodegradation [8], and adsorption
[9], have been developed for treating dye containing wastewater.
Among various treatment technologies, adsorption technique is
quite popular due to its simplicity and high efciency, as well as the
availability of a wide range of adsorbents. Activated carbon is the
most popular adsorbent for removal of dyestuffs from wastewater
[1018]. However, adsorbent grade carbon is cost prohibitive and
both regeneration and disposal of the used carbon often very
difcult. Therefore, there is a growing need to nd locally available,
low cost and effective materials for the removal of dyes. A number of
non-conventional, low cost adsorbents such as wood [19], bagasse
pith [20], maize cob [21], rice hull ash [22], Azadirachta indica leaf
powder [23], palm kernel bre [24], fungi [25], bentonite [26],
Organo-attapulgite [27] have been used for the removal of dye from
aqueous solutions. However, some of these adsorbents do not have
good adsorption capacities for anionic dyes because most have
hydrophobic or anionic surfaces. Hence, there is a need to search for
more effective adsorbents. In the present study, CNS has been used
as an adsorbent for the removal of CR from its aqueous solutions.
The objective of the present work is to introduce a new low cost
adsorbent such as CNS and also to examine its effectiveness in
removing CR from aqueous solution. The inuence of experimental
parameters such as pH, contact time, temperature, CNS dosage and
initial CR concentrations were studied. Also the sorption of CR at
solidliquid interfaces has been studied extensively under equilibrium and various thermodynamic conditions. Further the kinetic
and the mechanistic steps involved in the sorption process were
evaluated at different initial CR dye concentrations.
53
2. Experimental
2.1. Adsorbent
Cashew nut shells were collected from Pudukkottai District,
Tamilnadu, India and were used as an adsorbent. This natural waste
was thoroughly rinsed with water to remove dust and soluble
material and was then allowed to dry at room temperature. The
above dried natural waste was crushed into powder and sieved
through the sieves. 20030 mesh size particles of CNS were taken for
the adsorption studies. The proximate and ultimate analysis of cashew
nut shells are shown in Table 1.
2.2. Adsorbate
Congo red (CI = 22,120) was supplied by Merck (India). A stock
solution of CR dye was prepared (100 mg/L) by dissolving a required
amount of dye powder in deionized water. The stock solution was
diluted with deionized water to obtain desired concentration ranging
from 20 to 100 mg/L. The chemical structure of CR is shown in the
Fig. 1.
2.3. Analysis
The concentration of CR in the experimental solution was
determined from the calibration curve prepared by measuring
absorbance of different determined concentrations of CR solutions
at max 497 nm using a UVvis Spectrophotometer (Shimadzu, Japan).
The pH of solution was measured with a Hanna pH meter using a
combined glass electrode (Model HI 9025C, Singapore).
2.4. Adsorption experiment
Adsorption experiments were conducted by varying pH, contact
time, CNS dose, temperature, initial CR concentration under the
aspects of thermodynamic study, adsorption isotherms and adsorption kinetics. The experiments were carried out in 250 mL Erlenmeyer
asks and the total volume of the reaction mixture was kept at
100 mL. The pH of solution was maintained at a desired value by
adding 0.1 M NaOH or HCl. The asks were shaken for the required
time period in a water bath shaker. The kinetic studies was carried out
by agitating 250 mL asks containing 20 g/L of CNS and 100 mL CR dye
solutions of different concentrations i.e. from 20 to 100 mg/L, in water
bath shaker. The mixture was agitated at 120 rpm at 30 C. The
contact time was varied from 0 to 120 min. At predetermined time,
the asks were withdrawn from the shaker and the residual dye
concentration in the reaction mixture was analyzed by centrifuging
the reaction mixture and then measuring the absorbance of the
supernatant at the wavelength that correspond to the maximum
absorbance of the sample. Dye concentration in the reaction mixture
was calculated from the calibration curve. The max values of the
wastewater samples varied 10 nm from the max values of pure
dyes at a xed pH. For thermodynamic study, the experiments were
performed by varying temperature from 30 to 60 C using 20 g/L CNS
Ci Ce V
W
Table 1
Properties of the cashew nut shells.
Proximate analysis
(wt.%)
Volatile matter
Moisture
Ash
Fixed carbon
65.21
9.83
2.75
22.21
Ultimate analysis
(wt.%)
Carbon
Hydrogen
Oxygen
Nitrogen
Sulphur
Moisture
Ash
Silica
Iron oxide
Aluminium oxide
Calcium oxide
Magnesium oxide
Sodium oxide
45.21
4.25
37.75
0.21
Nil
9.83
2.75
64.53
3.27
2.19
26.89
2.49
0.63
Fig. 2. FT-IR spectrum of cashew nut shell and CR loaded on cashew nut shell.
54
Fig. 4. Effect of CNS dose on CR removal (the initial dye concentration = 50 mg/L and
time = 2 h).
Fig. 3. Effect of pH for the adsorption of CR onto CNS (the initial dye concentration = 50 mg/L, CNS dose = 20 g/L and time = 2 h).
Fig. 5. Effect of initial dye concentration for the adsorption of CR onto CNS (the initial
dye concentration = 20 to 100 mg/L, CNS dose = 20 g/L and time = 2 h).
55
G = RT ln Kc
o
3
o
G = H TS
Fig. 6. Effect of contact time for the adsorption of CR onto CNS (the initial dye
concentration = 20 to 100 mg/L, CNS dose = 20 g/L and time = 2 h).
log Kc =
So
H o
2:303R 2:303RT
56
Table 2
Thermodynamic parameters for the adsorption of CR onto CNS.
Initial CR concn.
(mg/L)
Ho
(kJ/mol)
So
(J/mol/K)
Go (kJ/mol)
30 C
40 C
50 C
60 C
20
40
60
80
100
59.567
31.650
22.651
20.066
15.844
163.976
81.069
55.431
49.476
37.873
10.576
7.268
6.022
5.176
4.458
7.288
6.005
5.102
4.503
3.867
6.306
5.404
4.656
3.987
3.547
5.545
4.794
4.349
3.715
3.317
qe =
aCe
1 + bCen
qe =
Qmax KS Ce1 = n
1=n
1 + KS Ce
10
fCe
qe =
1
g + Ce d =d
qe =
qe = Kf Ce
=n
KR Ce
1+
R Ce
11
12
qe = qm e
13
14
solid from innity in the solution and can be computed using the
relationship:
1
E = p
2
15
Table 3
The value of parameters for each isotherm models used in the studies.
Isotherm model
Parameter
R2
Equation
Langmuir
qm = 5.184
KL = 0.273
KF = 1.357
n = 2.279
KR = 5.548
R = 3.186
= 0.638
a = 1.454
b = 0.102
n = 0.543
Qmax = 14.29
KS = 0.102
n = 1.841
f = 67.39
g = 1.013
d = 0.178
A = 3.767
B = 0.444
qm = 3.852
= 1.656 107
E = 1736.62
0.981
qe =
0.998
qe = 1.357C0.439
e
0.999
qe =
5:548Ce
1 + 3:186Ce0:638
0.999
qe =
1:454Ce0:543
1 + 0:102Ce0:543
0.999
qe =
1:453Ce0:543
1 + 0:102Ce0:543
0.999
qe =
0.976
qe = 0.444 ln (3.767Ce)
0.801
qe = 3.852e 1.656 10
Freundlich
RedlichPeterson
57
KobleCorrigan model
Sips
Toth
Temkin
DubininRadushkevich
1:415Ce
1 + 0:273Ce
67:39Ce
1:013
5:618
+ Ce 0:178
7 2
16
qe
qe qt
=
kad
t
2:303
17
kad
t
2:303
18
Dyes
Adsorbents
qm (mg/g)
Reference
Congo red
Congo red
7.08
6.70
[42]
[43]
5.184
4.11
3.53
1.88
1.33
This work
[44]
[45]
[44]
[44]
Congo red
Methylene blue
Methylene blue
Congo red
Methylene blue
58
19
qt = kp t
=2 + C
22
1
qe qt
1
=
+ kt
qe
20
21
Table 5
Comparison between the adsorption rate constants, qe, estimated and correlation coefcients associated with pseudo-rst-order and to the pseudo-second-order rate equations and
intraparticle diffusion.
Initial CR concn.
(mg/L)
20
40
60
80
100
kad (min1)
qe (mg/g)
R2
k (g mg1 min1)
qe , cal (mg/g)
h (mg g1 min1)
R2
Intraparticle diffusion
kp (mg/g. min1/2)
R2
0.074
0.067
0.071
0.069
0.074
1.367
2.483
4.102
5.105
6.637
0.912
0.897
0.875
0.901
0.898
0.096
0.045
0.031
0.022
0.019
1.096
2.123
3.086
4.016
4.831
0.115
0.203
0.294
0.361
0.451
0.982
1.889
2.741
3.538
4.261
0.999
0.999
0.999
0.999
0.999
0.063
0.124
0.184
0.245
0.294
0.436
0.805
1.145
1.417
1.737
0.903
0.937
0.918
0.927
0.910
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