Desalination 261 (2010) 52–60

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Desalination
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d e s a l

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
Department of Chemical Engineering, SSN College of Engineering, Chennai, 603 110, India
b
Department of Chemical Engineering, University of Louisiana at Lafayette, LA 70504, United States
c
Environmental Management Laboratory, AC Tech, Anna University-Chennai, 600 025, India

a r t i c l e i n f o a b s t r a c t

Article history: Cashew nut shell (CNS) — a novel, low cost adsorbent prepared from agricultural waste has been utilized as
Received 27 March 2010 the adsorbent for the removal of Congo red (CR) dye from an aqueous solution. The effect of pH, adsorbent
Received in revised form 13 May 2010 dose, initial dye concentration, time and temperature on adsorption was studied. The results indicate that
Accepted 17 May 2010
CNS can be employed as a low cost alternative compared to other commercial adsorbents in the removal of
Available online 9 June 2010
dyes from wastewater. The experimental data were analyzed by Langmuir, Freundlich, Redlich–Peterson,
Koble–Corrigan, Sips, Toth, Temkin and Dubinin–Radushkevich adsorption isotherms. The characteristic
Keywords:
Adsorption
parameters for each isotherm and related correlation coefficients have been determined using MATLAB 7.1.
Cashew nut shell Thermodynamic parameters such as ΔGo, ΔHo and ΔSo have also been evaluated and it has been found that
Congo red dye the sorption process was feasible, spontaneous and exothermic in nature. Pseudo-first-order, pseudo-
Isotherm second-order and intraparticle diffusion models were used to fit the experimental data. Kinetic parameters,
Kinetics rate constants, equilibrium sorption capacities and related correlation coefficients, for each kinetic model
Thermodynamic were calculated and discussed. It was shown that the adsorption of CR could be described by the pseudo-
second-order equation, suggesting that the adsorption process is a presumably chemisorption.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction
Wastewater effluents 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 difficult
to biodegrade due to their complex aromatic structures, which
provide them physico-chemical, thermal and optical stability [3],
thus bringing some difficulties 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
flocculation [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
⁎ Corresponding author. Tel.: +91 44 32909855, +91 9884823425; fax: +91 44
27475063.
E-mail addresses: senthilkumarp@ssn.edu.in, senthilchem8582@gmail.com
(P. Senthil Kumar).
quite popular due to its simplicity and high efficiency, as well as the
availability of a wide range of adsorbents. Activated carbon is the
most popular adsorbent for removal of dyestuffs from wastewater
[10–18]. However, adsorbent grade carbon is cost prohibitive and
both regeneration and disposal of the used carbon often very
difficult. Therefore, there is a growing need to find 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 fibre [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 influence of experimental
parameters such as pH, contact time, temperature, CNS dosage and
initial CR concentrations were studied. Also the sorption of CR at
solid–liquid interfaces has been studied extensively under equilib-
rium and various thermodynamic conditions. Further the kinetic
and the mechanistic steps involved in the sorption process were
evaluated at different initial CR dye concentrations.

0011-9164/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2010.05.032
 P. Senthil Kumar et al. / Desalination 261 (2010) 52–60 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. 200–30 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.
Fig. 1. Chemical structure of Congo red.
added to 100 mL of CR solution in 250 mL flasks. The flasks were
shaken at 120 rpm for 120 min. The initial CR concentration used in
this study was 20 to 100 mg/L. The equilibrium study was performed
using various concentrations of CR solutions i.e. from 20 to 100 mg/L.
A 20 g/L CNS with 100 mL CR solutions of various initial concentra-
tions was shaken at 120 rpm for 120 min at 30 °C. All the experiments
were performed in duplicates. The amount of dye adsorbed onto CNS,
qe (mg/g), was calculated by the following mass balance relationship:
ðCi −Ce ÞV
qe = ð1Þ
W

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 λmax 497 nm using a UV–vis 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 adsorp-
tion kinetics. The experiments were carried out in 250 mL Erlenmeyer
flasks 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 flasks were shaken for the required
time period in a water bath shaker. The kinetic studies was carried out
by agitating 250 mL flasks 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 flasks 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 λmax values of the
wastewater samples varied ±10 nm from the λmax values of pure
dyes at a fixed pH. For thermodynamic study, the experiments were
performed by varying temperature from 30 to 60 °C using 20 g/L CNS
where Ci and Ce are the initial and equilibrium concentrations (mg/L)
of CR dye solution respectively; V is the volume (L); and W is the mass
(g) of the adsorbent.
3. Results and discussion
3.1. Characterization of CNS
The adsorption capacity of CNS depends upon porosity as well as
chemical reactivity of functional groups at the surface. This reactivity
creates an imbalance between forces at the surface when compared to
those within the body, thus leading to molecular adsorption by the
van der Waals force. Knowledge on surface functional groups would
give insight to the adsorption capability of the CNS. The FT-IR
spectrums of the CNS and CR loaded on CNS are shown in Fig. 2. OH
and NH stretching is between 3100 and 3500 cm−1, C–H aromatic is
between 3000 and 3100 cm−1, and C–H aliphatic is between 2800 and
3000 cm−1. The spectrum shows a broad band near 3399 cm−1 which
indicates the presence of hydroxyl groups on the CNS surface. The
stretching was attributed to the absorbed water on the surface of CNS.
The peak at 2925 cm−1 is due to C–H stretching of CH2 groups. The
stretching frequencies of the aromatic C = C and aromatic C–H groups
give rise to peaks at 3011 and 2854 cm−1 respectively. The bands near
1630 cm−1 indicates fingerprint region of C = O, C–O and O–H
groups that exist as functional groups of CNS. The peaks at 1542 and
1515 cm−1 is assigned to a conjugated hydrogen bonded carboxyl
group. The peak at 1454 cm−1 (vC–O) indicates the presence of
carboxylic groups. The peak at 1374 cm−1 indicates the presence of C–

Table 1
Properties of the cashew nut shells.

Proximate analysis Ultimate analysis Ash chemical composition

(wt.%) (wt.%) (wt.%)

Volatile matter 65.21 Carbon 45.21 Silica 64.53

Moisture 9.83 Hydrogen 4.25 Iron oxide 3.27
Ash 2.75 Oxygen 37.75 Aluminium oxide 2.19
Fixed carbon 22.21 Nitrogen 0.21 Calcium oxide 26.89
Sulphur Nil Magnesium oxide 2.49
Moisture 9.83 Sodium oxide 0.63
Ash 2.75
Fig. 2. FT-IR spectrum of cashew nut shell and CR loaded on cashew nut shell.
54 P. Senthil Kumar et al. / Desalination 261 (2010) 52–60
H aliphatic bending. The peak at 1232 cm−1 indicates the presence of
C–N from amine. The two peaks at 1156 cm−1 (P = O) and 1035 cm−1
(P–OH) was characteristic of PO2 stretching. These results agree with
the surface chemistries of other agricultural by-products, such as
coconut coir pith [28] and rubber wood saw dust [29]. The region
between 700 and 900 cm−1 contains various bands related to
aromatic, out of plane C–H bending with different degrees of
substitution [30]. After adsorption of CR, peaks of –NH and –NH2
disappeared, –NH rocking peak shifted to a higher wave number,
indicating the significant role of amine groups in the adsorption
process. The stretching vibration of the second –OH group shifted to a
lower wave number. But vibration for the first –OH group did not
change much. It can be concluded from the FT-IR spectroscopy that
amine and the second –OH group were included in the adsorption of
CR.
The specific surface area and pore structure of the CNS was
determine by using surface area and pore size analyzer (Quanta-
chrome, Autosorb-I) on nitrogen adsorption at 77 K. The specific
surface area was calculated by BET equation [31]. It was found that the
BET surface area, pore volume, average pore diameter and bulk
density of the CNS were 395 m2/g, 0.4732 cm3/g, 5.89 nm and 0.415 g/
cm3, respectively.
3.2. Effect of pH
The pH of the system exerts profound influence on the adsorptive
uptake of CR molecule presumably due to its influence on the surface
properties of the CNS and ionization/dissociation of the CR molecule.
The variations in removal of CR dye from aqueous solution at various
system pH are shown in Fig. 3. From the figure, it is evident that the
maximum removal of dye is observed at pH 3 and below. Low pH
leads to an increase in H+ ion concentration in the system and the
surface of the CNS acquires positive charge by absorbing H+ ions. As
the CNS surface is positively charged at low pH, a significantly strong
electrostatic attraction appears between the positively charged CNS
surface and anionic dye molecule leading to maximum adsorption of
dye. As the pH of the system increases, the number of negatively
charged sites increases and the number of positively charged sites
decreases. A negatively charged surface site on the CNS does not favor
the adsorption of anionic dye molecules due to the electrostatic
repulsion. Furthermore, lower adsorption of the CR dye in alkaline
medium is also due the competition from excess OH− ions with the
anionic dye molecule for the adsorption sites.
3.3. Effect of adsorbent dose
Fig. 4 shows the plot between the % CR removals against adsorbent
dose. From figure it was noted that the % CR removal is varied with
varying sorbent mass and it increased with increase in adsorbent
Fig. 3. Effect of pH for the adsorption of CR onto CNS (the initial dye concentra-
tion = 50 mg/L, CNS dose = 20 g/L and time = 2 h).
Fig. 4. Effect of CNS dose on CR removal (the initial dye concentration = 50 mg/L and
time = 2 h).
dose. The % CR removal increases from 56.33 to 99.34% for an increase
in adsorbent dose from 5 to 30 g/L. At higher CNS to CR concentration
ratios, there is very fast superficial sorption onto the CNS surface that
produces a lower CR concentration in the solution than when the
biomass to CR concentration ratio is lower. This is because a fixed dose
of CNS can only adsorb a certain amount of dye. Therefore, the more
the adsorbent dosage, the larger the volume of effluent can be
purifying with a fixed dosage of CNS. The decrease in amount of CR
adsorbed on to an adsorbent qe (mg/g) with increasing CNS dose is
due to a split in the flux or the concentration gradient between CR
concentration in the solution and the CR concentration in the surface
of the CNS. Thus with increasing CNS dose, the amount of dye
adsorbed onto unit weight of CNS gets reduced, thus causing a
decreasing in qe value with increasing CNS dose (not shown in the
figure).
3.4. Effect of initial dye concentration
The effect of initial dye concentration in the range of 20 to 100 mg/
L on adsorption was investigated and is shown in Fig. 5. It is evident
from the figure that the percentage CR removal decreased with the
increase in initial concentration of CR. The initial dye concentration
provides the necessary driving force to overcome the resistance to the
mass transfer of CR between aqueous phase and the solid phase. The
increase in initial dye concentration also enhances the interaction
between CR and CNS. Therefore, an increase in initial concentration of
CR enhances the adsorption uptake of CR. This is due to increase in the
driving force of the concentration gradient, as an increase in the initial
dye concentration. While the percentage CR removal was found to be
98.52% for 20 mg/L of initial concentration, this value was 85.44% for
that of 100 mg/L.
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).
 P. Senthil Kumar et al. / Desalination 261 (2010) 52–60 55

3.5. Effect of contact time

Effect of contact time for the removal of CR by the CNS at Co = 20

to 100 mg/L for the adsorbent dose of 20 g/L showed rapid adsorption
of dye in the first 60 min and, thereafter, the adsorption rate
decreased gradually and the adsorption reached equilibrium in
about 90 min as shown in Fig. 6. Increase in contact time up to
120 min showed that the CR removal by CNS was only by about 0.2%
over those obtained for 90 min contact time. Aggregation of dye
molecules with the increase in contact time makes it almost
impossible to diffuse deeper into the adsorbent structure at highest
energy sites. This aggregation negates the influence of contact time as
the micropores get filled up and start offering resistance to diffusion of
aggregated dye molecules in the adsorbents. This is the reason why an
insignificant enhancement in adsorption is effected in 120 min as
compared to that in 90 min. Since the difference in the adsorption
values at 90 min and at 120 min is very small, after 90 min contact, a
steady-state approximation was assumed and a quasi-equilibrium
situation was accepted. Further experiments were conducted for
90 min contact time only. The adsorption curves were single, smooth
and continuous leading to saturation and indicated the possible
monolayer coverage on the surface of adsorbents by the dye
molecules [32,33].
3.6. Effect of temperature
The adsorption of CR on CNS was investigated as a function of
temperature and maximum removal of CR was obtained at 30 °C.
Experiments were performed at different temperatures of 30, 40, 50
and 60 °C for the initial CR concentrations of 20–100 mg/L at constant
adsorbent dose of 20 g/L. The adsorption decreased from 98.52 to
88.11%, 94.71 to 84.96, 91.61 to 82.79, 88.64 to 79.28 and 85.44 to
76.82% for the initial CR concentrations of 20, 40, 60, 80 and 100 mg/L
respectively with the rise in temperature from 30 to 60 °C (Fig. 7). This
is mainly due to the decreased surface activity suggesting that
adsorption between CR and CNS was an exothermic process.
3.7. Thermodynamic study
Thermodynamic parameters such as free energy (ΔGo), enthalpy
(ΔHo) and entropy (ΔSo) change of adsorption can be evaluated from
the following equations ((2), (3), (4)):
C an important role in the determination of the maximum capacity of
Kc = Ae
Ce
o
ΔG = −RT ln Kc
o o o
ΔG = ΔH −TΔS
Fig. 7. Effect of temperature on CR removal by CNS (the initial dye concentration = 20
to 100 mg/L, CNS dose = 20 g/L and time = 2 h).
ΔSo ΔH o
log Kc = − ð5Þ
2:303R 2:303RT
where Kc is the equilibrium constant, Ce is the equilibrium concentration
in solution (mg/L) and CAe is the amount of CR adsorbed on the
adsorbent per liter of solution at equilibrium (mg/L). ΔGo, ΔHo and ΔSo
are changes in Gibbs free energy (kJ/mol), enthalpy (kJ/mol) and
entropy (J/mol/K), respectively. R is the gas constant (8.314 J/mol/K), T
is the temperature (K). The values of ΔHo and ΔSo are determined from
the slope and the intercept of the plots of logKc versus 1/T (Fig. 8). The
ΔGo values were calculated using Eq. (3). Adsorption of CR on CNS
decreased when the temperature was increased from 303 to 333 K is
shown in Fig. 8. The process was thus exothermic in nature. The plots
were used to compute the values of thermodynamic parameters
(Table 2). The value of enthalpy change (ΔHo) and the entropy change
(ΔSo) recorded from this work were presented in the Table 2. The
negative ΔGo value indicates the process be feasible and spontaneous
nature of adsorption; negative ΔHo value suggests the exothermic
nature of adsorption and the ΔSo can be used to describe the
randomness at the CNS-solution interface during the sorption.
3.8. Adsorption equilibrium study
The capacity of the adsorption isotherm is fundamental, and plays
ð2Þ
adsorption. It also provides a panorama of the course taken by the
system under study in a concise form, indicating how efficiently an
ð3Þ adsorbent will adsorb and allows an estimate of the economic viability
of the adsorbent commercial applications for the specified solute. In
ð4Þ order to adapt for the considered system, an adequate model that can
reproduce the experimental results obtained, equations of Langmuir,

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). Fig. 8. Thermodynamic study.
56 P. Senthil Kumar et al. / Desalination 261 (2010) 52–60

Table 2 β = 1, the Langmuir will be the preferable isotherm, while if β = 0, the

Thermodynamic parameters for the adsorption of CR onto CNS. Freundlich isotherm will be the preferable isotherm.
Initial CR concn. ΔHo ΔSo ΔGo (kJ/mol)
(mg/L) (kJ/mol) (J/mol/K) 3.8.4. Koble–Corrigan model
30 °C 40 °C 50 °C 60 °C
Koble–Corrigan model [37] is another three parameter empirical
20 −59.567 −163.976 −10.576 −7.288 −6.306 −5.545
model depends on the combination of the Langmuir and Freundlich
40 −31.650 −81.069 −7.268 −6.005 −5.404 −4.794
60 −22.651 −55.431 −6.022 −5.102 −4.656 −4.349 isotherm equations in one non-linear equation for representing the
80 −20.066 −49.476 −5.176 −4.503 −3.987 −3.715 equilibrium adsorption data. It is commonly expressed by Eq. (9):
100 −15.844 −37.873 −4.458 −3.867 −3.547 −3.317

n
aCe
qe = ð9Þ
Freundlich, Redlich–Peterson, Koble–Corrigan, Sips, Toth, Temkin and 1 + bCen
Dubinin–Radushkevich have been considered.
where a, b and n are the Koble–Corrigan parameters.
3.8.1. The Langmuir isotherm
The theoretical Langmuir sorption isotherm [34] is based on the 3.8.5. The Sips isotherm
assumption that the maximum adsorption occurs when a saturated The sips isotherm [38] has been used in the following form:
monolayer of solute molecules is present on the adsorbent surface, the
energy of adsorption is constant and there is no migration of
adsorbate molecules in the surface plane. The non-linear equation of Qmax KS Ce1 = n
qe = 1=n
ð10Þ
Langmuir isotherm model is expressed as follow: 1 + KS Ce

qm K L C e
qe = ð6Þ where KS is the Sips constant related with affinity constant (mg/L)−1 / n
1 + KL Ce
and Qmax is the Sips maximum adsorption capacity (mg/g).

where Ce is the supernatant concentration at the equilibrium state of 3.8.6. The Toth isotherm
the system (mg/L), qm and KL are the Langmuir constants, represent- The equation of Toth [39] combines the characteristics of Langmuir
ing the maximum adsorption capacity for the solid phase loading and and Freundlich model, which can be presented as:
the energy constant related to the heat of adsorption respectively.

3.8.2. The Freundlich isotherm fCe

qe =
1 ð11Þ
The Freundlich isotherm model [35] is the earliest known g + ðCe Þd =d
relationship describing the sorption process. The model applies to
adsorption on heterogeneous surfaces with interaction between
where f, g and d are Toth constants.
adsorbed molecules and the application of the Freundlich equation
also suggests that sorption energy exponentially decreases on
3.8.7. The Temkin isotherm
completion of the sorptional centers of an adsorbent. This isotherm
The Temkin isotherm model [40] contains a factor that explicitly
is an empirical equation can be employed to describe heterogeneous
takes into account adsorbing species-adsorbate interactions. This
systems and is expressed as follows:
model assumes the following: (i) the heat of adsorption of all the
1 molecules in the layer decreases linearly with coverage due to
=n
qe = Kf Ce ð7Þ adsorbent–adsorbate interactions, and that (ii) the adsorption is
characterized by a uniform distribution of binding energies, up to
where Kf is the Freundlich constant (L/g) related to the bonding some maximum binding energy. The derivation of the Temkin
energy. Kf can be defined as the adsorption or distribution coefficient isotherm assumes that the fall in the heat of sorption is linear rather
and represents the quantity of dye adsorbed onto adsorbent for unit than logarithmic, as implied in the Freundlich equation. The Temkin
equilibrium concentration. 1/n is the heterogeneity factor and n is a isotherm has commonly been applied in the following form:
measure of the deviation from linearity of adsorption. Its value
indicates the degree of non-linearity between solution concentration qe = B ln ðACe Þ ð12Þ
and adsorption as follows: if the value of n is equal to unity, the
adsorption is linear; if the value is below to unity, this implies that where A and B are Temkin isotherm constants.
adsorption process is chemical; if the value is above unity adsorption
is a favorable physical process. 3.8.8. Dubinin–Radushkevich isotherm
The Dubinin–Radushkevich [41] has the following form
3.8.3. The Redlich–Peterson isotherm −βε2
The Redlich–Peterson isotherm [36] is a combination of Langmuir– qe = qm e ð13Þ
Freundlich model. It approaches the Freundlich model at high
concentration and is in accord with the low concentration limit of where qm is the Dubinin–Radushkevich monolayer capacity (mg/g), β
the Langmuir equation. The equation is given as: a constant related to sorption energy, and ε is the Polanyi potential
which is related to the equilibrium concentration as follows
KR Ce  
qe = ð8Þ 1
1+ αR Ceβ ε = RT ln 1 + ð14Þ
Ce

where KR is Redlich–Peterson isotherm constant (L/g), αR is Redlich– where R is the gas constant (8.314 J/mol K) and T is the absolute
Peterson isotherm constant (L/mg) and β is the exponent which lies temperature. The constant β gives the mean free energy, E, of sorption
between 0 and 1. The constant β can characterize the isotherm as: if per molecule of the sorbate when it is transferred to the surface of the
 P. Senthil Kumar et al. / Desalination 261 (2010) 52–60 57

solid from infinity in the solution and can be computed using the Table 3
relationship: The value of parameters for each isotherm models used in the studies.

Isotherm model Parameter R2 Equation

1:415Ce
Langmuir qm = 5.184 0.981 qe =
1 1 + 0:273Ce
E = pffiffiffiffiffiffi ð15Þ KL = 0.273
2β Freundlich KF = 1.357 0.998 qe = 1.357C0.439
e
n = 2.279
5:548Ce
Redlich–Peterson KR = 5.548 0.999 qe = 1 + 3:186Ce0:638
αR = 3.186
The experimental data on the effect of an initial concentration of
β = 0.638
CR on the CNS of the test medium were fitted to the isotherm models Koble–Corrigan model a = 1.454 0.999 qe =
1:454Ce0:543
1 + 0:102Ce0:543
using MATLAB 7.1 and the graphical representations of these models b = 0.102
are presented in Fig. 9a and b. All of the constants are presented in n = 0.543
1:453Ce0:543
Sips Qmax = 14.29 0.999 qe =
Table 3. Since the value of R2 nearer to 1 indicates that the respective 1 + 0:102Ce0:543
KS = 0.102
equation better fits the experimental data. The representations of the n = 1.841
experimental data by all models equation result in non-linear curve Toth f = 67.39 0.999 qe = 67:39Ce
5:618
½1:013 + ðCe Þ0:178 
with R2 values of a least 0.801 as tabulated in Table 3. The g = 1.013
experimental data yielded excellent fits with in the following d = 0.178
Temkin A = 3.767 0.976 qe = 0.444 ln (3.767Ce)
isotherms order: Redlich–Peterson N Toth N Koble–Corri gan N Sips N
B = 0.444
Freundlich N Langmuir N Temkin N Dubinin–Radushkevich, based on Dubinin–Radushkevich qm = 3.852 0.801 qe = 3.852e − 1.656 × 10
−7 2
ε

its R2 values. The plotted equations obtained from the graph are β = 1.656 × 10−7
presented in Table 3. The comparison of maximum monolayer E = 1736.62
adsorption capacity of some dyes onto various adsorbents was
presented in Table 4. It shows that the CNS studied in this work has
large adsorption capacity. This is due to its high surface area (395 m2/g). 3.9. Adsorption kinetics

In order to examine the controlling mechanism of adsorption

processes such as mass transfer and chemical reaction, pseudo-first-
order, pseudo-second-order and intraparticle diffusion kinetic equa-
tions were used to test the experimental data. The pseudo-first-order
kinetic model was suggested by Lagergren [46] for the adsorption of
solid/liquid systems and its formula is given as:

dqt
= kad ðqe −qt Þ ð16Þ
dt

After integration by applying the initial conditions qt = 0 at t = 0

and qt = qt at t = t, Eq. (16) becomes:
 
qe kad
log = t ð17Þ
qe −qt 2:303

Eq. (17) can be rearranged to obtain a linear form:

kad
log ðqe −qt Þ = log qe − t ð18Þ
2:303

where qt is the adsorption capacity at time t (mg/g) and kad (min−1) is

the rate constant of the pseudo-first order adsorption, was applied to
the present study of CR dye adsorption. The rate constant, kad and
correlation coefficients of the dye under different concentrations were
calculated from the linear plots of log(qe − qt) versus t (Fig. 10) and
listed in Table 5. The correlation coefficients for the pseudo-first-order
kinetic model are low. Moreover, a large difference of equilibrium
adsorption capacity (qe) between the experiment and calculation was

Table 4
Comparison of maximum monolayer adsorption of some dyes onto various adsorbents.

Dyes Adsorbents qm (mg/g) Reference

Congo red Acid activated red mud 7.08 [42]

Congo red Activated carbon prepared 6.70 [43]
from coir pith
Congo red Cashew nut shell 5.184 This work
Methylene blue Apricot stones-AC 4.11 [44]
Methylene blue Walnut shell-AC 3.53 [45]
Congo red Activated carbon (LR) 1.88 [44]
Methylene blue Almond shell-AC 1.33 [44]
Fig. 9. (a and b) The non-linear adsorption isotherm for CR with CNS at 30 °C.
58 P. Senthil Kumar et al. / Desalination 261 (2010) 52–60

Fig. 11. Pseudo-second-order kinetic fit for adsorption of CR onto CNS at 30 °C.

Fig. 10. Pseudo-first-order kinetic fit for adsorption of CR onto CNS at 30 °C.

observed, indicating a poor pseudo-first-order fit to the experimental
data.
The kinetic data were further analyzed using Ho's pseudo-second-
order kinetics model [47]. This model is based on the assumption that
the sorption follows second-order chemisorption. It can be expressed
as:
dqt 2
= kðqe −qt Þ
dt
Integrating Eq. (19) and applying the boundary conditions, gives:
 
1 1
= + kt
qe −qt qe
Eq. (20) can be rearranged to obtain a linear form:
t 1 1
= + t ð21Þ
qt h qe
where h = kq2e (mg g−1 min−1) can be regarded as the initial
adsorption rate as t → 0 and k is the rate constant of pseudo-second-
order adsorption (g mg−1 min−1). The plot t / qt versus t (Fig. 11)
should give a straight line if pseudo-second-order kinetics is
applicable and qe, k and h can be determined from the slope and
intercept of the plot, respectively. At all studied initial dye
concentrations, the straight lines with extremely high correlation
coefficients (N0.998) were obtained. In addition, the calculated qe
values also agree with the experimental data in the case of pseudo-
second-order kinetics. These suggest that the adsorption data are well
represented by pseudo-second-order kinetics and this supports the
assumption [47] that the rate-limiting step of CR onto CNS may be
chemical sorption or chemisorption. From Table 5, the values of the
rate constant k decrease with increasing initial dye concentration for
the CNS. The reason for this behavior can be attributed to the lower
competition for the sorption surface sites at lower concentration. At
higher concentrations, the competition for the surface active sites will
be high and consequently lower sorption rates are obtained. Similar
phenomena have been observed in the adsorption of acid dyes on
surfactant-modified bentonites [48,49].
In order to gain insight into the mechanisms and rate controlling
steps affecting the kinetics of adsorption, the kinetic experimental
results were fitted to the Weber's intraparticle diffusion [50]. The
kinetic results were analyzed by the intraparticle model to elucidate
the diffusion mechanism, which model is expressed as:
ð19Þ
1
=2 + C
qt = kp t ð22Þ
where C is the intercept and kp is the intraparticle diffusion rate
constant, (mg/gmin1/2), which can be evaluated from the slope of the
ð20Þ
linear plot of qt versus t(1/2) as shown in Fig. 12. The intercept of the
plot reflects the boundary layer effect. The larger the intercept, the
greater the contribution of the surface sorption in the rate controlling
step. The calculated intraparticle diffusion coefficient kp values are
listed in Table 5. If the regression of qt versus t(1/2) is linear and passes
through the origin, then intraparticle diffusion is the sole rate-limiting
step. However, the linear plots at each concentration did not pass
through the origin. This indicates that the intraparticle diffusion was
not only a rate controlling step.
4. Conclusion
CNS used in this investigation is freely, abundantly and locally
available; the resulting adsorbent is expected to be economically viable
for removal of CR from aqueous solution. The results obtained from FT-
IR spectrum shows that the CNS can be a viable option for its usage as an
alternate adsorbent for CR removal. The specific surface area, pore
volume and average pore diameter calculated by BET equation states the
effectiveness of CNS adsorbent for the removal of CR from aqueous
solution. The effect of pH of aqueous solution decreases the removal
efficiency with the increase in pH due to the ionic effect. The % CR
removal increases from 56.33 to 99.34% for an increase in adsorbent
dose from 5 to 30 g/L because of the concentration gradient between CR
concentration in the solution and the CR concentration in the surface of
the CNS. The increase in initial dye concentration also enhances the

Table 5
Comparison between the adsorption rate constants, qe, estimated and correlation coefficients associated with pseudo-first-order and to the pseudo-second-order rate equations and
intraparticle diffusion.

Initial CR concn. Pseudo-first-order rate equation Pseudo-second-order rate equations Intraparticle diffusion
(mg/L)
kad (min−1) qe (mg/g) R2 k (g mg−1 min−1) qe , cal (mg/g) h (mg g−1 min−1) qe, exp (mg/g) R2 kp (mg/g. min1/2) C R2

20 0.074 1.367 0.912 0.096 1.096 0.115 0.982 0.999 0.063 0.436 0.903
40 0.067 2.483 0.897 0.045 2.123 0.203 1.889 0.999 0.124 0.805 0.937
60 0.071 4.102 0.875 0.031 3.086 0.294 2.741 0.999 0.184 1.145 0.918
80 0.069 5.105 0.901 0.022 4.016 0.361 3.538 0.999 0.245 1.417 0.927
100 0.074 6.637 0.898 0.019 4.831 0.451 4.261 0.999 0.294 1.737 0.910
 P. Senthil Kumar et al. / Desalination 261 (2010) 52–60
Fig. 12. Intraparticle diffusion model for adsorption of CR onto CNS at 30 °C.
interaction between CR and CNS which results in the decreased
percentage of CR removal with the increase in initial concentration of
CR. In the effect of contact time, the percentage removal increases with
time up to 90 min and remains almost constant. There is not much
significant increase in the % of dye removal in view of the fact that the
aggregation of solid particles on the pore volume counteracts the
influence of contact time as the micro pores get filled up and start
offering resistance to diffusion of aggregated dye molecules in the
adsorbents. The temperature has adverse effect on the percentage of dye
removal due to the decreased surface activity suggesting that adsorption
between CR and CNS was an exothermic process. The equilibrium data
have been analyzed using Langmuir, Freundlich, Redlich–Peterson,
Koble–Corrigan, Sips, Toth Temkin and Dubinin–Radushkevich
isotherms. The characteristic parameters for each isotherm and related
correlation coefficients have been determined. The experimental data
yielded excellent fits within the following isotherms order: Redlich–
Peterson N Toth N Koble–Corrigan N Sips N Freundlich N Langmuir N
Temkin N Dubinin–Radushkevich, based on its correlation coefficient
values. The thermodynamic analysis indicates that the system is
spontaneous and exothermic. The suitability of the pseudo-first- and
second-order equations and intra particle diffusion kinetic model for the
sorption of CR onto CNS is also discussed. The pseudo-second-order
kinetic model agrees very well with the dynamical behavior for the
adsorption of CR onto CNS for different initial CR concentrations over the
whole range studied. The CNS appeared to be suitable for the removal of
CR from aqueous solutions.
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