Journal of the Taiwan Institute of Chemical Engineers 61 (2016) 306315

Contents lists available at ScienceDirect

Journal of the Taiwan Institute of Chemical Engineers

journal homepage: www.elsevier.com/locate/jtice

Equilibrium, kinetic and thermodynamic studies of a new potential

biosorbent for the removal of Basic Blue 3 and Congo Red dyes:
Pineapple (Ananas comosus) plant stem
Siew-Ling Chan a, Yen Ping Tan a,, Abdul Halim Abdullah a, Siew-Teng Ong b
a

Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor Darul Ehsan, Malaysia
Department of Chemical Science, Faculty of Science, Universiti Tunku Abdul Rahman, Jalan Universiti, Bandar Barat, 31900 Kampar, Perak Darul Ridzuan,
Malaysia

a r t i c l e

i n f o

Article history:
Received 2 July 2015
Revised 13 November 2015
Accepted 12 January 2016
Available online 12 February 2016
Keywords:
Pineapple plant stem
Adsorption
Basic Blue 3
Congo Red
Batch Study

a b s t r a c t
The waste management becomes particular nowadays and waste conversion into valuable materials is one
of the promising alternative capable of reducing the resource depletion rate. The performance of lignocellulosic residues, pineapple plant stem (PPS) for cationic (Basic Blue 3, BB3) and anionic (Congo Red, CR)
dyes removal has been evaluated in a batch process, using different parameters such as, pH, contact time,
agitation rate, initial dye concentration and sorbent dosage. The kinetics of both dyes sorption tted well
with pseudo-second order kinetic model. Boundary layer effect and intraparticle diffusion models were
applied to study the rate-limiting step. The isotherm data of BB3 could be well described by Freundlich
model (r2 = 0.998) whilst high coecient of determination of CR obtained from Langmuir (r2 = 0.999) and
Temkin (r2 = 0.996) models. The maximum sorption capacities for BB3 and CR were found to be 58.983
and 11.966 mg g1 , respectively under a favourable sorption process. The BB3 and CR adsorption on PPS
was found to be exothermic. The result suggests that PPS has higher anity on cationic than anionic dye.
The promising regeneration capability of PPS using acid, implied PPS was a potential biosorbent for BB3
removal.
2016 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction
In textile industry, large amount of euent is discharged from
dyeing and nishing processes whereby 1015% of dyes are estimated to be lost in the euent [1]. The requirement to minimise
residual dyes in the euent becomes a major public concern due
to the stringent restriction and regulation has been established on
industrial euents. Although wastewater undergoes conventional
wastewater treatment before being discharged into aquatic systems, a low concentration of dyes remaining in the euent water along with other chemical substances can affect the aesthetic
and transparency of water stream [2]. Besides, dyes discharged into
the aquatic system not only reduce the dissolved oxygen concentration but also affect the aquatic ecosystem resulted from the toxicological properties of dyes, since most of the dyes are known to
be toxic, carcinogenic and mutagenic toward the aquatic life [35].
With the prediction of freshwater shortages in the future due to
climate change, treated euent becomes second water source for

Corresponding author. Tel.: +60 389466789.

E-mail address: typ@upm.edu.my, yptan100@gmail.com (Y.P. Tan).

non-potable usage in industrial, businesses and household sectors.

The colour removal process thus becomes one of the crucial steps
to ensure the quality of the reclaimed water, but additional procedures in the textile euent treatment inevitably increase the cost
of overall treatment and cause harmful secondary pollution.
Pineapple (Ananas comosus), belongs to Bromeliaceae family, is
a perennial monocotyledons plant with terminal inorescences
and a terminal multiple fruit [6]. Pineapple plant only fruits once
in the whole lifecycle, but slips and suckers produced from the
mother stem are basically used as commercial vegetative propagation. Therefore, the stems, the leaves and the roots are served
as pineapple residues after vegetative shoots were removed from
the mother stem. Nowadays, pineapple becomes the third most
important commercial tropical fruit crop in the world. Pineapple
production in Malaysia is about 316,0 0 0 tons for the year 2013
[7], whereby a large scale of the plantation has cultivated on
peat soil. About 13 tons per hectare of pineapple residues are produced in every growing season [8], and these residues on the
peat soil are recycled by in situ burning after the harvest, subsequently attributed to global warming by carbon sequestration [9].
Alternatively, pineapple residues can be removed by shredding or
plowing before subsequent replanting. However, the use of heavy

http://dx.doi.org/10.1016/j.jtice.2016.01.010
1876-1070/ 2016 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

S.-L. Chan et al. / Journal of the Taiwan Institute of Chemical Engineers 61 (2016) 306315

machinery transportation for low loading capacity of pineapple

residues may increase the overall expenses. Therefore, one of the
challenges of agricultural waste management in Malaysia is to establish an environmental green technique to handle these residues.
There is a strong need to establish value added product from
pineapple residues in order to defray the cost of residues removal
operation and conquer the environmental pollution. Since no study
has been applied on the conversion of pineapple plant stem into
wastewater remediation, the native pineapple plant stem was used
in present study to study the sorption process of cationic BB3 and
anionic CR dyes.
2. Materials and methods

307

which are 654.0 and 499.0 nm for BB3 and CR, respectively. Dilution was carried out when necessary to t the linearity of calibration curve. All the samples were conducted duplicated and mean
values were calculated with relative standard deviation (RSD) of
5% or lower.
The amount of dye adsorbed at equilibrium, qe (mg g1 ) and the
percentage uptake of dye (%) was calculated by Eqs. (1) and (2):

qe = (Co Ce )V/W

(1)

Removal percentage = (Co Ce )/Co x 100 %

(2)

where Co and Ce are the initial and equilibrium dye concentration

(mg L1 ), V is the volume of the solution (L), and W is the mass of
dry adsorbent (g).

2.1. Sorbent preparation and characterisation

2.3. Determination of point of zero charge
Pineapple plant was collected after the harvest from the plantation located at Sepang, Malaysia. Pineapple plant stem (PPS) was
cut into slices after the cortex was removed using knives, followed by being dried at 90 2 C hot air oven up to a constant
weight before ground into smaller particle size. The PPS particles
were boiled with distilled water twice to remove residues and
to avoid any interference in optical density measurement before
proceeded to reheating procedure. The dried PPS particles were
screened through a set of sieves to the geometrical size of 106
10 0 0 m, while 106250 m particle size of PPS was used in the
studies, unless otherwise stated.
FTIR (Perkin-Elmer model 1725) was used for the determination of functional group on the surface of PPS. The dried mixture was ground homogeneously with KBr to form a thin and ne
pellet after compression in order to obtain observable absorption
spectra in the range of 40 040 0 0 cm1 . Elucidation of the surface
morphology of PPS was performed using scanning electron microscope (VPSEM, LEO 1455) operated at a 20.0 kV accelerating potential with working distance of 13.0 mm. Prior to the observation,
the surface of the sample was coated with a thin, electric conductive gold lm. The physical characteristics of PPS were studied by the means of surface area, pore volume and pore size distribution performed by BET surface area analyser (Autosorb AS-1,
Quantachrome).

Point of zero charge (pHpzc ) of PPS was determined by the modied solid addition method [10]. 20 mL of 0.1 mol dm3 of NaCl solution with pH varying from 2 to 10 and each solution was adjusted by adding 0.10 mol dm3 of hydrochloric acid or sodium
hydroxide. The initial pH of the solution was accurately measured
and recorded as pHi . 0.03 g of the PPS was added and the suspensions were shaken at 150 rpm for 24 h. The pH values of the supernatant were measured and denoted as pHf . The difference between
the initial and nal values is given by pH = pHi pHf , was plotted against pHi . The pHpzc of PPS was corresponded to the point of
intersection when pH = 0.
2.4. Statistical analysis
The non-linear regression method of kinetic and isotherm models were carried out using the software Origin-Pro (Ver. 8.0, OriginLab Co., MA). In present study, the coecient of determination (r2 ),
the sum of square of error (SSE), and the chi-square ( 2 ) tests as
shown in Eqs. (3) to (5) were applied to evaluate the applicability
of each model quantitatively [11,12].


r 2 = (qe,meas qe,calc )2 /

(qe,meas

qe,calc )


+ (qe,meas qe,calc )

(3)

2.2. Sorbate preparation

(qe,meas qe,calc )2

Synthetic dye solution of Basic Blue 3 (C.I. = 51,004, FW = 359.9,

max = 654.0 nm, Aldrich 25% purity) and Congo Red (C.I. = 22,120,
FW = 696.7, max = 499.0 nm, Aldrich 91% purity) were used as sorbate in the present study. Both dyes were used without any further
purication. Working dyes solution from 50 to 200 mg L1 were
freshly prepared by weighing suitable amount of dyes for the sake
of getting accurate concentration and avoiding degradation of dyes.

SSE =

2.2. Batch adsorption studies

2.5. Reversibility and reusability studies

Batch studies was carried by weighing 0.03 g PPS and added

into 50 mL graduated centrifuge tube. After 20 mL of dye solution
was added into sorbent-containing tube, the mixture was agitated
at 150 rpm using rotary shaker. The whole batch studies were carried out at ambient temperature (25 2 C) for 300 min, unless
otherwise stated. Besides, sample without sorbent was served as
a control throughout the experiments to ensure the sorption process was performed solely by the sorbent not the inner surface
of centrifuge tube. Phase separation between dye-adsorbed PPS
and remaining dye solution was performed naturally within 5 min
by gravity. The liquid phase was extracted and proceeded to optical density measurement with a double-beam spectrophotometer (Lambda 35, Perkin-Elmer) at respective maximum wavelength,

The reusability of PPS was evaluated using four different mediums, namely distilled water, 0.1 M NaOH, 0.1 M HCl and methanol.
Similar adsorption condition was conducted and the spent PPS was
placed into desorbing solvent at room temperature for 5 h. The
adsorption-desorption study with the same parameters were conducted for another 2 consecutive cycles.

2 =

[(qe,meas qe,calc )2 /qe,calc ]

(4)
(5)

where qe,meas and qe,calc are the measured and calculated sorption
capacity (mg g1 ), respectively. Given that qe,calc is the average of
qe,calc .

3. Result and discussion

3.1. Properties of pineapple plant stem
A number of adsorption peaks appeared in FTIR spectrum of
PPS (Fig. 1), revealed that PPS is a lignocellulosic complex due to

308

S.-L. Chan et al. / Journal of the Taiwan Institute of Chemical Engineers 61 (2016) 306315

Fig. 1. FTIR spectrum of PPS.

the presence of three major constituents namely, cellulose, hemicellulose, and lignin. The strong asymmetric absorption band at
3335 cm1 indicated the presence of O-H stretching owing to vibration of silanol group and hydroxyl group [13]. The bands at
2913 and 1368 cm1 corresponded to C-H stretching and bending vibration, respectively. The characteristic peaks at 1727 and
1634 cm1 revealed the existence of ketone or aldehydes carbonyl
stretching, while latter conjugated with aromatic rings. The characteristic bands of cellulose and hemicellulose were indicated by
the presence CO stretching at 1424 and 1248 cm1 , respectively
[14], whilst a strong band at 1027 cm1 was due to CO, C=C and
CCO vibrational stretches of cellulose, hemicellulose and lignin
constituents in PPS. Similar trends are observed in other studies,
such as maize stem [10], coffee grounds [15], wheat straws [13],
and banana stems [16]. The morphology of pineapple plant stem
(PPS) was ascertained by SEM as shown in Fig. 2. The presence
of pores with the average diameter of 30 m in a honeycomb
shape (Fig. 2a), indicated porosity of PPS are mainly attributed to
the sorbate adhesion. Besides, tiny holes and roughness of the internal surface (Fig. 2b) accredited to the higher surface area of
the PPS. The total surface area of PPS was determined using BET
analysis. It was found to be 2.39 m2 g1 with total pore volume
of 0.02 cm3 g1 and mean pore diameter 3.86 nm. PPS particles
are predominantly mesopores, which are further conrmed by the
presence of porous structure in PPS micrograph.
3.2. Effect of particle size
The effect of particle size on the adsorption of BB3 and CR
molecules, respectively, were conducted using four different
particle sizes in the range of 106250, 250315, 315500, and

50 010 0 0 m, as depicted in Fig. 3. Increasing trends were observed for both dye systems, the smaller particle size contributed
to the expanded total surface area per unit volume of PPS particles. Diffusion of dye molecules from the bulk solution toward the
solid phase was enhanced as the active sites exposed to the surrounding greatly increased with decreasing particle size. Besides,
distribution of smaller particles in the bulk solution withstands
higher freedom than the larger particles, mainly caused by the
diffusional resistance. Not only longer diffusional path length and
higher mass transfer resistance in large particle diameter, but the
blocked internal surface of the particle may not be available for
adsorption [17]. The higher diffusion rate of smaller particles from
bulk solution toward the solid phase is correlated to the depressed
intraparticle diffusion resistance and boundary layer effect which
is consistent with the study reported [18]. At the same turbulence
condition, higher sorption capacity was contributed by larger shear
force applied on the smaller particle and depleted boundary layer
thickness.
3.3. Dissolution properties of dyes
Basic Blue 3 is an extremely weak base with three mesomeric
structures whereby the positive charge can be allocated on the nitrogen in either one of the amine groups or on the central oxygen
atom in the aromatic ring. The sorption points out range of pH 3
to pH 10 were excluded in this experiment due to precipitation
overwhelmed adsorption. The increase of the solution acidity converted BB3 cations into the protonated form BB3H2+ [BB3H2+
BB3+ + H+ ], facilitated the formation of aggregates. It is expected
that beyond pH 10 the monoelectronic charge of BB3 was reduced
in the presence of excessive hydroxyl ions, attenuated its water

S.-L. Chan et al. / Journal of the Taiwan Institute of Chemical Engineers 61 (2016) 306315

309

Fig. 3. Effect of particle size on the sorption of BB3 and CR in single dye solutions
onto PPS. Condition: 0.03 g of sorbent in 20 mL of 50 mg/L BB3 and CR in single dye
solution at 150 rpm for 5 h at room temperature of 25 2 C.

Fig. 4. (a) Point of zero charge of PPS. (b) Effect of pH on the sorption of BB3 and
CR in single dye solutions onto PPS, in water or buffer medium. Condition: 0.03 g
of sorbent in 20 mL of 50 mg/L BB3 and CR in single dye solution at 150 rpm for 5 h
at room temperature of 25 2 C.

3.4. Effect of pH
Fig. 2. SEM micrograph of PPS particle at (a) 10 m and (b) 2 m.

solubility. Despite of having the similar absorption bands along the

visible region the exceptional sorption points have signicantly low
absorbance intensities.
The acidic diazo Congo Red in aqueous solution consists of
three absorption bands, a main band at 499.0 nm assigned to
the anionic monomer, and the absorption bands at 235 and
347 nm, designated to the benzoic and naphthalene rings, respectively. CR dye solution was found to have similar absorption bands
and absorbance intensities from pH 5 to 10 yet bathochromic shift
( 511 nm) at pH < 5 are attributed to self-association of CR
monomers through face-to-face correspondence to form dimers
and reduce the hydrophobic interaction with water [19]. It is commonly known that protonation of azo dyes occurred in acidic
medium while CR accompanied by four N atoms with high potential to be protonated in acidic solution.

The uptake percentages of BB3 and CR by PPS between pH 3

and 10 in two different mediums, water and buffer medium were
depicted in Fig. 4b. pH is one of the most inuencing parameters affecting both aqueous chemistry and surface binding sites
of the adsorbents [20]. The electrostatic interactions are diminished by increasing the solution acidity to an extent where the
negative charge of the systems becomes negligible [21,22]. Under
high acidity condition, the volume of the mesopores of PPS relative to the molecular size of dye molecules became pronounced.
It became apparent at pH 3, relatively low uptake of BB3 and CR
in both mediums was observed. The removal of BB3 was slightly
higher than CR due to its smaller molecular size, regardless of ionic
charges.
When the solution pH was higher than point of zero charge of
PPS, pHzpc = 4.05 (Fig. 4a), the functional groups would be deprotonated to form anionic-dominated surface. The BB3 adsorption increased gradually at higher pH and the optimal pH for maximum
BB3 removal was at pH 10. Conversely, CR is an anionic dye, the

310

S.-L. Chan et al. / Journal of the Taiwan Institute of Chemical Engineers 61 (2016) 306315

Fig. 5. Effect of contact time and non-linearised kinetic models of BB3 and CR adsorption onto PPS. Condition: 0.03 g of sorbent in 20 mL of 50, 100, 200 mg/L BB3
and CR in single dye solution at 150 rpm for 5 h at room temperature of 25 2 C.

Fig. 6. Effect of agitation rate on the sorption BB3 and CR in single dye solutions
onto PPS. Condition: 0.03 g of sorbent in 20 mL of 50 mg/L BB3 and CR in single dye
solution at 100,150, 200 rpm for 5 h at room temperature of 25 2 C.

adsorption uptake of CR decreased at higher pH, indicated that repulsive electrostatic force predominated in the adsorption process.
At optimum pH at which maximum CR adsorption attained was pH
4, the protonated CR and deprotonated PPS exhibited simultaneously, induced sorbentsorbate attractive electrostatic interactions.
In buffer medium, the surface of PPS was primarily covered by
a layer of negative ions, followed by a diffused layer of positive
charges that hindered the penetration of BB3 but enhanced the
diffusion of CR onto the surface. The result was in agreement with
the theory stated because adsorbed amount of BB3 was reduced by
half but a vefold increase in the removal uptake of CR. The indifferent electrolyte in buffer medium only affected the PPS through
double layer compression without altering its surface charge, similar adsorption trends of BB3 and CR were obtained, in water and
buffer mediums.
The quantitative result of CR in buffer medium was inconclusive. The adsorption-enhancing effect was mainly caused by the
formation of aggregates in the positive diffused layer. When CR
molecules exceeded the available binding sites, the residual unbounded CR pushed the equilibrium toward the formation of complex. This complex formation was highly unstable, whereby CR
molecules would dissociate back to its aqueous form if rinsed with
water.

In present study, agitation rate did not improve sorption capacity remarkably as shown in the Fig. 6. Similar equilibrium sorption capacity of BB3 at 150 and 200 rpm, and of CR at 100 and
150 rpm were observed. Some studies [2325] revealed that variation of agitation has remarkable effect on the sorption capacity,
as well as the rate of sorption process whereby boundary layer of
the sorbent was minimised at high shaking rate. In contrast, studies carried out by Sag and Aktay (20 0 0) [18] showed that slight
effect of agitation rate was observed in chitin. This phenomenon
can be explained that shaking rate plays a vital role to conquer external mass transfer resistance only in a certain range of particle
size whereby small particle size (106 m) in present study possessed slight effect from the external mass transfer resistance with
the shaking rate in between 100 to 200 rpm.

3.5. Effect of initial dye concentration and agitation rate versus

contact time
The sorption of dyes on PPS as a function of contact time
for three different concentrations (50, 10 0, and 20 0 mg L1 ) were
showed in Fig. 5, indicated that amount of dyes adsorbed per unit
mass of PPS increased with an increase in the initial concentration
of each dye. The studies revealed that fast reaction happened at
the initial 15 min followed by second slow adsorption stage until
equilibrium established. Although an increase in initial concentration of respective dyes did not signicantly inuence the time of
achieving equilibrium, it accelerated the diffusion of dye molecules
from bulk solution onto PPS. As compared to CR, sorption capacity
of BB3 was affected remarkably with an increment of 10 mg per
unit mass of PPS for every doubled concentration. The surface of
PPS probably consists of very limited active sites which compatible with CR molecules. The equilibrium sorption capacity of CR at
100 and 200 mg L1 possessed almost similar amount, even though
one-fold increase in the initial concentration.

3.6. Kinetic models of sorption and mass transfer studies

The knowledge of kinetic studies of sorption process is required
to understand the sorption mechanism of PPS on different types of
dyes. The calculated equilibrium sorption capacities expressed by
pseudo-rst-order [26] and pseudo-second order [27] and Elovich
[28] kinetic models, as shown in Fig. 5, indicated that a narrow
range of deviation was obtained from the experimental values. The
evaluation was further analysed using error analysis (Table 1) and
conrmed that pseudo-second order kinetic model as the best-t
expression to represent the kinetic uptake of BB3 and CR onto PPS,
along with higher coecient of determination (r2 ) but lower SSE
and 2 values. Pseudo-second-order kinetic was proposed based
on the assumption that the adsorption system might be chemical process, which is controlled by a chemical adsorption mechanism involving electron sharing or electron transfer between PPS
and dye molecules. Besides, pseudo-rst-order kinetic model tted the experimental data well, especially for BB3. The rate of BB3
adsorption rate was based on the unoccupied active site on PPS at
time, t. The kinetic behaviour of BB3 and CR was suitably described
by Elovich model with a rising tendency at higher concentration. It
was revealed that the adsorption behaviour of dyes on PPS was not
only chemisorption, but involving ion exchange reactions [29].
Literatures indicate that the adsorption process is not constrained by bulk solution transfer and adsorption under experimental conditions. It is assumed that lm resistance or particles diffusion into the solid phase would be the rate-determining
step that regulated the adsorption performance of PPS by using

S.-L. Chan et al. / Journal of the Taiwan Institute of Chemical Engineers 61 (2016) 306315

311

Table 1
Comparison between the pseudo-rst order, pseudo-second order, and Elovich kinetic models for the adsorption of BB3
and CR onto PPS.
Kinetic model

Pseudo-rst order
qt = qe (1 eK1 t )

Parameter

BB3

Co (mg L1 )

50

100

200

50

100

200

qe ,exp (mg g1 )
qe,cal (mg g1 )

23.036
22.484

34.213
33.857

43.300
42.708

5.205
4.955

7.591
7.381

7.843
7.808

K1 (min1 )
r2
SSE

0.312
0.995
2.033
0.254
23.043

0.411
0.999
1.001
0.125
34.369

0.677
0.998
2.853
0.357
43.020

0.053
0.912
2.164
0.271
5.373

0.067
0.954
2.484
0.311
7.986

0.404
0.985
0.758
0.095
7.943

qe,cal (mg g1 )

Pseudo-second order
qt = K2 q2e t/(1 + K2 qe t )

K2 (g mg1 min1 )
r2
SSE

0.035
0.998
0.926
0.116
6.32E8

0.042
0.999
1.036
0.129
2.38E17

0.099
0.999
1.375
0.172
6.58E37

0.014
0.958
1.043
0.130
1.555

0.012
0.986
0.752
0.094
3.269

0.168
0.987
0.623
0.078
7.77E12

(g mg1 )

1.11
0.986
5.731
0.716

1.33
0.993
6.448
0.806

2.158
0.999
0.799
0.100

1.156
0.965
0.873
0.110

0.816
0.978
1.182
0.148

4.575
0.985
0.727
0.091

2
(mg g1 min1 )

Elovich qt =
1/ ln + 1/ ln t

CR

r2
SSE

qe and qt are sorption capacities at equilibrium, and at time, t (mg g1 ), respectively,

K1 and K2 are rate constant of pseudo-rst order (min1 ), pseudo-second order (g mg1 min1 ), respectively,
(mg g1 min1 ) and (g mg1 ) are the initial adsorption rate of the Elovich equation and the desorption constant related
to the extent of surface coverage and activation energy constant for chemisorption.
Table 2
Boundary layer effect and intraparticle diffusion parameters for different stirring speed and initial concentration, respectively of BB3 and CR.
Dye system

BB3

CR

Stirring speed (rpm)

100
150
200
100
150
200

Boundary layer effect

[d (Ct /Co )/dt ]t=0 = L S

InitialConc. (mg/L)

L S (cm min1 )

C (mg g1 )

0.004
0.004
0.002
0.001
0.001
0.002

0.459
0.454
0.389
0.933
0.940
0.930

0.988
0.666
0.705
0.894
0.906
0.936

50
100
200
50
100
200

Intraparticle diffusion
qt = K p t 0.5 + C
Kp (mg g1 min0.5 )

C (mg g1 )

1.179
2.293
0.679
0.384
0.612
0.606

16.331
24.824
39.727
1.177
1.924
5.500

0.767
0.942
0.921
0.925
0.902
0.862

Co and Ct are referred to initial concentration and liquid phase solutes concentration at time, t (mg L1 ).
L is external mass transfer coecient (cm min1 ), and S is specic surface area for the mass transfer.
qt and Kp are sorption capacities at time, t (mg g1 ) and rate constant of intraparticle diffusion (mg g1 min0.5 ), respectively.

boundary layer effect model and intraparticle diffusion model [30].

From Table 2, adsorption of BB3 molecules were governed by
boundary layer effect rather than intraparticle diffusion. Increase
agitation rate raise up L value as lm boundary layer surrounding the PPS particles are reduced at higher shaking rate until a certain limit. When the agitation rate was beyond the limit, strong
shear forces may interfere sorption process by damaging the structure of the sorbent. Mainly owing to boundary layer effect, the
slopes of Weber and Morris intraparticle diffusion plot do not pass
through the origin. The values of initial average boundary thickness
and intraparticle diffusion rate constants were increased with initial concentration. Contrastingly, shaking rate increased from 100
to 150 rpm did not increase L value, indicating the boundary layer
effect was not the rate-limiting step in CR adsorption mechanism.
It can be further conrmed by intraparticle diffusion model as
the slopes pass through the origin, revealing CR molecules transfer process was controlled solely by intraparticle diffusion at the
initial 15 min. However, further increase in turbulence in CR solution enhances the boundary layer effect in the system.
3.7. Adsorption isotherms
Sorption isotherm describes the properties and fundamental
physiochemical data of an equilibrium sorption, which expresses
the relationship between the amount of the adsorbed dye by

the PPS and unbound dye remained in the bulk solution. The
applicability of sorption process as a unit operation can be expressed by one or more of isotherm models [31]. In present study,
three isotherm models, namely Langmuir [32], Freundlich [33],
and Temkin [34] models are used to study sorption behaviours of
both BB3 and CR onto PPS using non-linear regression methods
(Table 3).
The Langmuir isotherm is best described as monolayer sorption
of dye onto homogeneous surface of PPS with no interaction between adsorbed dye molecules. Based on Langmuir analysis, the
maximum monolayer adsorption capacity (qm ) of the BB3 and CR
is 58.983 and 11.966 mg g1 , respectively, which is reasonably corresponded to the experimentally equilibrium sorption capacity. The
values of qm about some other adsorbents quantity towards BB3
and CR were listed in Table 4 in order to show the application
prospect of PPS. The value of qm of BB3 and CR onto PPS was relatively comparable to some materials listed although lower performance than commercial activated carbon. This suggests that, PPS
is a potential alternative with considerable adsorption capacity in
feasible and affordable dye adsorption system.
Langmuir isotherm can be expressed in terms of dimensionless
parameter (RL ) to predict the anity between the sorbate and sorbent whether is favourable or adverse.

RL =

(1 + KLCo )

(11)

312

S.-L. Chan et al. / Journal of the Taiwan Institute of Chemical Engineers 61 (2016) 306315
Table 3
Langmuir, Freundlich, and Temkin isotherm model parameters for BB3 and CR.
Isotherm

Parameter

BB3

CR

qmax (mg g )
KL (l mg1 )
r2
SSE

58.983
0.035
0.932
47.572
15.857

11.966
0.012
0.999
0.012
0.004

Freundlich qe = KF Ce

KF [(mg g1 ) (L mg1 )(1/ n ) ]]

1/nF (L g1 )
r2
SSE

Temkin qe = BT ln(AT Ce )

AT (L g1 )
BT (J mol1 )
r2
SSE

6.992
0.408
0.997
2.054
0.685
0.517
11.408
0.948
34.945
11.982

0.609
0.506
0.986
0.242
0.081
0.114
2.815
0.996
0.071
0.024

Langmuir qe = qm KLCe /(1 + KLCe )

1/n f

Ce is the equilibrium concentration of dye in bulk phase (mg L1 ), qe is the amount of adsorbed dye at equilibrium (mg g1 ), qmax is the maximum monolayer adsorption capacity
(mg g1 ),
KL is Langmuir constant related to the energy of adsorption (L mg1 ),
KF and 1/nF are Freundlich constant (L1 mg) and heterogeneity factor, respectively,
BT is heat of adsorption (J mol1 ), BT = RT/bT ; T is absolute temperature (K), R is the gas
constant (8.314 J mol1 K1 ), bT is Temkin constant, and AT is Temkin equilibrium binding
constant (L g1 ).
Table 4
Comparison of the maximum monolayer adsorption capacity of the PPS for BB3 and CR removal with
the other adsorbents.
Dye

Adsorbent

qm (mg g1 )

References

Basic Blue 3

Activated carbon from Kenaf

Activated carbon from Hevea brasiliensis seed coat
Aleppo pine-tree sawdust
Pineapple plant stem
Durian husk
Acrylic resin
Peat
Sugarcane bagasse
Risk Hull
Activated carbon (Commercial)
Activated carbon from apricot stone
Cattail root
Activated carbon from pine cone
Banana peel
Orange peel
Pineapple plant stem
Bagasse y ash
Rice Husk
Raw pine cone
Activated carbon from pomegranate
Rice Husk Ash
Activated carbon from coir pith
Cashew nut shell
Activated carbon (Laboratory)
Activated carbon (Commercial)

666.67
227.27
65.36
58.98
49.50
46.95
41
23.64
13.41
300
32.85
34.59
20.25
18.2
14.0
11.97
11.89
11.10
10.28
10.00
7.05
6.72
5.18
1.88
0.64

[35]
[36]
[37]
Present study
[38]
[39]
[40]
[41]
[42]
[43]
[44]
[45]
[46]
[20]
[20]
Present study
[47]
[48]
[49]
[50]
[51]
[52]
[53]
[47]
[47]

Congo
Red

The value of the dimensionless constant separation factor

(RL ) showed that both dyes adsorption process are favourable
(0 < RL < 1), but the values decreased with increasing initial
concentration.
In contrast to Langmuir isotherm, which assumes monolayer
coverage of adsorbate over a homogenous adsorbent surface, Freundlich isotherm model is, commonly used to study the heterogeneous surface of adsorbent, possessing multilayer adsorption. A
greater value of Freundlich capacity constant (KF ) indicates that
BB3 (6.992 L mg1 ) exhibited higher sorption capacity than CR
(0.609 L mg1 ) on PPS. It can be concluded that PPS has higher
anity on cationic than anionic dyes. The value 1/nF < 1, representing that the sorption is chemical process whereby the closer
the value of 1/nF toward zero, the more heterogeneous the surface
of PPS is.

Temkin and Pyzner in 1940 proposed that the heat of adsorption of all molecules in the layer reduces linearly with surface coverage due to indirect adsorbateadsorbate interaction on heterogeneous surface, and the adsorption is characterised by a uniform
distribution of the bonding energies up to some maximum binding energy. In fact, Temkin isotherm is derived from the Langmuir
adsorption isotherm. The positive heat of adsorption (BT > 0), indicated both dye sorption process are exothermic.
According to the obtained correlation coecients, high coecient values of CR obtained from Langmuir (R2 = 0.999) and
Temkin isotherm (R2 = 0.996) models indicated monolayer coverage of CR molecules on the heterogeneous surface PPS by uniform distribution of the bonding energies. In contrast to this, Freundlich isotherm exhibited good t to the experimental sorption
data of BB3 (R2 = 0.997), revealed non-uniform distribution of BB3

S.-L. Chan et al. / Journal of the Taiwan Institute of Chemical Engineers 61 (2016) 306315

313

Fig. 7. Effect of sorbent dosage on the sorption BB3 and CR in single dye solutions
onto PPS. Condition: 0.010.07 g of sorbent in 20 mL of 50 mg/L BB3 and CR in single dye solution at 150 rpm for 5 h at room temperature of 25 2 C.

over the heterogonous surface. The multi-site adsorption of BB3 on

PPS showed that the fractional coverage was not constant at different solution concentration. This was probably due to the multilayer
coverage formation.
3.8. Effect of Sorbent dosage
Sorbent dosage is one of the vital parameter to control the
sorption eciency in the study. As the number of sorbent increased, the sorption capacity is assumed to increase with increasing available sorption active sites of PPS. An upward trend
in the BB3 sorption uptake was observed yet the sorption capacity encountered a downward trend with increasing sorbent dosage
(Fig. 7). Conversely, the density of CR adsorbed on PPS remained
nearly constant, subsequently promoted the sorption uptake percentage with increasing sorbent dosage. The minimum amount of
PPS corresponding to the maximum adsorption is found to be the
optimum dosage, which is 0.03 g for both BB3 and CR.
The reduced sorption capacity at higher PPS dosage is attributed to the unsaturation of adsorption sites as aggregation
might form between the sorbent, resulting in a decrease of external surface area and an increase of diffusional path length. Besides,
the extent of desorption of dye molecules, which are slightly or reversibly bound to the surface, for instance BB3, will be promoted
owing to the higher collision frequency between the sorbent. Fig. 7
reveals that the strong interaction between CR and the solid phase
sorbent might be irreversible and resulted in a constant amount of
solute adsorbed per unit mass of sorbent.
3.9. Thermodynamic studies
Temperature is an inuencing factor in the actual application
as textile dye euents was normally discharged at temperature
ranges of 313 to 333 K. Fig. 8 showed that the uptake percentage of
BB3 and CR declined with increasing of temperature from 303 to
343 K. The dependence of BB3 and CR adsorption on temperature
was validated by vant Hoff plot .The distribution coecient, KD of
both dyes systems decreased linearly with increasing temperature,
indicating the substantivity of both dyes on PPS are highly temperature dependence. Elevated temperature enhanced dyes solubility in bulk solution more signicantly than adsorbent. As detailed
in Table 5, negative enthalpy value (H) indicates dye adsorption on PPS is exothermic nature which has been previously stated

Fig. 8. (a) Effect of temperature on the sorption BB3 and CR in single dye solutions
onto PPS. Condition: 0.03 g of sorbent in 20 mL of 50 mg/L BB3 and CR in single dye
solution at 150 rpm for 5 h. (b) Thermodynamic studies for BB3 and CR adsorption
onto PPS.

in Temkin isotherm whereby negative entropy value (S) reveals

dyes molecules in the adsorbed phase of PPS possess smaller randomness than the dyes molecules in bulk solution.
The distribution of dye molecules from the bulk solution to the
adsorbent is associated with a reduction in the Gibbs free energy
of bulk solution but an increment in the adsorbent. The temperature dependence Gibbs free energy for BB3 were negative at low
temperature (< 333 K) but it turned to become positive when temperature exceeded 343 K. BB3 adsorption by PPS is exothermic nature, resulting from the excess energetics released from the intermolecular interactions relative to those involved in breaking of
intramolecular interactions. At elevated temperature, the distribution coecient becomes more governed by the entropy change. Although thickness of the boundary layer diminished at high temperature, high tendency of the adsorbed BB3 detached from the
surface of PPS back to the bulk solution.
In contrast, increasing and positive G values were obtained
in this study for CR with elevating temperature although it is
an exothermic adsorption process. The unfavourable Gibbs free
energy reveals that CR adsorption is a feasible reaction yet the
solutesorbent interactions were not occurred naturally. The latter
interaction was governed by the formation of hydrogen bond
between the two terminal groups of carboxyl and hydroxyl in PPS
and amine in CR. However, the bond formation could only form
in applicable geometrical correspondence, which is energetically
unfavourable, especially in stronger electrostatic repulsion.
3.10. Reversibility and reusability
It is always desirable to regenerate exhausted adsorbent for
further application and to recover adsorbate. Desorption using different type of solvents can assist in elucidation of the

314

S.-L. Chan et al. / Journal of the Taiwan Institute of Chemical Engineers 61 (2016) 306315
Table 5
vant Hoff parameters for BB3 and CR at different temperature.
o
o
vant Hoff plot ln KD = RS RTH

Dye

BB3
CR

S (J mol1 K 1 )

41.40
60.36

H (kJ mol1 )

14.15
13.71

G (kJ mol1 ) Go = RT ln KD

303 K

313 K

323 K

333 K

343 K

1.61
4.58

1.19
5.18

0.78
5.79

0.37
6.40

0.05
7.00

Fig. 9. Uptake percentage of (a) BB3 and (b) CR for 3 consecutive cycles, and desorption of (c) BB3 and (d) CR in 4 different mediums.

adsorption/desorption mechanisms. It can been seen from

Fig. 9 that desorption of BB3 was favourable in HCl solution
and methanol, BB3 removal capability was depressed up to 20%
for the next 2 consecutive cycles. The attachment of BB3 to the
PPS was regarded as ion exchange while the un-desorbed portion
of BB3 could be explained by complex formation with the active
sites of PPS. Relatively poor removal eciencies of CR in four
different mediums were observed (desorption < 30%), but the
adsorption capacity of PPS regenerated in distilled water, was only
slightly decreased in another 2 consecutive cycles. It demonstrated
that the regeneration capacities of PPS in 0.1 M HCl and distilled
water for recovery of BB3 and CR, respectively were nearly similar
but relatively cost-effective to methanol.
3.11. Adsorption mechanism
The surface phenomenon is a manifestation of complicated interactions among PPS, dye molecules and the uids. The studied
parameters emphasised that a comparative sorption processes exhibited between BB3 and CR onto PPS. PPS surface carried negatively charged functional groups, resulting pronounced surfacesorbate electrostatic attraction as the driving force for BB3 adsorption onto PPS. It can be seen from higher rate constant of
BB3 relative to CR. The BB3 adsorption mechanism onto PPS is
proposed that the monolayer was formed on the PPS surface before the formation of the subsequent layers, and such interaction was the rate-limiting step. The rst adsorbateadsorbent layer

possessed stronger bonding as hydrogen bonding exhibited in between the hydrophilic functional groups on the surface and BB3
molecules, other than ion exchange reaction. The presence of adsorbed BB3 molecules makes easier the adsorption of other BB3
molecules. Since adsorbed BB3 molecules act as adsorption sites,
this behaviour is typical of systems where the adsorbateadsorbent
interactions have similar strength to the interactions between adsorbate molecules. Both Elovich kinetic model and desorption results emphasised that the dominated attachment of the dye to the
sorbent is regarded as ion exchange and physisorption, whereby
most of the bound BB3 could be detached back into uids using
acid and methanol. The extent of these interactions decreases with
increasing temperature.
Similar sorbatesorbent interaction happened between CR
molecules and PPS but such interaction was governed by the formation hydrogen bond and it could only formed in applicable geometrical correspondence where repulsive force was dominant over
attractive force. The G values of CR further conrmed that CR
adsorption onto PPS was thermodynamically unfavourable.
4. Conclusions
The good feasibility study of PPS to remove BB3 and CR
from aqueous solution was demonstrated in present study. The
honeycomb-shaped porous structure of PPS is predominated by
the presence of anionic active sites attributed to higher cationic
dyes sorption than anionic. The batch studies results indicated that

S.-L. Chan et al. / Journal of the Taiwan Institute of Chemical Engineers 61 (2016) 306315

adsorption capacity of PPS was affected by particle size, pH, initial dye concentration, contact time, and temperature yet less affected by agitation rate. The optimal pH for the removal of BB3
and CR was favoured at pH 10 and 4, respectively. Equilibrium data
of BB3 showed good correlation to Freundlich isotherm whereby
CR tted well with both Langmuir and Temkin isotherm models.
The maximum sorption capacity was 58.984 mg g1 for BB3 and
11.966 mg g1 for CR which is comparable to most of the lignocellulosic materials. The kinetic analysis showed that the adsorption achieved equilibrium within 120 min, both system tted well
in pseudo-second order kinetics. Thermodynamic studies indicated
the adsorption was exothermic and high temperature was no benecial for the adsorption. The desorption study demonstrated that
regeneration of PPS using water and HCl were highly feasible for
CR and BB3 system, respectively.
Acknowledgement
The authors would like to thank Wan Tee Longan Farm for the
supply of pineapple plants, and Ministry of Education, Malaysia for
the Mybrain 15 Scholarship (S.-L. Chan).
References
[1] Babu BR, Parande AK, Raghu S, Kumar TP. Cotton textile processing: waste generation and euent treatment. J Cotton Sci 2007;11:14153.
[2] Christie RM. Colour chemistry. United Kingdom: Royal Society of Chemistry;
2001.
[3] Srivastava S, Sinha R, Roy D. Toxicological effects of malachite green. Aquat
Toxicol 2004;66(3):31929.
[4] Schneider K, Hafner C, Jger I. Mutagenicity of textile dye products. J Appl Toxicol 2004;24(2):8391.
[5] de Arago Umbuzeiro G, Freeman HS, Warren SH, de Oliveira DP, Terao Y,
Watanabe T, Claxton LD. The contribution of azo dyes to the mutagenic activity of the Cristais River. Chemosphere 2005;60(1):5564.
[6] Anon. The biology & ecology of pineapple (Ananas comosus Var. comosus) in
Australia. Canberra: Oce of the Gene Technology Regulator; 2003.
[7] FAO. FAOSTAT database collections. Rome: Food and Agriculture Organization
of the United Nations; 2013.
[8] Ahmed OH, Husni MHA, Awang Noori AG, Hana MM. The removal and burning of pineapple residue in pineapple cultivation on tropical peat: an economic
viability comparison. J Trop Agric Sci 2002;25(1):4751.
[9] Ahmed OH, Husni MHA, Anuar AR, Hana MM. Economic viability of pineapple
residues recycling. J Sustain Agric 2003;21(4):12937.
[10] Vuc urovic VM, Razmovski RN, Miljic UD, Puka VS. Removal of cationic and
anionic azo dyes from aqueous solutions by adsorption on maize stem tissue.
J Taiwan Inst Chem Eng 2014;45(4):17008.
[11] Chowdhury S, Saha P. Pseudo-second-order kinetic models for the sorption of
Malachite green onto Tamarindus indica seeds: comparison of linear and nonlinear methods. Desalin Water Treat 2011;30(1-3):22936.
[12] Subramanyam B, Das A. Linearised and non-linearised isotherm models optimization analysis by error functions and statistical means. J Environ Health Sci
Eng 2014;12:927.
[13] Han R, Zhang L, Song C, Zhang M, Zhu H, Zhang L. Characterization of modied
wheat straw, kinetic and equilibrium study about copper ion and methylene
blue adsorption in batch mode. Carbohydr Polym 2010;79(4):11409.
[14] Adapa PK, Schonenau LG, Canam T, Dumonceaux T. Quantitative analysis of
lignocellulosic components of non-treated and steam exploded barley, canola,
oat and wheat straw using Fourier transform infrared spectroscopy. J Agric Sci
Technol 2011;1:17788.
[15] Azouaou N, Sadaoui Z, Djaafri A, Mokaddem H. Adsorption of cadmium from
aqueous solution onto untreated coffee grounds: equilibrium, kinetics and
thermodynamics. J Hazard Mater 2010;184(13):12634.
[16] Fernandez NB, Mullassery MD, Anirudhan TS. Adsorptive removal of arsenic(III)
ions from industry wastewaters using a weak anion exchanger prepared from
banana stem. J Appl Polym Sci 2012;125(S2) E262EE71.
[17] Shukla A, Zhang YH, Dubey P, Margrave JL, Shukla SS. The role of sawdust in
the removal of unwanted materials from water. J Hazard Mater 2002;95(1
2):13752.
[18] Sag Y, Aktay Y. Mass transfer and equilibrium studies for the sorption of
chromium ions onto chitin. Process Biochem 20 0 0;36(12):15773.
[19] Yaneva ZL, Georgieva NV. Insights into Congo red adsorption on agro-industrial
materials- spectral, equilibrium, kinetic, thermodynamic, dynamic and desorption studies. A review. Int Rev Chem Eng 2013;4(2):12746.
[20] Annadurai G, Juang R-S, Lee DJ. Use of cellulose-based wastes for adsorption
of dyes from aqueous solutions. J Hazard Mater 2002;92(3):26374.
[21] Newcombe G, Drikas M. Adsorption of NOM onto activated carbon: electrostatic and non- electrostatic effects. J Carbon 1997;35:123950.

315

[22] Gmez JM, Galn J, Rodrguez A, Walker GM. Dye adsorption onto mesoporous
materials: pH inuence, kinetics and equilibrium in buffered and saline media.
J Environ Manag 2014;146:35561.
[23] Low KS, Lee CK, Tan BF. Quaternized wood as sorbent for reactive dyes. Appl
Biochem Biotech 20 0 0;87:23345.
[24] Batzias FA, Sidiras DK. Simulation of methylene blue adsorption by saltstreated beech sawdust in batch and xed-bed systems. J Hazard Mater
2007;149(1):817.
[25] Kyzas GZ. Commercial coffee wastes as materials for adsorption of heavy metals from aqueous solutions. Materials 2012;5(10):182640.
[26] Lagergren S. Zur theorie der sogenannten adsorption gelosterstoffe. Kungliga
Sven Vetenskapsakademiens 1898;24(4):139.
[27] Ho YS, McKay G. Pseudo-second order model for sorption processes. Process
Biochem 1999;34(5):45165.
[28] Zeldovich J. ber den mechanismus der katalytischen oxydation von CO an
MnO2 . Acta Physicochim URSS 1934;1:364499.
[29] Cao JS, Lin JX, Fang F, Zhang MT, Hu ZR. A new absorbent by modifying walnut shell for the removal of anionic dye: kinetic and thermodynamic studies.
Bioresour Technol 2014;166:199205.
[30] Weber WJ, Morris JC. Kinetic of adsorption on carbon from solution. J Sanit
Eng Div 1963;89(2):3160.
[31] Crini GG, Pierre-Marie B. Sorption processes and pollution: conventional and
non-conventional sorbents for pollutant removal from wastewaters. Besancon:
Presses universitaires de Franche-Comte; 2010.
[32] Langmuir I. The constitution and fundamental properties of solids and liquids.
Part I. Solids. J Am Chem Soc 1916;38:222195.
[33] Freundlich HMF. Uber die adsorption in losungen. J Phy Chem 1906;57:385
470.
[34] Temkin MJ, Pyzhev V. Recent modications to Langmuir isotherms. Acta
Physicochim URSS 1940;12:21722.
[35] Aber S, Sheydaei M. Application of physicochemically prepared activated carbon ber for the removal of basic blue 3 from water. Desalin Water Treat
2011;28(1-3):97102.
[36] Hameed BH, Daud FBM. Adsorption studies of basic dye on activated carbon derived from agricultural waste: hevea brasiliensis seed coat. J Chem Eng
2008;139(1):4855.
[37] Ouazene N, Lounis A. Adsorption characteristics of CI Basic Blue 3 from aqueous solution onto Aleppo pine-tree sawdust. Color Technol 2012;128(1):217.
[38] Ong ST, Tan SY, Khoo EC, Lee SL, Ha ST. Equilibrium studies for Basic blue 3
adsorption onto durian peel (Durio zibethinus Murray). Desalin Water Treat
2012;45(1-3):1619.
[39] Brsa nescu A, Buha ceanu R, Dulman V. Removal of Basic Blue 3 by sorption
onto a weak acid acrylic resin. J Appl Polym Sci 2009;113(1):60714.
[40] Contreras E, Martinez B, Seplveda L, Palma C. Kinetics of basic dye adsorption
onto Sphagnum Magellanicum peat. Adsorpt Sci Technol 2007;25(9):63746.
[41] Khoo EC. Removal of basic dyes using sugarcane bagasse [Dissertation].
Malaysia: Universiti Tunku Abdul Rahman; 2012.
[42] Ong ST, Lee CK, Zainal Z. Removal of basic and reactive dyes using Ethylenediamine modied rice hull. Bioresour Technol 2007;98(15):27929.
[43] Purkait MK, Maiti A, DasGupta S, De S. Removal of Congo red using activated
carbon and its regeneration. J Hazard Mater 2007;145(12):28795.
[44] Abbas M, Trari M. Kinetic, equilibrium and thermodynamic study on the removal of Congo red from aqueous solutions by adsorption onto apricot stone.
Process Saf Environ Prot 2015;98:42436.
[45] Hu Z, Chen H, Ji F, Yuan S. Removal of Congo red using activated carbon and
its regeneration. J Hazard Mater 2010;173(13):2927.
[46] Dawood S, Sen T, Phan C. Synthesis and characterisation of novel-activated
carbon from waste biomass pine cone and its application in the removal of
Congo red dye from aqueous solution by adsorption. Water Air Soil Pollut
2013;225(1):116.
[47] Mall ID, Srivastava VC, Agarwal NK, Mishra IM. Removal of Congo red from
aqueous solution by bagasse y ash and activated carbon: Kinetic study and
equilibrium isotherm analyses. Chemosphere 2005;61(4):492501.
[48] Pan H, Chen S, Jiyun S, Yinli L, Runping H. Adsorption of Congo red from solution by rice husk in batch mode. In: Proceedings of the 4th international conference on bioinformatics and biomedical engineering, iCBBE Jun 1820,2010.
Chengdu, China. New York: IEEE; 2010. p. 14.
[49] Dawood S, Sen TK. Removal of anionic dye Congo red from aqueous solution by raw pine and acid-treated pine cone powder as adsorbent: equilibrium, thermodynamic, kinetics, mechanism and process design. Water Res
2012;46(6):193346.
[50] Ghaedi M, Tavallali H, Shari M, Kokhdan SN, Asghari A. Preparation of low
cost activated carbon from Myrtus communis and pomegranate and their ecient application for removal of Congo red from aqueous solution. Spectrochim
Acta Part A 2012;86:10714.
[51] Chowdhury AK, Sarkar AD, Bandyopadhyay A. Rice husk ash as a low cost adsorbent for the removal of Methylene blue and Congo red in aqueous phases.
CLEAN Soil Air Water 2009;37(7):58191.
[52] Namasivayam C, Kavitha D. Removal of Congo red from water by adsorption
onto activated carbon prepared from coir pith, an agricultural solid waste.
Dyes Pigment 2002;54(1):4758.
[53] SenthilKumar P, Ramalingam S, Senthamarai C, Niranjanaa M, Vijayalakshmi P,
Sivanesan S. Adsorption of dye from aqueous solution by cashew nut shell:
studies on equilibrium isotherm, kinetics and thermodynamics of interactions.
Desalination 2010;261(12):5260.