Arabian Journal of Chemistry (2013) xxx, xxxxxx

King Saud University

Arabian Journal of Chemistry

www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

Equilibrium, kinetics and thermodynamics of Cadmium

(II) biosorption on to composite chitosan biosorbent
Suguna Madala a,*, Siva Kumar Nadavala b, Sreenivasulu Vudagandla a,
Veera M. Boddu c, Krishnaiah Abburi a

a
Biopolymers and Thermo Physical Laboratories, Department of Chemistry, Sri Venkateswara University, Tirupati 517 502,
A.P., India
b
Department of Biological & Agricultural Engineering, Faculty of Engineering, Universiti Putra Malaysia, 43400 UPM Serdang,
Selangor Darul Ehsan, Malaysia
c
US Army Engineering Research and Development Center, CERL, Champaign, IL 81822, USA

Received 4 September 2012; accepted 17 July 2013

KEYWORDS Abstract A composite chitosan biosorbent (CCB) was prepared by coating chitosan onto ceramic
Biosorption; alumina. The uptake capacity of CCB for Cadmium (II) was studied under equilibrium conditions
Cadmium(II); in the temperature range 298318 K. The sorbent was characterized by high temperature, pyrolysis,
Composite chitosan biosor- porosimetry, FTIR, SEM, EDAX and XRD analyses. The adsorption capacity of the biosorbent is
bent (CCB); investigated as a function of initial pH, contact time, initial concentration of adsorbate, amount of
Isotherm models; biomass and temperature. The data were analyzed using different kinetic and isotherm models.
Kinetics; Pseudo-second-order model and Elovich equation provided a better representation of the experimen-
Thermodynamics
tal data. Among the adsorption isotherm models, Langmuir model gave a better t of the equilibrium
data. The calculated thermodynamic parameters showed that the biosorption of Cd(II) ions is feasi-
ble, spontaneous and endothermic in nature. Experimental results indicated that the CCB beads
appear to be a promising biosorbent material for the removal of Cd(II) ions from aqueous media.
2013 Production and hosting by Elsevier B.V. on behalf of King Saud University.

1. Introduction metals have been continuously released into the environment

Heavy metal removal from ground water and industrial waste
water is currently an important environmental concern. Heavy
* Corresponding author. Tel.: +91 9393621986.
E-mail address: madala.suguna@gmail.com (S. Madala).
Peer review under responsibility of King Saud University.
Production and hosting by Elsevier
1878-5352 2013 Production and hosting by Elsevier B.V. on behalf of King Saud University.
http://dx.doi.org/10.1016/j.arabjc.2013.07.017
due to rapid industrialization and have created a major global
concern. The removal of these metal ions from drinking water
is a real challenge due to their trace quantities, formation of
complexes with natural organic matter and toxic even at very
low concentrations (Vieira and Beppu, 2006). Unlike some or-
ganic pollutants, heavy metals are not biodegradable and can-
not be metabolized or decomposed. Heavy metals can easily
enter into the food chain through a number of pathways and
cause progressive toxic effects with gradual accumulation in
living organisms over their life span. Many toxic metals are of-
ten detected in industrial waste water which originates from

Please cite this article in press as: Madala, S. et al., Equilibrium, kinetics and thermodynamics of Cadmium (II) biosorption on to
composite chitosan biosorbent. Arabian Journal of Chemistry (2013), http://dx.doi.org/10.1016/j.arabjc.2013.07.017
2 S. Madala et al.
metal plating, mining activities, smelting, battery manufacture,
printing, paint and pigment industries etc., (Niu et al., 2010;
Hu et al., 2011; Shukla and Sakhardande, 1992).
Cadmium is a dangerous pollutant that is released into aqua-
tic medium from electro-plating industries, batteries, phosphate
fertilizers, mining, pigments, stabilizers and alloys. Cadmium
nds its way to the water streams through waste discharge
(Low and Lee, 1991; Salim et al., 1992). Cadmium has been clas-
sied as a human carcinogen and teratogen impacting lungs,
kidneys, liver renal dysfunction, hypertension, hepatic injury
and reproductive organs (Waalkes, 2000; Sharma, 2008; Maha-
lik et al., 1995; Kazi et al., 2008a, b). The World Health Organi-
zation has set a maximum guideline concentration of
0.003 mg L1 for Cd in drinking water (WHO, 2008). Therefore,
it is very essential to control the concentration of heavy metals in
waste water before its disposal into the environment.
The techniques that have been widely used to remove toxic
metals from industrial efuents are ion exchange, chemical
precipitation, complexation, elecrodeposition, liquidliquid
extraction, reverse osmosis, oxidationreduction process,
evaporation, membrane separation and adsorption. But these
methods are expensive and ineffective especially when the hea-
vy metal ions are present in the waste water at low concentra-
tions. Adsorption is one of the most economical, effective and
widely used methods for the removal of toxic metals from
aqueous environment.
Recent researchers have been focused on the modication of
chitosan. Coating chitosan as a thin layer onto an immobiliza-
tion support increases the accessibility of its binding sites, and
improves the mechanical stability (Wan et al., 2004). Several
studies of metal ion adsorption by modied chitosan have been
carried out in recent years, such as isotherm, kinetic and thermo-
dynamic studies of lead and copper uptake by H2SO4 modied
chitosan (Kamari and Ngah, 2009), the removal of lead and cop-
per by chitosan coated sand (Wan et al., 2010), adsorption
characterization of Pb(II) and Cu(II) by chitosan- tripolyphos-
phate beads (Ngah and Fatinathan, 2010), removal of lead by
glutaraldehyde cross linked chitosan beads (Suguna et al.,
2011), removal of copper, lead and nickel by chitosan immobi-
lized on bentonite (Futalan et al., 2011), removal of copper
and nickel by chitosan coated PVC beads (Popuri et al., 2009),
removal of Cu(II) and Cd(II) by chitosan crosslinked with epi-
chlorohydrin-triphosphate (Laus and de Favere, 2011), removal
of Hg(II), Cd(II) and Zn(II) by cross-linked magnetic chitosan-
phenylthiourea resin (Moneir and Abdel Latif, 2012). Krish-
napriya and Kandaswami (2010) synthesized a new chitosan
biopolymer derivative and studied adsorption of metal ions.
Gupta et al. (2012) have studied the adsorptive removal of
Pb(II), Co(II) and Ni(II) by hydroxyapatite/chitosan composite
from aqueous solution. Monier et al. (2012) studied the adsorp-
tion of Cu(II), Cd(II) and Ni(II) ions by cross-linked magnetic
chitosan-2-aminopyridine glyoxal schiffs base. Boddu et al.
(2003) prepared CCB beads and studied the removal of hexava-
lent chromium from waste water and also studied about the re-
moval of copper (II) and nickel (II) ions from aqueous solutions
(Boddu et al., 2008).
Chitosan contains reactive hydroxyl and amino groups that
have the potential to bind heavy metals. Pure chitosan has the
property to agglomerate and form a gel in aqueous medium, so
most of the hydroxyl and amino groups are inaccessible for
metal binding. To improve its adsorption capacity and en-
hance the sorption rate, the design and exploration of novel
Please cite this article in press as: Madala, S. et al., Equilibrium, kinetics and thermodynamics of Cadmium (II) biosorption on to
composite chitosan biosorbent. Arabian Journal of Chemistry (2013), http://dx.doi.org/10.1016/j.arabjc.2013.07.017
adsorbents are still necessary. Transport of the metal contam-
inants to the binding sites plays a very important role in the
process design. With an objective to provide a physical support
to withstand the mechanical pressure in a hydrodynamic envi-
ronment, to improve its resistance toward dissolution in acidic
medium, to make the binding sites readily available for the
adsorbate and to increase the porosity thereby to achieve en-
hanced adsorption rates, we have prepared a composite chito-
san biosorbent by coating chitosan on alumina.
The primary objective of the present study was to evaluate
the removal efciency of the CCB for Cd(II) ions from aque-
ous solutions. Various spectroscopic and microscopic examin-
ations were done to characterize the material and evaluate its
performance for Cd(II) uptake. Experimental parameters
affecting the biosorption process such as effect of pH, initial
metal ions concentration, biomass dosage, contact time and
temperature were studied. The experimental equilibrium
adsorption data were analyzed by different kinetic and iso-
therm models. The thermodynamic parameters such as DG,
DH and DS for biosorption process were evaluated.
2. Materials and methods
2.1. Materials
Medium molecular weight chitosan (7585% deacetylated),
oxalic acid dehydrate, and 150 mesh-activated alumina were
obtained from SigmaAldrich Chemicals (St. Louis, MO,
USA). All the necessary chemicals used were of analytical
grade and obtained from M/S Qualigens Fine Chemicals,
Mumbai, India. Stock solution (1000 mg L1) was prepared
by dissolving Cd(NO3)2.4H2O. This was further diluted to ob-
tain the desired concentration for practical use. The pH of the
solution was measured with a Digisun electronics digital pH
meter using a solid electrode calibrated with a standard buffer
solution. A ame atomic absorption spectrophotometer (Shi-
madzu AA-6300, Japan) with deuterium background corrector
was used. All measurements were carried out in an air/acety-
lene ame. A 10 cm long slot burner head, a lamp and an
air-acetylene ame were used. The operating parameters for
working element were set as recommended by the manufac-
turer. The FTIR spectra were recorded using Thermo-Nicolet
FTIR, Nicolet IR- 200 series, Germany. Scanning Electron
Microscopy (Model Evo15, CarlZeiss, England) has been used
to study the surface morphology of the biosorbent. The syn-
thetic solutions were prepared by diluting Cd(II) standard
stock solutions (concentration 1000 3 mg L1). Fresh dilu-
tions were used in each experiment.
2.2. Synthesis of composite chitosan biosorbent
CCB was synthesized following the procedure described by
Boddu et al. (2003). Ceramic alumina with 150 mesh sizes
was dried in oven for 4 h at 110 C followed by stirring with
oxalic acid for 4 h at room temperature, ltering, washing
twice with DI water, and drying in an oven at 70 C under vac-
uum for 24 h. About 50 g of medium molecular weight chito-
san was slowly added to 1000 mL of 10 wt.% oxalic acid
solution with stirring. The acid and chitosan formed a viscous
mixture (gel), which was heated to 4050 C to facilitate mix-
ing. Approximately 500 mL of the chitosan gel was diluted
Equilibrium, kinetics and thermodynamics of Cadmium (II) biosorption on to composite chitosan biosorbent
with water and heated to 4050 C while stirring vigorously.
About 500 g of the acid treated alumina was slowly added to
the diluted gel and stirred for about 36 h at constant stirring
rate. The contents are allowed to settle, and the clear liquid
was ltered out under vacuum with Whatman no 41 lter pa-
per. The composite biosorbent was washed twice with DI
water and dried in the oven at 55 C under vacuum for 24 h.
The coating process was then repeated on the once coated bio-
sorbent to increase loading of chitosan onto the alumina. Ex-
cess oxalic acid in the composite biosorbent was neutralized by
treatment with aqueous NaOH. The mixture was then ltered
with Whatman No. 41 lter paper and washed with DI water
to remove excess NaOH. Twice-coated biosorbent was then al-
lowed to dry in the oven under vacuum at 55 C for about
48 h. The biosorbent was sieved and the beads between 32
and +60 mesh were used for the experimental work.
2.3. Batch studies
Batch adsorption experiments were carried out in Erlenmeyer
asks by adding 0.1 g of CCB in 100 mL of aqueous Cd(II)
solution at desired initial pH, metal ion concentration and
temperature. The initial pH was adjusted with solutions of
0.1 M HCl or 0.1 M NaOH. The asks were gently agitated
in a temperature controlled water bath shaker at 200 rpm for
a period of 3 h. All the experiments were performed in tripli-
cates at the desired initial conditions and the concurrent value
was taken. The contents of ask were separated from the bio-
sorbent by ltration, using Whatman No. 42 and the ltrate
was analyzed for remaining metal concentration in the sample
using atomic absorption spectrophotometer. The amount of
metal ion sorbed per unit mass of the biosorbent (mg g1)
was evaluated by using the following equation:
Ci  Ce V
qe 1 CCB loaded with metal ion. This observation provides evi-
m
where qe (mg g1) is the adsorption capacity at equilibrium, Ci
and Ce denote respectively the initial and equilibrium concen-
trations of metal ion (mg L1), V (L) is the volume of adsor-
bate and m (g) is the amount of adsorbent. To study the
effect of initial pH on the metal ion uptake by CCB, sorption
experiments were performed by using 100 mL of solution with
initial metal ion concentration of 100 mg L1 and adsorbent
dose of 0.1 g at 298 K by varying the pH of the solution.
The effect of adsorbent dose on adsorption of metal ions
was studied by agitating 100 mL of 100 mg L1 metal solution
with different amounts of adsorbent. Effect of initial metal ion
concentration was studied with initial metal ion concentrations
of 100, 200, 300 and 400 mg L1 keeping adsorbent and pH
constant. The effect of contact time on the removal of the me-
tal ion was studied by varying the contact time from 30 to
210 min at 298 K.
3. Results and discussion
3.1. Characterization of biosorbent
3.1.1. Determination of chitosan loading on alumina by pyrolysis
technique
High temperature pyrolysis indicated that pure alumina lost
about 2.1 wt.%, oxalic acid treated alumina lost 4.5 wt.%
Please cite this article in press as: Madala, S. et al., Equilibrium, kinetics and thermodynamics of Cadmium (II) biosorption on to
composite chitosan biosorbent. Arabian Journal of Chemistry (2013), http://dx.doi.org/10.1016/j.arabjc.2013.07.017
3
and single coating CCB lost 7.8 wt.%. The net amount of
chitosan on the twice coated biosorbent was found to be
21.1 wt.%. Pure chitosan leaves a residue of about 0.7 wt.%
after pyrolysis at 750 C. Chitin is obtained from crab shells
by acidbase extraction and chitosan is obtained from chitin
by the deacetylation process. The residue may be due to a
small amount of calcium carbonate that remains bound with
the chitin. Since the residue is in such a small amount, no at-
tempt was made to correct the chitosan net weight for this.
3.1.2. Surface area analysis
Surface area, pore volume and pore diameter of the CCB were
determined with a Micromeritics BET instrument by means of
adsorption of ultra pure nitrogen at 196 C. Average values
of these properties are 125.24 m2g1, 0.1775 cm3g1 and
71.12 A respectively.
3.1.3. FTIR analysis
FTIR spectral analysis is important in identifying the different
functional groups present on the surface of biosorbent which
are responsible for the binding of metal ions. FTIR spectra
in the range of 4000500 cm1 for the CCB before and after
biosorption of Cd(II) are shown in Fig. 1(a) and (b) respec-
tively. The FTIR spectrum of CCB in Fig. 1(a) indicates the
presence of predominant peaks at 3379.8 cm1 (OH and
NH stretching), 2924.87 cm1 (CH stretching), 1661.0 cm1
(NH bending in NH2), 1393.3 cm1 (NH deformation
vibration in NH2) and 1065.1 cm1 (COC stretching).
This reveals that all functional groups present in chitosan are
intact even after coating on alumina and are available for
interaction with the metal ions. The intensity of transmittance
of peaks is relatively greater in the case of CCB loaded with
metal ions compared to the virgin CCB. This may be attrib-
uted to the presence of fewer free functional groups in the
dence that the functional groups such as NH2, and OH
are involved in binding the cadmium metal ion to CCB. The
proposed model for the formation of a complex between chito-
san and cadmium metal ion is shown in Supplementary
Figure 1.
3.1.4. Scanning electron microscopic studies
Scanning electron micrographs (SEM), recorded using soft-
ware controlled digital scanning electron microscope, are gi-
ven in Fig. 2(a) and (b). The SEM of CCB beads shows no
particular crystalline structure and it rather appears spheri-
cal. The SEM micrographs of CCB beads illustrate the sur-
face texture and porosity of CCB beads with holes and
small openings on the surface, thereby increasing the con-
tact area, which facilitates the pore diffusion during adsorp-
tion. The porous nature is clearly evident from these
micrographs.
3.1.5. EDAX analysis
The sample composition and element contents were analyzed
by using the energy dispersive analysis system of X-ray
(EDAX) (EDAX, Ltd., USA). EDAX analysis was conducted
to evaluate the adsorption of cadmium on CCB beads. The
EDAX spectrum of CCB beads indicated the presence of C,
O, Al, K, Na and Si in the structure (Fig. 3(a)) but did not
4 S. Madala et al.

Figure 1 FTIR spectra of (a) CCB beads before biosorption (b) Loaded with Cd(II).

show the characteristic signal of Cd ions on the surface of pure
CCB beads. An EDAX spectrum was also recorded for CCB
loaded with Cd(II) ions (Fig. 3(b)), which gives the character-
istic peak for Cd at 3.20 keV. This conrms the binding of the
cadmium ions to CCB surface.
3.1.6. X-ray diffraction studies
Powder X-ray diffraction patterns were recorded on a Bruker
D8-Advance diffractometer using graphite monochromatic
CuKa1 (1.5406 A) and Ka2 (1.54439 A) radiations. Fig. 4 (a)
and (b) shows the X-ray diffraction patterns of CCB biosor-
bent before and after adsorption of Cd(II). In Fig. 4(a) three
broad peaks are centered at 2 theta = 19.20, 29.95 and
41.61 and also half broad peak at 5, which indicate the amor-
phous nature of the biosorbent, so the metal ion could more
easily penetrate through the biosorbent surface. In Fig. 4(b),
3.2. Effect of pH
In order to evaluate the inuence of this parameter on the
adsorption of Cd(II) the experiments are carried out in the
pH range of pH 2.08.0. The experiments could not be con-
ducted at pH less than 2.0 to avoid dissolution of CCB beads
and could not be conducted above pH at 8.0 to avoid the pre-
cipitation of Cd(II) ions. The variation of adsorption capacity
of CCB beads with pH is graphically represented in Supple-
mentary Fig 2. The maximum uptake of Cd(II) ions takes
place at pH 6.0 and decreases in adsorption capacity on either
side of pH 6.0. The free amino groups (NH2) in chitosan
(Ch-) exist in equilibrium with the protanated amino group
in the presence of acidic aqueous solution.

Ch  NH2 H2 O $ Ch  NH
3 OH

one major broad amorphous peak at 2038, one minor broad The amino groups are protophillic and become NH3+ in an
amorphous peak at around 42.17 and one broad hump at acidic medium. At low pH values, protons occupy most of the
6.5210.33 also amorphous. sorption sites on the biosorbent surface resulting in adsorption

Please cite this article in press as: Madala, S. et al., Equilibrium, kinetics and thermodynamics of Cadmium (II) biosorption on to
composite chitosan biosorbent. Arabian Journal of Chemistry (2013), http://dx.doi.org/10.1016/j.arabjc.2013.07.017
Equilibrium, kinetics and thermodynamics of Cadmium (II) biosorption on to composite chitosan biosorbent
Figure 2 Scanning electron micrographs of (a) scanning electron
micrographs of the CCB at 100 (b) scanning electron micro-
graphs of the CCB at 800.
Figure 3 Energy dispersive X-ray (EDAX) analysis of (a) CCB
beads before biosorption (b) After biosorption of Cd(II).
Please cite this article in press as: Madala, S. et al., Equilibrium, kinetics and thermodynamics of Cadmium (II) biosorption on to
composite chitosan biosorbent. Arabian Journal of Chemistry (2013), http://dx.doi.org/10.1016/j.arabjc.2013.07.017
5
Figure 4 XRD pattern of (a) CCB beads before biosorption (b)
Loaded with Cd(II).
of smaller amounts of cadmium ions because of electrostatic
repulsion. With the increase of pH, the amino groups become
free from protanation due to a decrease in the concentration of
hydrogen ions leading to the decrease in competition of H+
with metal ions for sorption sites and thus the adsorption
capacity increases. However the precipitation of Cd(II) ions
could lead to the decrease of adsorption capacity above pH
8.0.
Cadmium in an aqueous solution is hydrolyzed with the
formation of various species, depending on the solution pH.
Moreover, Cd2+, which is the main hydrolyzed cadmium spe-
cies in the pH range 5.07.0 appears in the form of Cd(OH)+,
Cd(OH)2, and Cd(OH)3. Among them Cd2+ is the predomi-
nant species in the solution within this pH range. The fraction
of negatively charged hydrolysis products in the solution in-
creases as pH increases. Chitosan can form chelates with cad-
mium ions with the release of H+ ions. A chelate formation
may require the involvement of the two or more complexion
groups from the molecule. The Cd(II) ion may seek two or
more amine groups from chitosan to form the complex. This
should normally reduce the solution pH. In the case of chito-
san, the protanation of NH2 groups occurs at a rather low pH
range. The fact that the pH of the solution increased as the
adsorption progressed suggests that Cd(II) formed a covalent
bond with the NH2 group. The two NH2 groups could come
from two different glucosamine residues of the same molecule,
or from two different molecules of chitosan. Jha et al. (1988)
6 S. Madala et al.
compared the stability constants for ammonia and amino com-
plexes with those for chloro complexes of cadmium and noted
that the formation of covalent bond with amine nitrogen is the
more preferred reaction.
3.3. Effect of adsorbent dosage
To understand the effect of amount of adsorbent on adsorp-
tion of Cd(II), the experiments were performed at pH 6.0 with
100 ml of sorbate solution by varying the amount of adsorbent
from 0.05 to 0.5 g. The percent removal of Cd(II) ions in-
creases with increase of amount of CCB due to the greater
availability of binding sites of the biosorbent. The maximum
removal efciency is with 0.4 g of CCB and the maximum per-
cent removal is about 93.76% (Fig. 5).
3.4. Effect of contact time and initial metal ion concentration
The extent of adsorption increases with time and attained equi-
librium for all the concentrations Cd(II) studied (100
400 mg L1) at 180 min. The plot was drawn between time
and adsorption capacity (Supplementary Figure 3). In the ini-
tial stages the removal efciencies of the biosorbent increased
rapidly due to the abundant availability of active binding sites
on the biomass, and with gradual occupancy of these sites, the
sorption became less efcient in the later stages.
3.5. Adsorption kinetics
In order to investigate the mechanism and to determine the
rate controlling step of adsorption of Cd(II) on CCB, kinetic
models were used. The rate constants were calculated using
pseudo-rst-order and pseudo-second-order kinetic models
(Siva Kumar et al., 2012) and the rate controlling step was
determined by intra-particle diffusion model. The pseudo-
rst-order is represented by:
lnqe  qt ln qe  k1 t
where k1 is the pseudo-rst-order rate constant (min ) of
adsorption, qe and qt (mg g1) are the amounts of metal ion
adsorbed at equilibrium and time t (min), respectively. The va-
lue of k1 was calculated from the slope of the linear plot of log
140
Adsorption capacity
Adsorption capacity (mg/g)
120 % Removal
100
80
60
40
20
0.0 0.1 0.2 0.3 0.4
Amount of adsorbent (g/L)
Figure 5 Effect of biosorbent dose on percent removal of Cd(II)
onto CCB beads. (Experimental conditions: initial conc. 100 mg/
L, contact time 3 h, pH 6.0.).
Please cite this article in press as: Madala, S. et al., Equilibrium, kinetics and thermodynamics of Cadmium (II) biosorption on to
composite chitosan biosorbent. Arabian Journal of Chemistry (2013), http://dx.doi.org/10.1016/j.arabjc.2013.07.017
(qeqt) verses t. The linear form of pseudo-second-order equa-
tion can be written as:
t 1 1
t 3
qt k2 q2e qe
where k2 is the pseudo-second-order rate constant
(g mg1 min1). The values of k2 and qe were calculated from
the plot of t/qt vs. t (Supplementary Figure 4). The results of
kinetic parameters are shown in Table 1. The validity of each
model could be checked by the tness of the straight lines (R2
values). The qe (cal) values calculated from pseudo-rst-order
kinetic model differed appreciably from the experimental val-
ues. However, in the pseudo-second-order kinetic model the
calculated qe (cal) are very close to qe (exp) at all initial metal
ion concentrations. Further, the values of correlation coef-
cients (R2) of pseudo-rst-order model were less than pseu-
do-second-order model indicating that the pseudo-second-
order is better obeyed than the pseudo-rst-order model.
The intra-particle diffusion model is used to investigate the
diffusion controlled adsorption system. The probability of the
intra-particle diffusion was explored by using the following
equation (Weber and Morris, 1964):
qt kid t1=2 C 4
1
where qt (mg g ) is the adsorption capacity at any time t
(min), kid is the intraparticle diffusion rate constant
(mg g1 min1/2), C is the value of intercept which gives an idea
about the boundary layer thickness, i.e., the larger intercept;
the greater is the boundary effect. The plots of qt vs. the square
root of time obtained for the adsorption of Cd(II) onto CCB at
different concentrations are shown in Supplementary Figure 5.
The intraparticle rate constant kid (mg g1 min1/2) and inter-
cept C are given in Table 1. The plots are not linear over the
whole time range, indicating that more than one step is in-
volved in the adsorption of metal ions. If the intra-particle dif-
fusion is the only rate-controlling step then the plot should
pass through the origin, else the boundary layer diffusion af-
2 fects the adsorption to some degree. The linear curve is devi-
1
ated from the origin or near saturation because of the
differences in the mass transfer rate in the initial and nal
stages of adsorption. The plots are not passing through origin
indicating that the intra particle diffusion is not the only rate
determining factor.
Boyd model is applied to check whether sorption proceeds
via lm diffusion or intraparticle diffusion mechanism. The
model can be expressed in the following form (Boyd et al.,
140 1947):
 
120 6
F 1  2 expBt 5
100
P
where F = qt/qe; qe is the amount of metal ions adsorbed at
80
equilibrium (mg g1), qt represents the amount of ions ad-
60 sorbed at any time t (min) and Bt is a mathematical function
of F. Eq. (5) can be rearranged by taking the natural logarithm
40
to obtain the equation:
20
Bt 0:4977  ln1  F 6
0.5
The plots of Bt vs. t at different initial concentrations of Cd(II)
are shown in Supplementary Figure 6, which are linear with
the correlation coefcient (R2) greater than 0.987. The results
suggest that the adsorption process is controlled by lm
diffusion.
Equilibrium, kinetics and thermodynamics of Cadmium (II) biosorption on to composite chitosan biosorbent 7

The Elovich equation has been applied satisfactorily to

some chemisorption processes. The Elovich equation can be

0.988
0.986
0.974
0.963
R2 written in the following form (Kellner et al., 1998):
 
1 1
qt lnab ln t 7
b b
b 102(g/

where a (mg g1 min1) is the initial sorption rate and b

(g mg1) is the desorption constant related to the extent of sur-
mg)
7.5
8.2
6.0
5.6
Chemisorption

face coverage and activation energy for chemisorption. The

parameters (1/b) and (1/b) ln(ab) can be obtained from the
slope and intercept of the linear plot of qt vs. ln t (Supplemen-
696.0
931.1
10.7

9066.0
g min)
a(mg/

tary Figure 7). The plots are linear with good correlation coef-
cient values (Table 1). This suggests that the sorption process
follows the pseudo-second-order kinetic model based on the
112.5
153.0
201.5
68.6
qe,cal

assumption that the rate determining step may be chemisorp-

tion, involving valence forces through sharing or exchange of
electrons between adsorbent and adsorbate.
0.958
0.926
0.961
0.953
2
R

3.6. Adsorption isotherm modeling

Kid

2.8
2.4
3.4
3.7

Isotherms are the equilibrium relations between the concentra-

Weber-Morris

tion of adsorbate on the solid phase and its concentration in

(mg/

the liquid phase. From the isotherms the maximum adsorption

capacity can be obtained. These data provide information on
cal

112.6
152.9
201.5
68.5
qe,

the capacity of the adsorbent or the amount required to re-

g)

move a unit mass of pollutant under the system conditions.

0.997
0.999
0.999
0.998

Langmuir and Freundlich isotherms are the most common iso-

2

therms describing the solidliquid adsorption system. The

R

Langmuir model assumes that adsorption takes place at spe-

cic homogeneous sites on the surface of the adsorbent and
k210 (mg/

also, when a site is occupied by an adsorbate molecule, no fur-

ther adsorption can take place at this site. The Langmuir equa-
3

g min)
Pseudo-second-order

tion is expressed by the following expression (Langmuir, 1916):

0.39
0.64
0.45
0.37

1 1 1
Values of the parameters of kinetic models for Cd(II) onto CCB beads.

8
qe qm KL Ce qm
(mg/

where qe (mg g1) is the amount of metal ion adsorbed per unit
120.0
160.6
210.0
83.3
cal

mass of adsorbent, Ce (mg L1) is the equilibrium concentra-

qe,
g)

tion of metal ions, qm is the monolayer biosorption capacity

of the adsorbent (mg g1) and KL (mg L1) is the Langmuir
0.999
0.965
0.987
0.949

equilibrium constant, respectively. The graph of (Supplemen-

2
R

tary Figure 8) 1/qe vs. 1/Ce was plotted to determine qm and

KL and the values were shown in Table 2.
0.014
0.021
0.014
0.012
Pseudo-rst-order

The essential characteristics of Langmuir isotherm can be

k1

expressed by a dimensionless constant called separation factor

(mg/

(or equilibrium parameter), RL, which is dened by Weber and

Chakkravorti as (Weber and Chakkravorti, 1974):
cal

40.3
52.8
52.1
52.9

1
qe,
g)

RL 9
1 KL C0
(mg/

where C0 (mg L1) is the initial amount of adsorbate and KL is

the Langmuir sorption constant (L mg1) described above. RL
exp

114.2
155.9
205.7
70.9

indicates the nature of adsorption. Adsorption is favorable

qe,
g)

when the value of RL is between 0 and 1.The RL parameter

is considered as a more reliable indicator of the adsorption.
The value of RL indicates the type of the isotherm to be either
unfavorable (RL > 1), linear (RL = 1), favorable
(0 < RL < 1) or irreversible (RL = 0). The RL values for
Metal ions

Cd(II) ions were shown in Supplementary Table 1 at the tem-

Table 1

(mg/L)

perature range from 298 to 318 K. The values show that the
100
200
300
400

adsorption is favorable for the metal ions by CCB beads.

Please cite this article in press as: Madala, S. et al., Equilibrium, kinetics and thermodynamics of Cadmium (II) biosorption on to
composite chitosan biosorbent. Arabian Journal of Chemistry (2013), http://dx.doi.org/10.1016/j.arabjc.2013.07.017
8 S. Madala et al.

The Freundlich model assumes a heterogeneous surface

with the involvement of sites of different energies in adsorption

0.969
0.979
0.969
process. The Freundlich model is given as (Freundlich, 1906):
R2
1
log qe log KF log Ce 10
n
AT (J/mol)

where KF ((mg g1)(L mg1)1/n) is relating the biosorption

capacity and 1/n is an empirical parameter relating the bio-
1.07
1.14
2.00

sorption intensity. Values of n and KF for Cd(II) were calcu-

Langmuir, Freundlich, DubininRuduskevick and Temkin isotherm constants for biosorption of Cd(II) onto CCB beads at different temperatures.

lated at different temperatures (298, 308 and 318 K) from the

bT (L/mg)

slope and intercept of log Ce vs. log qe and are presented in Ta-
ble 2. The R2 values of Freundlich isotherm are greater than
118.6

120.3
97.0

0.969, but lower than 0.999, indicate that this model is unable
to describe adequately the relationship between the amounts of
Temkin

Cd(II) adsorbed by the biomass and its equilibrium concentra-

0.898
0.879
0.997

tion in the solution. The values of KF are found to be increas-

R2

ing with increase in temperature suggesting that adsorption

process is endothermic in nature. The values of n between 1
E (kJ/mol)

and 10 represent a favorable sorption.

The equilibrium data were examined by using Dubinin
8.0
8.5
9.1

Radushkevich isotherm (Dubinin and Radushkevich, 1947)

in order to determine the nature of the biosorption process
b 103 (mol2 kJ)

as physical or chemical. The DR sorption isotherm is more

general than the Langmuir isotherm as its derivation is not
based on ideal assumptions such as equipotent of the sorption
sites, absence of steric hindrance between sorbed and incoming
Dubinin-Ruduskevick

particles and surface homogeneity on microscopic level. The

8.0
7.0
6.0

linear presentation of DR isotherm equation is expressed by

(Dubinin and Radushkevich, 1947):
qm (mg/g)

ln qe ln qm  be2 11
48.6
59.6
67.9

where qe is the amount of metal ions adsorbed per unit mass of

biomass (mg g1), qm is the maximum biosorption capacity
(mg g1), b is the activity coefcient related to biosorption
0.998
0.969
0.998

mean free energy (mol2 kJ2) and e the Polanyi potential

R2

(e = RT ln(1 + 1/Ce)), R and T are the universal gas constant

(kJ mol1 K1) and the absolute temperature (K). The Dubi-
1.53
1.48
2.02

ninRadushkevich isotherm parameters for Cd(II) ions at

n

three temperatures are listed in Table 2. E is related to the

mean free energy of the sorption per mole of the sorbate
Freundlich
KF (mg/g)

(kJ mol1), as follows:

12.95
20.11
9.09

1
E p 12
2b
The biosorption mean free energy gives information about bio-
0.999
0.998
0.999

sorption mechanism. If E value is between 1 and 8 kJ mol1

R2

the biosorption process corresponds to physical sorption and

in the range 8-6 kJ mol1 for chemisorption (Chakravarty
b (L/mg)

et al., 2010). Therefore the results in Table 2, indicate that

0.087
0.158
0.256

the biosorption of Cd(II) on CCB beads might be following

chemical ion-exchange mechanism.
Temkin isotherm (Temkin and Pyzhev, 1940) contains a
qmax (mg/g)
Langmuir

factor that explicitly takes into account the adsorbentadsor-

bate interactions. The heat of adsorption of all the molecules
101.0
108.7
95.2

in the layer would decrease linearly with coverage due to

adsorbentadsorbate interactions. The adsorption is character-
ized by a uniform distribution of binding energies, up to some
maximum binding energy. The linear form of the Temkin iso-
therm is expressed as:
Temp K

   
Table 2

RT RT
qe ln A ln Ce 13
298
308
318

bT bT

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Equilibrium, kinetics and thermodynamics of Cadmium (II) biosorption on to composite chitosan biosorbent 9

Table 3 Comparison of maximum adsorption capacity (mg/g) of CCB beads for Cd(II) on different biosorbents from the literature.
Biosorbent Adsorption capacity Refs.
Chitosan crosslinked with epichlorohydrin-triphosphate 83.75 mg/g Laus and De Favere (2011).
Cross-linked magnetic Chitosan-phenylthiourea resin 120 mg/g Monier and Abdel-Latif (2012).
Thiourea-modied magnetic ion-imprinted chitosan/TiO2 composite 256.41 mg/g Chen et al. (2012).
Succinylated twice-mercerized sugarcane bagasse functionalized with 86.2 mg/g Leandro and Laurent (2009).
triethylenetetramine (MMSCB) MMSCB-3
MMSCB-5 106.4 mg/g
Crosslinked chitosan/polyvinyl alcohol blend beads 142.9 mg/g Kumar et al. (2009).
Spray-dried chitosan loaded with reactive orange 16 90.3 mg/g Vasconcelos et al. (2009).
Xanthated chitosan 357.1 mg/g Sankararamakrishnan et al. (2007).
Chitosan/activated carbon composite 52.63 mg/g Hydari et al. (2012).
Chitosan/perlite 179.6 mg/g Hasan et al. (2006).
Chitosan coated cotton ber 15.74 mg/g Zhang et al. (2008).
Composite chitosan biosorbent 108.7 mg/g Present study

where RT/bT = B (J mol1), which is the Temkin constant re- 4. Conclusion

lated to heat of sorption whereas AT (L g1) is the equilibrium
binding constant corresponding to the maximum binding en-
ergy. R (8.314 J mol1 K1) is the universal gas constant and
T (K) is the absolute solution temperature. All the correlation
coefcients, R2 values and the constants obtained from the four
isotherm models applied for adsorption of Cd(II) on the CCB
beads are summarized in Table 2. The Langmuir isotherm gave
R2 values close to unity indicating that the adsorption of Cd(II)
on the CCB beads which is best described by Langmuir model.
CCB beads showed comparable biosorption capacity toward
Cd(II) with previous literature results shown in Table 3.
3.7. Thermodynamic analysis
The thermodynamic parameters such as enthalpy change
(DH), the entropy change (DS) and the Gibbs free energy
change (DG) for the sorption process were calculated from
the variation of Langmuir constant (KL) with temperature
(T) using well known relations,
DG0 RT ln KL 14
DG0 DH0  TDS0 15
DS0 DH0
lnKL  16
R RT
where R is the universal gas constant (8.314
103 kJ mol1 K1) and KL is Langmuir constant. Enthalpy
change due to adsorption of metal ions by CCB over the temper-
ature range studied can be determined from the linear plots of ln
KL against 1/T using the least squares analysis (Supplementary
Figure 9). The values of DG, DH and DS for sorption of Cd
(II) by CCB at different temperatures (298318 K), given in Sup-
plementary Table 2, show that DG is small and negative but de-
creases with increasing temperature. The negative values of DG
demonstrate the process to be spontaneous and positive values
of DH indicating that the process requires some energy input
from the outside. Hence the process of the removal of Cd(II)
on CCB is endothermic in nature. The positive value of DS sug-
gested the increase of randomness at the solid/solution interface
during the biosorption of metal ions on CCB.
A composite chitosan biosorbent was prepared and used for
the removal of Cd(II) from aqueous medium over a wide range
of concentrations. The following conclusions are made based
on the results of the present study:
 The biosorbent was characterized by high temperature
pyrolysis, porosimetry, Fourier transform infrared spectros-
copy (FTIR) and scanning electron microscopy (SEM),
Energy dispersive X-ray (EDAX) and X-ray diffraction
analysis (XRD) techniques.
 Biosorption of Cd(II) was found to increase with increase in
contact time and initial concentration. When the adsorbent
dosage increases, the equilibrium adsorption capacity
(mg g1) of CCBbeads gradually decreases, whereas the
percent removal efciency increases.
 The experimental data are best correlated by pseudo-sec-
ond-order kinetic model and Elovich equation rather than
the pseudo-rst-order kinetics. The results of the intraparti-
cle diffusion model suggest that intraparticle diffusion is not
the only rate controlling step.
 Equilibrium data are tted to Langmuir, Freundlich, Dub-
ininRadushkevich and Temkin isotherm models and was
found that the equilibrium data are best described by the
Langmuir isotherm model. The maximum monolayer bio-
sorption capacity is 108.7 mg g1 at 318 K.
 The thermodynamic results show the feasibility, spontane-
ous and endothermic nature of biosorption of Cd(II) onto
CCB beads.
Based on the results, it can be concluded that the CCB is an
effective biosorbent for the removal of Cd(II) from aqueous
medium.
Acknowledgements
We are thankful to DST, New Delhi, India for the award of
Women Scientist and the nancial support of this research
project, SR/WOS-A/CS/76/2011.

Please cite this article in press as: Madala, S. et al., Equilibrium, kinetics and thermodynamics of Cadmium (II) biosorption on to
composite chitosan biosorbent. Arabian Journal of Chemistry (2013), http://dx.doi.org/10.1016/j.arabjc.2013.07.017
10
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.arabjc.
2013.07.017.
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