International Journal of Biological Macromolecules 34 (2004) 155161

Equilibrium and kinetics studies of adsorption of copper (II)

on chitosan and chitosan/PVA beads
W.S. Wan Ngah , A. Kamari, Y.J. Koay
School of Chemical Sciences, Universiti Sains Malaysia, 11800 Penang, Malaysia

Abstract

The adsorption of Cu(II) ions from aqueous solution by chitosan and chitosan/PVA beads was studied in a batch adsorption system.
Chitosan solution was blended with poly(vinyl alcohol) (PVA) in order to obtain sorbents that are insoluble in aqueous acidic and
basic solution. The adsorption capacities and rates of Cu(II) ions onto chitosan and chitosan/PVA beads were evaluated. The Langmuir,
Freundlich and BET adsorption models were applied to describe the isotherms and isotherm constants. Adsorption isothermal data could
be well interpreted by the Langmuir model. The kinetic experimental data properly correlated with the second-order kinetic model, which
indicates that the chemical sorption is the rate-limiting step. The Cu(II) ions can be removed from the chitosan and chitosan/PVA beads
rapidly by treatment with an aqueous EDTA solution. Results also showed that chitosan and chitosan/PVA beads are favourable adsorbers.
2004 Elsevier B.V. All rights reserved.

Keywords: Chitosan beads; Chitosan/PVA beads; Adsorption capacities; Adsorption rates; Adsorption isotherm; Desorption

1. Introduction biological origin is recognized as an emerging technique

The effluents of industrial wastewaters often contain con-
siderable amounts of toxic and polluting heavy metals. It is
well known that heavy metals such as Hg, Pb, Cr, Ni, Cu,
Cd and Zn are usually associated with tendency to accumu-
late in living organisms and are highly toxic when adsorbed
into body. Copper may be found as a contaminant in food,
especially shellfish, liver, mushrooms, nuts and chocolate.
Briefly, any processing or container using copper material
may contaminate the product such as food, water or drink
[1]. Excessive intake of copper results in an accumulation
in the liver. It is also toxic to aquatic organisms even at
very small concentrations in natural water [2]. The potential
sources of copper in industrial effluents include metal clean-
ing and plating baths, pulp, paper and paper board mills,
wood pulp production and the fertilizer industry, etc. [13].
Toxic metals ions in trace quantities are difficult to re-
move from aqueous solution. Adsorption is the promising
alternatives for such situations, especially using low-cost ad-
sorbents like clay material, agricultural wastes and seafood
processing wastes. Biosorption or sorption to material of
Corresponding author. Fax: +60-465-74854.
E-mail address: wsaime@usm.my (W.S. Wan Ngah).
for the treatment of wastewater containing heavy metals
[2]. Chitin, poly(1 4)-2-acetamido-2-deoxy--d-glucan
is a value-added biopolymer extracted commercially
from the shells of crustaceans such as prawns, crabs,
krill, insects and shrimps, and the second most abundant
biopolymer next to cellulose [4,5]. Chitosan, poly(1
4)-2-amino-2-deoxy--d-glucan is prepared from chitin by
partially deacetylating its acetamido groups with a strong
alkaline solution. Chitosan appears to be more useful as
compared to chitin, since it has both amine and hydroxyl
groups that can serve as chelating sites and can be chem-
ically modified [6]. Chitosan has been reported for the
high potentials of adsorption metal ions [79], noble ions
[1012], dyes [13,14], proteins [15] and humic acid [16,17],
etc.
Several methods have been used to modify raw chitosan
flake either physical [18,19] or chemical modifications
[10,20,21]. These modifications were proposed in order
to improve pore size, mechanical strength, chemical sta-
bility, hydrophilicity and biocompatibility. Cross-linking
enhances the mechanical strength and chemical resistance.
Some common cross-linking agents such as glutaraldehyde
[22,23], epichlorohydrine [24,25] and ethylene glycol digly-
cidyl ether [26] have widely been used in cross-linking of
chitosan beads. Although cross-linking increases the chem-

0141-8130/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.ijbiomac.2004.03.001
156 W.S. Wan Ngah et al. / International Journal of Biological Macromolecules 34 (2004) 155161
ical stability of the biosorbents in such acidic solutions
but cross-linking has been found decreases the adsorption
capacity of chitosan [2].
In recent years, polymer blending has become one of the
effective methods for providing new desirable polymeric
materials for practical applications. Chitosan blended with
poly(vinyl alcohol) (PVA) has been reported to have good
mechanical and chemical properties [27]. PVA is a nontoxic,
water soluble, biocompatible and biodegradable synthetic
polymer, which offers good tensile strength, flexibility and
barrier properties to oxygen and aroma [28,29]. As a topic
of great interest, PVA has widely been used in biomedi-
cal and biochemical applications [30,31]. Chitosan/PVA has
been used in the removal of lead ions from aqueous solution
[27]. However, the adsorption properties and mechanisms of
the chitosan/PVA blend for metal removal have been seldom
studied.
In this study, the equilibria of adsorption Cu(II) ion onto
chitosan and chitosan/PVA beads from water were inves-
tigated in detail. The influence of experimental conditions
such as pH, agitation period, agitation rate and initial con-
centration will be studied. The Langmuir, Freundlich and
BET equations were used to fit the equilibrium isotherm. The
adsorption rates were determined quantitatively and com-
pared by the first- and second-order kinetic model. This in-
formation will be useful for further applications of system
design in the treatment of practical waste effluents.
2. Material and methods
2.1. Materials
Samples of chitosan flakes with average molecular weight
105 106 and with a deacetylation percentage of approxi-
mately 55.9% (defined by an IR method), prepared from
shells of prawns were kindly donated from Chitin-Chitosan
Research Centre, Universiti Kebangsaan Malaysia, Bangi.
PVA (98% hydrolysed, average molecular weight 22,000)
purchased from BDH was analytical-reagent grade. All the
reagents used were of analytical-reagent grade. Doubly dis-
tilled water used to prepare all the solutions.
2.2. Preparation of chitosan beads
Chitosan beads were prepared according to the same pro-
cedure described previously [2,6]. Chitosan solution was
prepared by dissolving 2.0 g of chitosan flakes into 60 ml
of 5% (v/v) acetic acid solution. The chitosan solution was
sprayed into a precipitation bath containing 500 ml of 0.5 M
NaOH, which neutralized the acetic acid within the chitosan
gel and thereby coagulated the chitosan gel to spherical uni-
form chitosan gel beads. A magnetic stirrer used to stir the
aqueous NaOH solution. The wet chitosan gel beads were
extensively rinsed with distilled water to remove any NaOH,
filtered and finally air-dried to remove the water from the
pore structure (hereafter called chitosan beads). The beads
were then ground by using a laboratory jar mill and sieved
to a constant size (<250 m) before use.
2.3. Preparation of chitosan/PVA beads
An 8.0 g amount of chitosan flakes was dissolved in
100 ml of 5% (v/v) acetic acid solution. The chitosan solu-
tion was left 24 h at room temperature. PVA in an amount
of 6.0 g was dissolved in 100 ml of distilled water in a
beaker and agitated on a magnetic stirrer at about 500 rpm
at 70 C for 5 h. The two solutions were then blended to-
gether with stirring on the magnetic stirrer at about 500 rpm
at 70 C for 2 h and followed by another 48 h under room
temperature to obtain a homogeneous gel blend. The gel
blend was sprayed into a precipitation bath containing
500 ml of 0.5 M NaOH, which neutralized the acetic acid
within the chitosan gel and thereby coagulated the chitosan
gel to spherical uniform chitosan gel beads. The aqueous
NaOH solution was agitated at about 300 rpm. Freshly
prepared wet chitosan/PVA gel beads were filtered and in-
tensively washed and finally air-dried. The newly formed
blended beads (hereafter called chitosan/PVA beads) were
then ground by using a laboratory jar mill and sieved to
a constant size (<250 m) before use. The chitosan/PVA
beads (as shown in Fig. 1) obtained were confirmed by a
Perkin-Elmer FT-IR System 2000 Model spectrometer.
2.4. Dissolution and swelling test of chitosan and
chitosan/PVA beads
Chitosan and chitosan/PVA beads were tested with regard
to their solubility in each of 5% (v/v) acetic acid, distilled
water and 0.1 M sodium hydroxide solution by adding 0.1 g
of chitosan and chitosan/PVA beads in each of the dilute
acid, distilled water and dilute alkaline solution for a period
of 24 h with stirring at room temperature.
The swelling studies of chitosan and chitosan/PVA beads
were carried out in dilute acid, distilled water and dilute
alkaline solution at room temperature for a period of 24 h.
The percentage of swelling of these beads were calculated
by using the following equation:
Ws W
percentage of swelling = 100 (1)
W
where Ws is the weight of swollen beads (g) and W is the
weight of dry beads (g).
2.5. Batch adsorption experiments
Stock solutions (1000 ppm) of Cu(II) ions was prepared
by using analytical-reagent grade Cu metal (BDH). The
stock solution was then diluted to give standard solutions of
appropriate concentrations. Batch adsorption experiments
were conducted in 250 ml beakers and equilibrated using a
magnetic stirrer. Then 50 ml aliquots of these standard solu-
 W.S. Wan Ngah et al. / International Journal of Biological Macromolecules 34 (2004) 155161 157

CH2 CH
n
O
H
Intermolecular
HOH2C
HOH2C O
O
O
O
O NH2
NH2 HO
HO
Intermolecular
H
Intramolecular
O

CH2 CH
n

Fig. 1. Proposed structure of chitosan/PVA beads [27].

tions were placed in 250 ml beakers and added with 0.01 g riod of 30 min and agitation rate was fixed at 500 rpm.
of chitosan or chitosan/PVA beads. After filtration, the con- Cu(II)-loaded chitosan and chitosan/PVA beads were col-
centration of Cu(II) ions in supernatant was analysed at lected, gently washed with distilled water to remove any
wavelength 325 nm using an atomic absorption spectropho- unadsorbed Cu(II). The amount of Cu(II) adsorbed per
tometer (Perkin-Elmer 3100 Model). The effect of Cu(II) gram of chitosan and chitosan/PVA were determined by
adsorption was studied in pH range 16. The pH of the using the supernatant Cu(II) concentration. The chitosan
initial solution was adjusted to the required pH value us- and chitosan/PVA beads were agitated with 50 ml of EDTA
ing either 0.1 M HCl or 0.1 M NaOH. Chitosan and chi- and HNO3 of various concentration (102 105 M) and the
tosan/PVA beads were equilibrated at the particular pH for percentage of desorption of Cu(II) was calculated from the
about 30 min at 500 rpm and at an initial Cu(II) concentra- following expression:
tion of 5 ppm. The effect of agitation period and agitation mr
percentage of desorption = 100% (3)
rate also studied to determined the optimum condition for m0
adsorption of Cu(II) ions.
where mr is the amount of Cu(II) ions desorbed (mg) and
Adsorption equilibrium studies were conducted at opti-
m0 is the amount of Cu(II) ions adsorbed (mg).
mum condition using a contact time of 50 min at pH 6 for
chitosan whereas for chitosan/PVA beads, a contact time of
70 min at pH 6. Isotherm studies were conducted with a
3. Results and discussion
constant chitosan and chitosan/PVA beads weight (0.01 g)
and varying initial concentration of Cu(II) in the range of
3.1. Solubility and swelling test of chitosan and
014 ppm. The amount of adsorption was calculated based
chitosan/PVA beads
on the difference of Cu(II) concentration in aqueous solu-
tions before and after adsorption, the volume of aqueous so-
It was shown that after blending with PVA, the blended
lution (50 ml) and the weight of the beads (0.01 g) according
chitosan was found to be insoluble in acidic and alkaline me-
to:
dia as well as distilled water (Table 1). It is well known that
(C0 Ce )V chitosan is soluble in dilute organic acid solutions. This due
adsorption capacity (qe ) = (2)
W to each of the accessible amine groups is protonated in acid
where C0 is the initial Cu(II) concentration (ppm), Ce is media. Table 2 reports the percentage of swelling behaviour
the final or equilibrium Cu(II) concentration (ppm), V is the of chitosan and chitosan/PVA beads. A convenient proof of
volume of the Cu(II) solution (ml) and W is the weight of blending is the swelling behaviour of the blended chitosan
the chitosan and chitosan/PVA beads (g). beads in dilute acetic acid. This may suggests that blending
For batch kinetic studies, 0.01 g chitosan and chi- treatment should be necessary to reinforce the chemical sta-
tosan/PVA beads were equilibrated at optimum condition
as mentioned earlier. The beads and Cu(II) solution (5 ppm) Table 1
were placed in 250 ml beakers and stirred by a magnetic Solubility effect of chitosan and chitosan/PVA beads
stirrer. Every time, after filtration the concentration of Cu(II) Beads Solubility effect
in supernatant were determined. 5% acetic acid Distilled water 0.10 M NaOH
For the desorption studies, 0.01 g of chitosan and chi-
tosan/PVA beads were loaded with Cu(II) using 50 ml Chitosan Soluble Insoluble Insoluble
Chitosan/PVA Insoluble Insoluble Insoluble
of 5 ppm Cu(II) solution at optimum pH, agitation pe-
158 W.S. Wan Ngah et al. / International Journal of Biological Macromolecules 34 (2004) 155161

Table 2 25
Swelling behaviour of chitosan and chitosan/PVA beads
Beads Swelling (%) 20
5% acetic acid Distilled water 0.10 M NaOH
qCu(II) (mg g )
-1

15
Chitosan Soluble 57.1 42.9 Chitosan/PVA
Chitosan/PVA 12.4 7.8 6.5 Chitosan
10

bility of the beads in such acidic solution. Meanwhile, the 5

less swelling behaviour of blended beads was important so
they can be used in an adsorption column. 0
0 20 40 60 80 100
3.2. Effect of pH
Agitation Period (min)

In this study, knowledge of pH is important because the
pH of solution strongly affects the adsorption capacity of the
chitosan and chitosan/PVA beads. Fig. 2 shows the effect of
pH on the adsorption of Cu(II) by chitosan and chitosan/PVA
beads. The maximum adsorption of Cu(II) on chitosan and
chitosan/PVA beads was found at pH 6.0, respectively. At
pH values higher than 7, Cu(II) precipitation occurred si-
multaneously. pH 6 was chosen for the adsorption of Cu(II)
ions to avoid the formation of Cu(II) hydroxide which will
affect the adsorption by the beads. The adsorption increases
(i.e., the difference in absorbance increases) with increasing
pH of the solution. This could be explained by the fact that
at low pH, more protons will available to protonate amine
groups to form groups NH3 + , reducing the number of bind-
ing sites for the adsorption of Cu(II). While, at higher pH
adsorption of Cu(II) increases due to the inhibitory effect of
H+ decreased with the increase in pH.
3.3. Effect of agitation period
Fig. 3 shows the effect of agitation period on the adsorp-
tion of Cu(II) by chitosan and chitosan/PVA beads. The op-
timum period for the adsorption of Cu(II) on chitosan and
chitosan/PVA can be observed by looking at the difference
in absorbance of Cu(II) solution after adding chitosan and
Fig. 3. Effect of agitation period on the adsorption of Cu(II) on chitosan
and chitosan/PVA beads.
chitosan/PVA beads. The adsorption of Cu(II) increases with
agitation period and attains equilibrium at about 50 min for
chitosan and 70 min for chitosan/PVA beads for an initial
Cu(II) concentration of 5 ppm. It shows that the adsorption
of Cu(II) remained constant, implying equilibrium has been
reached.
3.4. Effect of agitation rate
Fig. 4 shows the effect of agitation rate on the adsorp-
tion of Cu(II) by chitosan and chitosan/PVA beads. The ad-
sorption of Cu(II) increases with agitation rate and attains a
constant value at about 500 rpm for both beads. The agita-
tion rate of 500 rpm was chosen because the agitation above
this has little effect on adsorption rate. Therefore, the opti-
mum agitation rate for adsorption of Cu(II) was 500 rpm for
chitosan and chitosan/PVA beads.
3.5. Adsorption equilibrium
The equilibrium adsorption of Cu(II) on the chitosan and
chitosan/PVA beads as a function of the initial concentra-

30 25

25 20
qCu(II) (mg g )

qCu(II) (mg g )

20
-1

-1

15
Chitosan/PVA Chitosan/PVA
15
Chitosan Chitosan
10
10

5 5

0 0
0 2 4 6 8 0 200 400 600 800
pH Agitation Rate (rpm)

Fig. 2. Effect of pH on the adsorption of Cu(II) on chitosan and chi- Fig. 4. Effect of agitation rate on the adsorption of Cu(II) on chitosan
tosan/PVA beads. and chitosan/PVA beads.
 W.S. Wan Ngah et al. / International Journal of Biological Macromolecules 34 (2004) 155161 159

50 Table 4
RL values based on the Langmuir equation

40 Cu(II) initial concentration (ppm) RL value

Chitosan Chitosan/PVA
qe (mg g )
-1

30
Chitosan/PVA 4 0.1007 0.1097
Chitosan 6 0.0695 0.0759
20
8 0.0530 0.0580
10 0.0429 0.0470
10 12 0.0360 0.0395

0
0 2 4 6 8 The BET equation is given by:
Ce (ppm)
Fig. 5. Equilibrium adsorption of Cu(II) from aqueous solutions using
chitosan and chitosan/PVA beads.
tion of Cu(II) is shown in Fig. 5. There was a gradual in-
crease of adsorption for both Cu(II) ions until an equilibrium
was attained. An equilibrium concentration of Cu(II) ions
was reached at about 5 ppm for chitosan and chitosan/PVA
beads. Adsorption isotherm is important to describe how
solutes interact with adsorbent. The Langmuir, Freundlich
and BET models are often used to describe equilibrium
sorption isotherms. The most widely used Langmuir equa-
tion, which is valid for monolayer sorption on to a sur-
face with a finite number of identical sites and is given
by:
Ce Ce 1 pressed in terms of a dimensionless constant separation fac-
= +
qe Q Qb
where Q is the maximum adsorption at monolayer (mg g1 ),
Ce is the equilibrium concentration of Cu(II) (ppm), qe is the
amount of Cu(II) adsorbed per unit weight of chitosan and
chitosan/PVA beads at equilibrium concentration (mg g1 )
and b is the Langmuir constant related to the affinity of
binding sites (ml mg1 ) and is a measure of the energy of
adsorption. A linearized plot of Ce /qe against Ce gives Q
and b.
The widely used empirical Freundlich equation based on
sorption on a heterogeneous surface is given by:
1
log qe = log KF + log Ce
n bents may involve three steps: (i) diffusion of the ions to
where KF and n are Freundlich constants indicating sorption
capacity (mg g1 ) and intensity, respectively. KF and n can
be determined from linear plot of log qe against log Ce .




Ce 1 B1 Ce
= + (6)
(Ci Ce )(qe ) BQ BQ Ci
where Q is the maximum adsorption at monolayer (mg g1 ),
Ce is the equilibrium concentration of Cu(II) (ppm), Ci is
the saturation concentration of the solute (ppm), qe is the
amount of Cu(II) adsorbed per unit weight of chitosan and
chitosan/PVA beads at equilibrium concentration (mg g1 )
and B is the BET constant expressive of the energy of inter-
action with surface.
The calculated results of the Langmuir, Freundlich and
BET isotherm constants are given in Table 3. It is found that
the adsorption of Cu(II) on the chitosan and chitosan/PVA
beads were correlated well (R > 0.99) with the Langmuir
equation as compared to Freundlich and BET equation under
the concentration range studied.
The essential features of a Langmuir isotherm can be ex-
(4) tor or equilibrium parameter, RL that is used to predict if an
adsorption system is favourable or unfavourable. The
separation factor, RL is defined by:
1
RL = (7)
1 + bC0
where C0 is the initial Cu(II) concentration (ppm) and b is
the Langmuir adsorption equilibrium constant (ml mg1 ).
Table 4 lists the calculated results. Based on the effect of
separation factor on isotherm shape, the RL values are in the
range of 0 < RL < 1, which indicates that the adsorption of
Cu(II) on chitosan and chitosan/PVA beads are favourable.
Thus, chitosan and chitosan/PVA beads are favourable ad-
(5) sorbers. The mechanism of ion adsorption on porous adsor-
the external surface of adsorbent; (ii) diffusion of ions into
the pores of adsorbents; (iii) adsorption of the ions on the
internal surface of adsorbent.

Table 3
Langmuir, Freundlich and BET isotherm constants and correlation coefficients
Beads Langmuir Freundlich BET

Q (mg g1 ) b (ml mg1 ) R KF (mg g1 ) n R Q (mg g1 ) B R

Chitosan 33.44 2232 0.9991 21.61 3.57 0.9816 15.70 39.81 0.9730
Chitosan/PVA 47.85 2029 0.9992 29.53 3.10 0.9858 35.59 15.61 0.9895
160 W.S. Wan Ngah et al. / International Journal of Biological Macromolecules 34 (2004) 155161

50 2.00

40 1.60
t/qt (min g mg )
-1
qt (mg g )

30 1.20
-1

Chitosan/PVA Chitosan/PVA
Chitosan Chitosan
20 0.80

10 0.40

0 0.00
0 20 40 60 0 20 40 60
t (min) t (min)

Fig. 6. Time profiles of Cu(II) adsorption using chitosan and chitosan/PVA Fig. 7. Test of second-order equation for adsorption of Cu(II) using
beads. chitosan and chitosan/PVA beads.

1.60
3.6. Kinetics of adsorption
1.20
Fig. 6 shows the time profiles of Cu(II) adsorption onto
log (qe - q t )

chitosan and chitosan/PVA beads with an initial concen-

Chitosan/PVA
tration of 5 ppm. The adsorption capacity of chitosan/PVA 0.80
Chitosan
beads is greater than chitosan beads. It is known that the lone
pair electrons present in the amine (NH2 ) groups and lone
0.40
pairs of electrons of the hydroxyl (OH) groups can estab-
lish bonds with transition metal ions. In this study, blending
chitosan with PVA increases the number of hydroxyl group 0.00
on the chitosan chain. As the results, the adsorption ability 0 20 40 60
of Cu(II) ions on chitosan/PVA beads with is superior due to t (min)
it higher content of hydroxyl and amine groups as compared Fig. 8. Test of first-order equation for adsorption of Cu(II) using chitosan
to chitosan beads. and chitosan/PVA beads.
In order to examine the controlling mechanism of adsorp-
tion processes such as mass transfer and chemical reaction, The validity of both kinetic models is checked and de-
the first- and second-order equations were used to test the picted in Figs. 7 and 8 by each linear plot of t/qt against
experimental data. The first-order kinetic model is given as t and log(qe qt ) against t, respectively. Fig. 7 shows a
[14,25]: good agreement of dynamical data with second-order kinetic
k1 model. On the contrary, the first-order kinetic model fits the
log(qe qt ) = log qe t (8) experimental data poorly as shown in Fig. 8. The results
2.303
of the kinetic parameters for Cu(II) adsorption are given in
where qe and qt are the amounts of Cu(II) adsorbed on Table 5. Based on the correlation coefficients, the adsorption
adsorbent (mg g1 ) at equilibrium and at time t, respectively, of Cu(II) is best described by the second-order equation. In
and k1 is the rate constant of first-order adsorption (min1 ). many cases the first-order equation of Lagergren does not
The straight-line plots of log(qe qt ) against t were used to fit well to the whole range of contact time and is generally
determine the rate constant, k1 and correlation coefficient, applicable over the initial stage of the adsorption processes
R values of the Cu(II) under different concentration range [32]. The first-order kinetic process has been used for re-
were calculated from these plots. The second-order equation versible reaction with an equilibrium being established be-
may be expressed as [9,13,23]:
Table 5
t 1 t Kinetic parameters for Cu(II) adsorption on chitosan and chitosan/PVA
= + (9)
qt k2 q e
2 qe beads at agitation period 50 min (C0 = 5 ppm)
Beads First order Second order
where k2 is the rate constant of second-order adsorption
(g mg1 min1 ). The straight-line plots of t/qt against t have k1 ( 102 , R k2 ( 103 , R
min1 ) g mg1 min1 )
been tested to obtain rate parameters and it suggests the
applicability of this kinetic model to fit the experimental Chitosan 4.55 0.9663 5.20 0.9998
Chitosan/PVA 4.00 0.9638 2.53 0.9996
data.
 W.S. Wan Ngah et al. / International Journal of Biological Macromolecules 34 (2004) 155161 161

Table 6 well fitted by the Langmuir equation. The adsorption pro-

Percentage of desorption of Cu(II) from complex Cu(II)chitosan and cess could be best described by the second-order equation.
chitosan/PVA beads
This suggests that the rate-limiting step may be the chem-
Desorption solution Concentration (M) Desorption (%) ical adsorption (chemisorption) but not the mass transport.
Chitosan Chitosan/PVA The Cu(II) ions can be easily removed from chitosan or
EDTA 1.0 102 87.4
chitosan/PVA beads by treatment with aqueous EDTA and
1.0 103 73.0 HNO3 solution. It can be concluded that chitosan and chi-
1.0 104 53.7 64.1 tosan/PVA beads are effective adsorbents for the collection
1.0 105 22.4 35.8 of metal ions.
HNO3 1.0 102 68.5
1.0 103 41.3
1.0 104 19.6 20.3 Acknowledgements
1.0 105 6.2 9.8
The authors thank Chitin-Chitosan Research Centre, Uni-
versiti Kebangsaan Malaysia, Bangi, Malaysia, for supply-
tween liquid and solid phases. Whereas, the second-order ing samples of chitosan. The authors also thank Universiti
kinetic model assumes that the rate-limiting step may be Sains Malaysia for the financial support under IRPA Short
chemical adsorption [23]. In many cases, the second-order Term Research Grant (Grant No. 305/PKIMIA/622183).
equation correlates well to the adsorption studies [9]. It is
more likely to predict that the adsorption behaviour may in- References
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[22] Guibal E, Dambies L, Milot C, Roussy J. Polym Int 1999;48:671.
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4. Conclusion 2000;77:3216.
[25] Chiou M-S, Li H-Y. J Hazard Mater 2002;B93:233.
[26] Tianwei T, Xiaojing H, Weixia D. J Chem Technol Biotechnol
The blended chitosan with PVA is insoluble in both acidic 2001;76:191.
and basic media. Chitosan/PVA beads also show a lower per- [27] Jin L, Bai R. Langmuir 2002;18:9765.
centage of swelling than chitosan beads. In this study, the [28] Schellekens R, Bastiansen CJ. J Appl Polym Sci 1991;43:2311.
capacity of chitosan and chitosan/PVA beads was examined. [29] Zheng H, Du Y, Yu J, Huang R, Zhang L. J Appl Polym Sci
2001;80:2558.
The adsorption capacity of chitosan/PVA beads is superior [30] Kim SJ, Park SJ, Kim SI. React Funct Polym 2003;55:53.
than chitosan beads. This is due to the higher content of [31] Zhao L, Mitomo H, Zhai M, Yoshii F, Nagasawa N, Kume T.
hydroxyl and amine groups of chitosan/PVA beads as com- Carbohydr Polym 2003;53:439.
pared to chitosan beads. The adsorption isotherms could be [32] McKay G, Ho YS. Water Res 1999;33:578.

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