ELSEVIER Reacti ve & Functional Polymers 50 (2002 ) 181- 190

REACTIVE
&
FUNCTIONAL
POLYMERS
\\WW.elsevier.corn/ locate/ react
. 1 l ~ C >
~
Removal of copper(II) ions frOITI aqueous solution onto
chitosan and cross-linked chitosan beads
W.s . Wan Ngah*, c.s. Endud, R. Mayanar
Schocl of Chemical Sciences. Universiti Saills Malaysia, 11800 Pulau Pinang, Malaysia
Received 10 March 2001: received in revised form 26 September 2001: accepted 10 October 200 I
Abstract
The adsorption of Cu(II J ions onto chitosan and cross-li nked chitosan beads has been investigated. Chitosan beads were
cross-linked with glutarald ehyde (GLA). epichl orohydrin (ECH) and ethylene glycol diglycidyl ether (EGDE) in order to
obtain sorbents that are insoluble in aqueou s acidi c and basic soluti on. Batch adsorption experiments were carried out as a
function of pH, agitation period, agitation rate and concent ratio n of Cut ll ) ions. A pH of 6.0 was found to be a opti mum for
Curll ) adsorpt ion on chitosan and cross-linked chitosan beads. Isother m studies indicate Cu(II) can be effectively removed
by chitosan and cross-linked chitosan beads. Adsorption isotherma l data could be well interpreted by the Langmuir equa tion.
Langmuir constants have been determi ned for chitosan and cross- linked chitosan beads . The experimental data of the
adsorption equil ibrium from Cu(II) solution correlated well with the Langmuir isotherm equation. The uptakes of Cu( II) ions
on chitosan bead s were 8C.71 mg Cu(ll )/g chitosan, on chitosan-GLA beads were 59.67 mg Cu(II )/g chitosan-GLA, on
chitosan-ECH beads were 62.47 mg Cu(II )/ g chit osan-ECH and on chitosan-EGDE beads were 45.94 mg Cut ll ) ,'g
chitosan-EGDE. The Cu(I1) ions can be removed from the chitosan and cross-li nked chitosan beads rapidly by treatment
with an aqueous EDTA so ution and at the same time the chitosan and cross-linked chi tosan beads can be regenerated and
also 'can be used again to idsorb heavy meta l ions. 2002 Elsevier Science B.Y. All rights reser ved.
Keywords: Chitosan beads; C 'oss-Iinked chitosan beads; Swelling; Adsorption isotherm; Capacity: Desorpti on
1. Introduction
The presence of he, vy metals in the environ-
ment has been of grea t concern because of thei r
increased disc harge, toxic nature and other
adverse effec ts on receiving waters. The po-
tential sources of copper in industrial effluents
include metal cleaning and plating baths, pulp,
paper and paper board mills. wood pulp pro-
"Corresponding author.
E-mail address:wsaime@u ;m.my (W.S. Wan Ngah).
duction, and the fertilizer industry, etc. ll l-
Excessive intake of copper results in an ac-
cumulation in the liver. It is also toxic to aquatic
organisms even at very small concentrations in
natur al water [I].
Various methods exist for the removal of
toxic metals from aqueous solution such as
ion-exchange, reverse osmosis, adsorption, com-
plexation and precipitation [2- 4]. Adsorption is
the most effective and widely used method.
Activated carbon and chelation ion-exchange
resins have become increasingly popular com-
1381-5148/ 02/ $ - see front n.atter 2002 Elsevier Science B.Y. All rights reserved.
PlI : 51 381 -5148(01 ) 001 3 -4
182 IVS. 11' ,, // 'v3,,11 et ul . / Reactive & Functional Polymers 50 (2002) 181- 190
pared to other techniq ues. In spite of its wide-
spread use in the water and waste industries,
activated carbon and commercial chelating res-
ins are still an expensive material and therefore
the production of low-cost alternatives has been
the focus of researchers in the area.
Biosorption or sorption to material of bio-
logical origin is recognized as an emergi ng
technique for the treatment of was tewater con-
taining heavy met al s. Chitosan is a biopolymer,
whic h is of interes t to research ers conc erning
the adso rption of metal ions on chitosa n.
Chitosan, also named pol y([3-1-4)-2-amino-2-
deoxy-o-gl ucopyranose, a poly(o-glucosamin e)
is prepared from chitin by deacetylating its
acetamido groups. Chitin or poly([3-1-4)-2-acet-
arnido-z-deoxy-c-glucopyranose is a natural
pol ymer ext racted from crustacean shells, such
as prawns, crabs, insects and shrimps. Chitosan
has been described as a suita ble natural polymer
for the collection of met als ions [5-13], since
the amine gro ups and hydroxyl gro ups on the
chitosan chain can act as chelation sites for
metal ions .
Several methods have been used to modi fy
raw chitosan flake either physical [8,14] or
chemical modifications [15-1 9]. These modi-
fications were proposed in order to improve
pore size , mechanical strength, chemical stabili -
ty. hydrophilicity and also biocompatibility.
Acid environments produc e the partial dissolu-
tion of the polymer and to make the pol ymer
insol uble in acidic medium, modification by
using cross- linking agent s used. Al though cross-
linking reduces the adsorption capacity but it
enhance the resistance of chitosan against acid,
alkali and chemical [15]. The cross-linked
chi tosan also are very stable and mainta in their
strength even in acidic and basic solutions [ 16].
These charac teristics are very import ant for a
adsorbent so that it can be used in a lower pH
environment. Cross-linking also can change the
crystalline nature of chi tosan and enhance sorp-
tion abilities [17].
The aim of this study was to compare the
adsorption behaviour of chitosan and cross -
linked chitosan beads. The equilib ria of ad-
sorption of Cu(II ) ion on these beads from
water were investigated. The influence of ex-
perimental conditions such as agitation period,
agitation rate , pH and Cu(lI ) ions concentrati on
will be studied. This information will be useful
for further appli cat ion in the treatment of was te
effluents.
2. Experimental
2. J. Chemical and reagent s
Chitosan was purchased from Fluka as a
flaked mat er ial, with a deacetylation percent age
of app roxi mately 57.72% (defi ned by an IR
method). Glutaraldehyde (GLA), epi-
chlorohydrin (ECH) . and ethylene glycol
diglycidyl ether (EGDE) purchased from Fluka
were analytical-reagent grade. All the reagents
used were of ana lytical-reagent grade . Doubly
distilled water used to prepare all the sol utions.
2.2. Preparation of chitosan beads
Chitosan solution was prepared by dissol ving
2.00 g chitosan flakes into 50 ml of 5% (v / v)
acetic acid solution. The sol ution wa s sprayed
into a precipitation bath containing 250 ml of
0.50 !VI NaOH, which neutralized the acetic acid
wi thin the chitosan gel and the reby coagulated
the chi tosan gel to spher ical uniform chitosan
gel beads. The aqueous NaOH solution was
stirred using magnetic stirrer. The wet chitosan
gel beads were extensively rinsed with distill ed
water to remove any NaOH, filtered and finally
air dried to remove the water from the pore
struc ture (hereafter called chitosa n beads) . The
beads were then ground by usi ng a labor ator y
jar mill and sieved to a constant size 250
urn) before use .
2.3. Preparation of cross-linked chitosan
beads
Three different cross-linking agents used to
modify chi tosan at a rati o of I : I (chitosan.cross-
linking agent) .
WS . \\ ' 111 Ngah et al. / Reacti ve & Functional Polymers 50 (2002) / 8/ -/90
- - - --- - -
183
2.3. 1. Glutara ldehyde t GLA)
Chirosan-glu raraldehyde beads were prepared
using a similar procedure to that descri bed by
Guibal et al . [18]. Recently prepared wet
chitosan beads (as described before) were sus-
pended in 0.05 M glutaral dehyde solution to
obtain a ratio of I : I with chitosan. The chitosan
beads in result ing glutaraldehyde solution were
left standing for 24 h at room temperature. After
24 h the cross-linked chitosan beads were
inten sively washed with distilled water, filtered
and air-dried. The newly formed beads (here-
after called chitosan- Gl.A beads) were ground
to a cons tant particle sze 250 urn) before
use. The chitosan-Gl. A beads (as shown in Fig.
I ) obtained were confirmed by a Perkin-Elmer
FT-IR System 2000 Me del spectrometer.
2.3.2. Epi chlorohydrin /ECH)
Chit osan- epichlorohydrin beads were pre-
pared according to the following procedure
desc ribed previously (l ()]. A solu tion of 0.010
M epichlorohydrin containing 0.067 M sodium
hydroxide was prepared (p H 10). Freshl y pre-
pared wet chitosan beads were added to this
epichlorohydrin solution to obtain a ratio of I: I
with chitosan . The chi tosan beads in epi-
chlorohydrin were heated to a temperature
between 40 and 50
cC
for 2 h and stirred
continuously. After 2 h the beads were filtered
and washed intensively with distilled water to
remove any unreacted epichlorohydrin and air-
dried. The newly forrred cross-linked beads
(hereafter called chitosan-Ef.H beads) were
ground to a constant size 250 u rn) before
use. The chitosa n-ECH beads (as shown in Fig.
I ) obtained were confirmed by a Per ki n-Elmer
FT-IR System 2000 Model spectrometer.
2.3.3. Ethylene gLycoLdiglycidyl ether
(EGDE)
Chitosan-ethylene glycol diglycidyl ether
beads were obtained by a procedure described
by Zeng and Ruckenstein [16]. Chitosan beads
were prepared as mentiened earlier. A sol ution
containi ng 5% (v/v) EGDE was prepared and
added to the wet chitosan beads with a I: I
stoichiometric ratio between amino funct ions
and ether groups. The resulting solution were
heated to a temperature 50-60C for 3 hand
stirred conti nuously . After 3 h. the newly cross-
linked chitosan beads were intensivel y was hed
and air-dried. The beads (hereafter called
chitosan- EGDE beads) were ground to a con-
stant particle size ( < 250 urn) before use. The
chitosan-EGDE beads (as shown in Fig. I )
obtained were confirmed by a Perkin-Elmer FT-
IR System 2000 Model spectrometer.
2.4. Di ssolution and swelling test of chitos an
and cross-linked chitosan beads
Chitosan and cross-linked chitosan beads
were tested with regard to their solubi lity in
each of 5% (v/ v) acetic acid. di stilled water and
0. 10 M sodium hydroxide solution by adding
0.10 g of chitosan and cross-li nked chitosan
beads in each of the dilute acid, dis tilled water
and dilute alkaline solutions for a period of 24 h
with stirring.
The swelling studies of chitosan and cross-
linked chitosan beads were carried out in dis-
tilled water at room tempe rature for a period of
24 h. The percentage of swelling of these beads
were calculated by using the following equa-
tion:
W
s
- W
Percentage of swelling = W X 100% (I )
where W, is the weight of swollen beads (g) and
W is the weight of dry beads (g).
2.5. Adsorption experiments
A stock solution (l000 ppm) of Cu(Il) ions
was prepared from analytical-reagent grade Cu
metal (BDH). This stock solution was then
diluted to give standard solution of 5 ppm.
Batch adso rption experiments were conducted
in 250 ml beaker and equilibrated usi ng a
magnetic stirrer. Then 100 ml aliquots of these
standard solutions were placed in 250 ml beak-
ers and equilibrated with 0.0109 of chitosan or
cross-linked chitosan beads. After filtration, the
184 11'.5. Wall 'vgah et al . 1 Reactive & Functional Polvmers 50 (lOOl ) 1IJ1 - 190
N
/
(a)
(c)
N
(b)
NH NH
b H C H C H ~ C H C H C H C H b H
I I
OH OH
(d)
Fig. I. Schematic represent ation of the chitosan and cross-li uked chitosan beads: (a) chitosun. (b) chitosan-glutaraldehyde (chitosan-Gl. A),
(c) chitosan -epichlorohydrin (chitosan-ECH). (d) chitosan-ethylene glycol diglycidyl ether (chitosan-EGDE).
concentration of Cl.i(lI) in supernatant was
analyzed using atomic absorption spec-
troph otoniet er (Instrumental Laborator y lLAAS
357 Model ). The effect of Cu (lI ) adsorption
was studied in the pH range of about 1-6. The
pH of the initial solution was adjusted to the pH
value using 0.10 M HN0
3
or 0.10 M NaOH.
Chitosan and cross-linked chitosan beads were
equilibrated at the particular pH for about 30
min and at an initial Cu (II ) concentration of 5
ppm. The effect of agitation peri od and agitation
rate al so studie d to det ermined the optimum
condition for adsorption of Cu(lI ) ions.
Adsorpti on equilibrium studies were COI1-
\V.S. I\'all ,vgail et al. I React i ve & Functi onal Polymer, 50 (lOOl ) 181 -190 185
duct ed using a contaet time of 60 min at pH 6.0
for chitosan, chitosa.i-Gl.A and chi tosan-ECH
beads wher eas for chitosan-EGDE beads, a
contact time of 90 min at pH 6.0. Isotherm
studies were conducted with a constant chitosan
and cross-linke d chitosan beads we ight (0.0 10
g) and varying initial concentrati on of CurIl ) in
the range 0-14 ppm. The amount of adsorpti on
was ca lculated based on the difference of Cut Il )
concentration in aqueous before and after ad-
sorption, the volume of aqueous solution ( 100
ml ) and the weight of the beads (0.0 109)
according to:
. " (Co - CJV
Adsorption capacrty (X) = W (2)
where Co is the initial Cu (ll ) concentration
(ppm). C ~ is the final or equilibrium Cu( ll )
concentration (ppm), 1/ is the volume of Cut ll)
solution (ml), and W is the weight of the
chitosan or cross-l inked chitosan beads (g) .
For desorption studies, 0.0 109 of chitos an
and cross-linked chit osan beads we re loaded
with rl1(TT) using HlO ml of 5 ppm Cut ll)
solution at optimum pH and an agitation period
of 60 mi n was given for chitosan, chitosan- ECH
and chitosan-Gl.A beads and 90 min for
chitosan- EGDE beads. The agitation rate was
fixed at 500 rpm for all the beads. Cu(ll)-Ioaded
chitosan and cross-l inked beads were co llect ed,
gentl y washed with distilled wa ter to remove
any unabsorbed Cut ll ). The amount of Cu (ll )
adsorbed per gram of chitosan and cross-li nked
chitosan beads were determined by usin g the
supernatant Cu (ll ) concentration. The chitosan
and cross-linked chitosan beads were agitated
with 100 ml of EDTA of vari ous concentrations
Table I
Solubility effect of chitosan anJ cross-lin king chitosan beads
00-
2-
10-
6
M) and the amount of desorbed
Cu(ll) was de termi ned as before .
3. Results and discussion
3.1. Solubility and swe lling test of chitosan
and cross- linked chitosan beads
It wa s shown that after cross-linking, the
cross-linked chitosan was found to be insoluble
in acidic and alkaline med ium as well as
di stilled water (Table I ). It is we ll known that
the hi gh hydr ophilicity of chi tosan beads or raw
chitosan due to a primary amine group makes
chitos an easily soluble in dilute ace tic or formic
acid solutions to yield a hydrogel in water. The
swelling behavio ur of chitosan also improved
after cross-linkin g. A co nve nient proof of cross-
linking is the swelli ng behaviour of the cross-
linked chitosan beads in dilute acetic acid. Thus,
cross-linking treatment should be nece ssary to
reinfor ce the chemical stability of the beads in
such ~ i c l i c sol ution. Meanwhile, the les s swell-
ing behaviour of cross-linked chitosan beads
was important so they can be used in an
ads orption column. The percentage of swelling
of chitosan and cross-li nked chitosan beads are
given in Table 2.
3.2. Effect of pH
Fig. 2 shows the effect of pH on the ad-
sorption of Cu (ll ) by chitosan and cross-linked
chitosan beads. The adsorption incr eases ( i.e.,
the di fference in abs orbance increases) with
increasing pH of the solution. This co uld be
Beads
Chi tosan
Chitosan-GLA
Chit osan-ECH
Chitosan-EGDE
Solubility effect
5% (v/ v) Acetic acid
Sol uble
Insoluble
Insoluble
Insoluble
Distilled water
Insoluble
Insoluble
Insoluble
Insoluble
0. 10 M NaO H
Insolu ble
Insolu ble
Insoluble
Insolu ble
-- - - - - - --- - - - - - - - - --- - - -
~ ~ ~ _
186 irS. mill Nguh et al . I Reactive & Functional Polymers 50 (2002) 181-190
Table 2
Swell ing beha viour of chi tosan and cross-linked chitosan bead s
Beads Swelli ng ( %)
5% (v / v) Acetic acid Disti lled water 0.10 M Na OH
Chitosan
Chitosan-GLA
Chitosan-EC H
Chi tosan -EGDE
Solub le
15.6
20.6
14. 1
39.8
11.9
17.5
6.2
35.9
9.5
13.6
4.5
--+- CS-ECH
___CS-EGDE
--CS-GLA
-.-CHITOSAN
0.160 ....-----------,
0. 120
0.000 +---t--t----t--+----j
o 20 40 60 80 100
Agitation Period (mi nutes)
0.080
~
E

' 0.040
Fig. 3. Effect of agitation period on the adsorption of Cu " on
chi tosan and cross-linke d chi tosan beads; A. absorbance.
8
--+-CS-ECH
___CS EGDE
--CS-GLA
-.-CHITOSAN
6 2
0.000 +-- -+- - +-- -+----j
o
0.120
~ 0.080
.t'
:m
E
<{ 0.040
4
pH
Fig. 2. Effec t of pH on the Cu " adsorpti on on chitos an and
cros s-linked chitosan beads; A. absorbance.
explained by the facr rhar M low pH (acidic
solution), amine groups in the beads easily form
prot onation which induced an electrostatic re-
pulsion of Cu(II ) ions. Therefore, competition
existed between protons and Cu(II ) ions for
adsorption sites and adsorpti on capacity was
decreased. At higher pH values (basic solution),
precipit ation of Cu(II ) hydroxide occurs simul -
taneously with the adsorption of Cu(II ) ions,
hence, one needs to be careful in interpreting
the adsorption capacity of the beads. pH 6.0 was
chosen for the adsorption of Cu(II ) ions to
avoid the formati on of Cu(II ) hydroxide which
will affect the adsorption by the beads.
the adsorption of Cu(ll) by chi tosan and cross-
linked chitosan beads. The adsorption of Cu(II )
increases with agitation period and attains
equilibrium at about 60 min for chitosan,
chit osan-GLA and chitosan-ECH beads, and 90
min for chitosan-EGDE beads for an initial
Cu(II ) concentration of 5 ppm. It shows that the
adsorpti on of Cu(ll ) remains constant after 60
min for chitosan, chit osan-Gl.A and chit osan-
ECH beads and 90 min for chit osan-EGDE
beads, implying that equilibrium has been
reached. Therefore the optimum agitation period
for adsorpti on of Cu(II ) was about 60 min for
chitosan, chitosan-Gl. A and chitosan-ECH
beads, and 90 min for chit osan-EGDE beads.
3.3. Eff ect of agitation period
The optimum period for the adsorption of
Cu(II ) on chitosan and cross-linked chitosan
beads can be observed by looking at the differ-
ence in absorbance of Cu(II) solution after
adding chitosan and cross-linked chit osan beads.
Fig. 3 shows the effect of agitation period on
3.4. Effect of agitation rate
Fig. 4 shows the effect of agitation rate on the
adsorpt ion of Cu(II ) by chitosan and cross-
linked chitosan beads. The adsorption of Cu(ll )
increases with agitation rate and attains a con-
stant value at about 500 rpm for all the beads.
~ - - - - - - -
IV.S. IVall Nguh et al. / Reactive & Funct ional Polymers 50 (2002 ) 181-/90
187
0.160 ,---- --------,
CS ECH
CS-EGDE
CS-GLA
X CHITOSAN
8 6 4
c. (ppm)
2
0.16 .,--- - - - - - - - - ---,
--
"
o 0.04
::J 0.12
E
C>
-S 0.08
X
cross-linked chitosan bead s at equi libri um con-
centration (mg g- I), X
ma x
is the maxi mum
adsorption at monol ayer coverage (mg g - I) and
b is the Langmuir adsorption equi librium con-
stant (ml mg- I) and is a measure of the energy
of adsorption.
A linearized plot of Ce/X versus C, (Fig. 6)
gives X
max
and b. Tabl e 3 lists the calculated
results. It shows that the Langmuir equation best
fits for Cu(II ) adsorption on the chitos an and
cross-linked chitosa n beads under the concen-
tration range studied (correlation coefficient, r>
0.99). Cross-linking treatment decr eases adsorp-
tion performances involving a decrease in the
numb er of free amine groups, a decrease in the
accessibility to the internal sites or block a
number of adsorption sites.
It has been report ed that the effect of iso-
therm shape with a view to predict ing if an
adsorption system is "favourable" or " un-
favourable" [20]. The essential features of a
(3 )
---CS-ECH
---+- CS-EGDE
--CS-GLA
.....- CHITOSAN
800 200 400 600
Agitation Rate (rpm)
0.120
0.000 +---+---1- - -+----4
o
0.040
"
s
<{
, 0.080

'c
<(-
3.5. Adsorp tion isother ill s
where C
e
is the equi librium or final concen-
tration of Cu(Il ) (ppm), X is the amount of
Cu(Il ) adsorbed per u.iit weight of chitosan or
Fig. 5 shows the experimental equilibrium
isotherms for adsorption of Cu( II) on chitosan,
chitosan- Gl.A, chit man-ECH and chi tosan-
EGDE beads. Their adsorption behaviours can
be described with the Langmuir ads orption
equat ion as :
Therefore the optimum agitation rate for ad-
sorption of Cu( II) was 500 rpm for chitosan and
cross-linked chitos an beads .
Fig. 4. Effec t of agitation rate on the adsorption of Cu
h
on
chitosan and cross -linked chitos an beads; .4. , absorba nce.
C. (ppm)
Fig. 5. Adsorption isot herms of Cu' - on chitosan and cross-
linked chitosan beads.
r
0.9998
0.999 3
0.9987
0.9987
2.40
4.84
2.27
2.16
80.7 1
59.67
62.47
45.62
Adsorption constant Beads
Chitosan
Chi tosan-Gl. A
Chitosan-ECH
Chitosan-EGDE
Fig. 6. Adsorption isotherms of Cu" on CS-ECH. CS-EG DE,
CS-GLA and chitosan beads, linearized according to the Langmuir
equation.
Table 3
Experimental Langmuir isotherm con stants and correlati on co-
efficients
___CS-ECH
---+- CS-EGDE
--CS GLA
-.-CHITOSAN
6 8
80
60
:
40
x
20
0
0 2 4
- -- - - - - - - -- - - --- - - - - - - - - - - - - - ----------- ----- -
- - - - - --- --- ----- - - - - -

188
W5. lIilll Ngah et al, / Reactive &: Functional Polyme rs 50 ( l OO:!) /8/ - /90
Langmuir isotherm can be expressed in terms of
a dimensionless constant separation factor or
equilibrium parameter, RL' which is defined by
[21]:
of adsorption may be affected by metal ion
concen trat ion, agitation period and rate. The last
step of the adsorption is considered as a rate-
determining step and as a relatively rapid pro-
cess .
where Co is the initial Cu(U) concentration
(ppm) , and b is Langmuir adsorption equi lib-
rium cons tant (ml mg - 1). The parameter indi-
cates the isotherm shape according to Table 4.
The values of R
L
calculated for different
initial Cu(lI) concentration for chitosan and
cross-linked chitosan beads are given in Table
5. The R
L
values show that favourable ad-
sorpti on of Cu(U) on chitosan and cross-linked
chit osan beads takes place. ther efore chit osan
and cross -linked chitosan beads are favourable
adsorbers.
Chit osan and cross-l inked chitosan beads can
be considered to be microporous biopolymers;
therefore pores are large enough to let CurIl )
ions through. The mechanism of ion adsorption
on porous adsorbents mainly follo ws three steps
[22]: (i ) diffusion of ions to the external surface
of adsorbe nt, (ii) diffusion of ions into the pores
of adsorbent, and (iii) adsorpti on of the ions on
the internal surface of adsorbent. The first step
RL = 1 + bC
o
Table 4
Effect of separat ion factor on isothe rm shape
RI. value
RI. > 1
R = 1
l.
O<Rl.< 1
RI.=0
Table 5
RI. val ues based on the Langmuir equation
(4)
Type of isotherm
Unfavo urable
Linear
Favou rable
Irreversible
3.6. Desorpti on studies
Desorption studies will help to elucidate the
natur e of adsorption proce ss and to recover the
Cut ll ) from chitosan and cross- linked chitosan
beads. Moreover , it also will help to regenerate
the chi tosan beads so that it can be used agai n to
adsorb metal ions. EDTA is used to do the
desorption studies. Chitosan beads were soluble
in higher concentration of EDTA solution and
only low concentration can be used. Whereas,
cross-linke d chitosan beads were not soluble in
EDTA solution although at higher concentra-
tion. Percentage desorptions of Cu(II ) from
chitosan and cross-linked chit osan beads by
using EDTA are listed in Table 6.
4. Conclusion
The cross-linked chitosan beads with glutaral-
dehyde, epichlorohydrin and ethylene glycol
digl yci dyl ether as cross-linke rs is insoluble in
both acidic and basic media. Chitosan and
cross-linked chitosan beads can be effecti ve
adsorbents for collection of Cut ll ) ions from
aqueous solution. Although chitosan beads show
higher adsorpti on capacity than cross-linked
chit osan beads but cross-linked chitosan beads
can be used in low pH solution and its also
Cu(II) initial RI. values
concentration (ppm) Chit osan Chitosan-GLA Chitosan-EC H Chitosan-EGDE
2 0. 172 0.09 4 0. 180 0. 188
4 0.094 0.049 0.099 0.104
6 0.065 0.03 3 0.068 0.072
8 0.050 0.025 0.082 0.055
10 0.040 0.020 0.042 0.044
- - - - - - - - - -- - -
II S. \1'<111 Ngah et al , / Reacti ve & Functional Po/villers j O (l001) 18 1- 190
Table 6
Percentage of desorpt ion of Cui II) from co mplex Cut ll j-chi tosan and cross-linked chitosan beads
189
Concentration
of EDTA (M )
LOX 10- '
LOX 10-
3
LOX 10-
LOX 10 -
5
LOX 10-
0
D (%)
Chitosan

34.3 1
5.88
Chitosan- GLA
95.38
86.82

34.40
10.6 1
Chitosan-ECH
97.67

71.09
22.22
7.0 1
Chi tosan-EGDE
82.30
63 .03

21. 90

show lower percentage of swelling. These two
characters are essentialtor an adsorbent so that
it can be used as a resin in ion-exchange
chro matography columns. More over , cross-
linked chitosan beads show better desorption
result s at higher concentration of EDTA, where-
as chitosan beads soluble in higher concen-
tration of EDTA. Therefore, cross-l inked
chitosan beads can be regenerated well com-
pared to chitosan beads.
5. Notation
X
ma x
Maximum adsorption capacity (mg
g- I )
Acknowledgements
The authors thank Universiti Sains Mal aysia
for the financial support under IRPA Short Term
Research Grant (grant No. 30SI PKI MIAI
622183).
References
A
A
li na ,
A ini t i aJ
b
ECH
EDTA
EGDE
FT-IR
GLA
rpm
V
W
W,
X
Absorbance of Cu(l!) the solution
Final absorbance Cu(lI ) solution
Initial absorbance of Cu(lI ) solution
Langmuir adsorpt ion equilibrium
- I
constan t (ml mg )
Final or equilibrium concentrat ion
of Cu(II ) solution (ppm)
Initial concentration of Cu(II ) solu-
tion (ppm)
Epichloroh ydri n
Ethylenediarr.inetetr aacetic acid
Ethylene glycol diglycidyl ether
Fourier transrorm infrared
Glutaraldehyde
Correlation coeffic ient
Dimensionless constant separation
factor or equ:librium parameter
Round per min
Volume of the Cu(II ) solution (ml )
Weight of dr y beads (g )
Weight of swollen beads (g)
Adsorpti on capacity (mg g - I )
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