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Article history:
Received 15 December 2008
Received in revised form
10 September 2009
Accepted 5 December 2009
Available online 30 December 2009
Chitosan-tripolyphosphate (CTPP) beads were synthesized, characterized and were used for the
adsorption of Pb(II) and Cu(II) ions from aqueous solution. The effects of initial pH, agitation period,
adsorbent dosage, different initial concentrations of heavy metal ions and temperature were studied. The
experimental data were correlated with the Langmuir, Freundlich and Dubinin-Radushkevich isotherm
models. The maximum adsorption capacities of Pb(II) and Cu(II) ions in a single metal system based on
the Langmuir isotherm model were 57.33 and 26.06 mg/g, respectively. However, the beads showed
higher selectivity towards Cu(II) over Pb(II) ions in the binary metal system. Various thermodynamic
parameters such as enthalpy (DH ), Gibbs free energy (DG ) and entropy (DS ) changes were computed
and the results showed that the adsorption of both heavy metal ions onto CTPP beads was spontaneous
and endothermic in nature. The kinetic data were evaluated based on the pseudo-rst and -second order
kinetic and intraparticle diffusion models. Infrared spectra were used to elucidate the mechanism of
Pb(II) and Cu(II) ions adsorption onto CTPP beads.
2009 Elsevier Ltd. All rights reserved.
Keywords:
Chitosan-tripolyphosphate beads
Adsorption
Heavy metal ions
Thermodynamic
Binary metal system
1. Introduction
The presence of heavy metal ions in various water resources has
stirred great concerns among the public. Among all the heavy metal
ions, special attention has been given to Pb(II) and Cu(II) ions. Pb(II)
ions can be found in efuents from battery recycling plants, lead
mining and electronic assembly plants and are known to cause brain
damage, dysfunction of the kidneys, liver and the central nervous
system in human beings due to its cumulative effect. On the other
hand, Cu(II) ions although known to be an essential trace element to
humans, have fatal effect if induced at high dosage (Ho et al., 2002).
The wide usage of Pb(II) and Cu(II) ions in various industries has
triggered the necessities of developing an efcient method to
remove these heavy metal ions from wastewaters. The existing
methods such as chemical precipitation and membrane separation
have proven to be effective in wastewater treatment, however there
are drawbacks as these methods are costly and cannot be applied to
wastewater with low concentration of heavy metal ions (Juang and
Shao, 2002; Li and Bai, 2005a). Recently, adsorption using materials
of biological origins has been considered as one of the most
Nomenclature
KF
DG
DH
DS
3
kint
M2
b
Ce
Co
CTPP
E
ho
ht
k
k1
k2
groups in chitosan will interact with the negatively charged counterion, TPP, through an ionic interaction creating ionic cross-linked
networks (Mi et al., 1999, 2003). Mi et al. (1999, 2003) studied on
the preparation of CTPP beads. These authors used different pH of
the sodium tripolyphosphate solution to control the degree of
cross-linking. The main purpose of these two works was to gain
insight of the mechanism involved during the formation of the
beads. The method used for the preparation of CTPP beads in this
present study was similar to the work by Lee et al. (2001). In the
work by Lee et al. (2001), the CTPP beads used were to adsorb Cu(II)
ions in a single metal system. The beads showed a very good
adsorption capacity for Cu(II) ions with almost 248.52 mg/g.
Although in this study, the kinetic of adsorption process was
studied, the effect of temperature and the ability of CTPP beads to
adsorb in binary metal system were not explored. In fact, the ability
of CTPP beads to adsorb other metal ions was also not reported. This
gave way for more adsorption studies to be conducted using CTPP
beads.
The present study aims to explore the adsorption of Pb(II) and
Cu(II) ions onto CTPP beads in single and binary metal system. The
inuence of initial pH of the heavy metal ions solution, agitation
period, adsorbent dosage and initial concentration of heavy metal
ions solution on the adsorption of Pb(II) and Cu(II) ions were
studied. The non-linear Langmuir, Freundlich and DubininRadushkevich isotherms were used to evaluate the equilibrium
adsorption data. The adsorption rates were also determined based
on the pseudo-rst and -second order kinetic and intraparticle
diffusion models. Thermodynamic parameters for the adsorption of
Pb(II) and Cu(II) ions were also studied. Fourier transform infrared
spectroscopy was used to elucidate the mechanism of Pb(II) and
Cu(II) ions adsorption onto CTPP beads. The desorption efciency
and reusability of the adsorbent were assessed based on three
consecutive adsorptiondesorption cycles.
2. Experimental
2.1. Materials
The chitosan akes sample with a degree of deacetylation of
61.55% (determined using an infrared spectroscopy method), was
n
Q
qe(exp.)
qe(theor.)
qe
Qm
qt
r
R
S
S
t
V
W
959
supplied by Chito-Chem (M) Sdn. Bhd., Malaysia. Sodium tripolyphosphate (STPP) was purchased from SigmaAldrich. All the
reagents used were analytical-reagent grade. Distilled water was
used throughout the study.
2.2. Preparation of CTPP beads
Chitosan was prepared by dissolving 2.00 g of chitosan akes in
60 mL of 5% (v/v) acetic acid and was left overnight. A 100 mL of
0.05 M of STPP solution was prepared and the pH of the solution
was adjusted to pH 8 using 0.1 M HCl. The viscous solution of
chitosan was then dropped into the STPP solution under continuous
stirring. The beads were left overnight in the solution. The slightly
yellowish CTPP beads were ltered, rinsed with distilled water and
nally air-dried. The CTPP beads were ground and sieved to
a constant particle size (<200 mm) before use.
2.3. Characterization of CTPP beads
The BET, Langmuir surface areas and pore diameter were
determined using a Micromeritics ASAP 2010 gas adsorption
surface analyzer. The CHN analysis of the beads was determined
using a PerkinElmer Series II 2400 CHNS/O Analyzer. The types of
functional groups on CTPP beads were conrmed by a PerkinElmer
FTIR System 2000 Model spectrometer. The surface structure of
CTPP beads before and after adsorption was observed using a Leica
Cambridge S360 scanning electron microscope (SEM) coupled with
energy dispersive X-ray spectroscopy (EDX).
2.4. Swelling test of chitosan-tripolyphosphate beads
The swelling study was conducted on CTPP beads according to
the method proposed by Denkbas and Odabasi (2000). About
0.050 g of CTPP beads was inserted into a tube with a diameter of
5 mm and a height of 100 mm. The level of the beads in the tube
was marked before lling it with 1 mL of 5% (v/v) acetic acid,
distilled water or 0.10 M NaOH solution and was left for 24 h. After
24 h, the height of the beads in the solution was measured. The
percentage of swelling was calculated based on the following
equation (Denkbas and Odabasi, 2000):
960
ht ho
100
S
ho
(1)
Adsorption capacityqe
Co Ce
V
W
(2)
Chitosan beads
1253
1594
1650
895
1319
1420
1379
2883
1152
1081
1029
3420
1416
1308
1529 1384
1255
1640
3449
2920
1090
1153
4000.0
3600
3200
2800
893
CTPP beads
2400
2000
1800
1600
1400
1200
1024
1000
cm-1
800
600
400.0
961
were very low at lower pH. This was due to the higher percentage of
swelling exhibited by CTPP beads at lower pH. This caused the
beads to be very brittle. However, as the pH increased, the
adsorption capacity also increased as the swelling effect was
reduced. The low adsorption capacities of Pb(II) and Cu(II) ions
observed at lower pH of the solution could be due to the repulsion
between the heavy metal ions and the surface active sites
(protonated amine groups). As the pH increased, there would be
a decrease in the positive surface active sites, which would lower
the electrostatic repulsion between the positively charged heavy
metal ions and the surface of the adsorbent, thus favoring
adsorption. The maximum adsorption capacity of Pb(II) and Cu(II)
ions occurred at pH 4.5. Therefore, pH 4.5 was used as the optimum
pH throughout the study.
As the adsorption process proceeded, the adsorbed solute tends
to desorb into the solution. Eventually, the rate of adsorption and
desorption will attain an equilibrium state and once the system
reaches equilibrium, no further net adsorption would occur
(Hawari and Mulligan, 2006). Based on Fig. 3, it was observed that
there was a rapid uptake within the rst 50 min and followed by
a slow increase until a state of equilibrium was attained after
90 min. This observation was almost similar to the ndings by
Panuccio et al. (2008). Therefore, 100 min of contact time was
chosen as the optimum contact time for the adsorption of Pb(II) and
Cu(II) ions onto CTPP beads.
The percentages of removal increased from 75 to 95% for both
Pb(II) and Cu(II) ions, respectively, as the adsorbent dosage was
increased from 0.025 to 1.00 g. The availability of the adsorption
sites for adsorbentadsorbate interaction contributed to this
observation. However, the adsorption capacity of Pb(II) and Cu(II)
ions decreased as the adsorbent dosage was increased. This was
due to the unsaturation of the adsorption sites involved during the
adsorption process (Aydin et al., 2008; Malkoc and Nuhoglu, 2007).
Further adsorption equilibrium study was conducted using 0.20 g
CTPP beads as the percentage of removal was the highest and
further increment in adsorbent dosage showed no changes.
3.4. Equilibrium adsorption isotherm (single metal system)
The adsorption isotherm is fundamental in understanding the
mechanism of adsorption. Important informations regarding how
the adsorbate molecules distribute between the liquid phase and
the solid phase once the equilibrium state is reached can be
interpreted based on the adsorption isotherm. The Langmuir,
12
12
10
Adsorption capacity, qe
(mg/g)
Adsorption capacity, qe
(mg/g)
Lead (II)
10
Copper (II)
8
6
4
8
6
4
Lead (II)
Copper (II)
0
0
0
0
50
100
150
Agitation period (min)
200
pH
Fig. 2. Effect of initial pH on the adsorption of Pb(II) and Cu(II) ions onto CTPP beads.
Fig. 3. Effect of agitation period on the adsorption of Pb(II) and Cu(II) ions onto CTPP
beads.
962
(3)
qe KF Ce
(4)
Q Qm exp k32
(5)
E 2k
0:5
40
Adsorption capacity, qe (mg/g)
bQCe
1 bCe
45
35
30
25
20
15
Experimental data
(Lead (II))
10
Experimental data
(Copper (II))
Langmuir isotherm
5
0
Freundlich isotherm
20
40
60
80
100
120
140
Equilibrium concentration, Ce (mg/L)
180
x 10
4
Experimental data
(Lead (II))
(6)
160
Fig. 4. Non-linear Langmuir and Freundlich isotherm for the adsorption of Pb(II) and
Cu(II) ions onto CTPP beads in a single metal species system.
Experimental data
(Copper (II))
3
Q (mol/g)
qe
50
D-R isotherm
0
2.5
3.5
4.5
5
2
5.5
6.5
7
8
x 10
Fig. 5. Non-linear D-R isotherm for the adsorption of Pb(II) and Cu(II) ions onto CTPP
beads in a single metal species system.
Pb(II) ions
Cu(II) ions
Pb(II) ions
Cu(II) ions
26.06
4.77 102
0.96
18.58
3.98 102
0.98
19.18
6.53 102
0.97
Langmuir isotherm
Q (mg/g)
57.33
b (L/mg)
1.39 102
r
0.98
Freundlich isotherm
2.52
KF (mg/g)
n
1.79
r
0.97
4.96
3.19
0.99
D-R isotherm
k (mol2/kJ2)
Qm (mol/g)
E (kJ/mol)
r
0.48
2.55 104
1.02
0.99
0.53
1.00 104
0.98
0.98
3.42
3.25
0.99
Table 2
Langmuir isotherm constants and thermodynamic parameters for the adsorption of
Pb(II) and Cu(II) ions onto CTPP beads.
Metal
T (K)
Langmuir isotherm
Q (mg/g)
b (mL/mg)
DG
DH
D S
(kJ/mol)
(kJ/mol)
(J/K mol)
Pb(II)
300
323
333
343
57.33
64.38
66.70
67.86
1.39
1.92
2.42
3.24
102
102
102
102
0.98
0.99
0.99
0.99
2.64
3.71
4.47
5.43
16.26
62.57
Cu(II)
300
323
333
343
26.06
24.98
26.96
28.77
4.77
1.46
1.78
2.46
102
101
101
101
0.96
0.96
0.97
0.98
2.76
5.99
6.72
7.83
32.64
118.44
4.88
3.87
0.99
963
system. Liu et al. (2008) stated that there were possibilities for
the adsorbed Pb(II) ions on the adsorbent to be released into
the solution during the competitive adsorption process. Thus,
another study was conducted whereby the CTPP beads loaded with
2.18 mg/g of Pb(II) ions was added into a 10 mg/L of Cu(II) ions
solution and was stirred under optimum conditions. The ltrate
was then analyzed and it showed that the amount of Cu(II) ions
adsorbed was 2.40 mg/g and about 0.81 mg/g (37%) of Pb(II) ions
were released into the solution. A blank experiment was also
conducted to prove that the displacement of the adsorbed ions only
occurred in the presence of another metal ion solution. Meanwhile,
when the CTPP beads which was loaded with 2.38 mg/g of Cu(II)
ions was used to adsorb Pb(II) ions (10 mg/L), it was found that the
amount of Pb(II) ions adsorbed was 1.92 mg/g and the displacement
of Cu(II) ions was merely 0.12 mg/g (5.21%). Based on these
observations, it showed that CTPP beads has higher afnity for
Cu(II) ions in comparison to Pb(II) ions. During the binary study,
Cu(II) ions were a strong competitor for lead (II) ions and the
presence of Cu(II) ions greatly depressed the adsorption of Pb(II)
ions. Apart from that, based on the Freundlich isotherm, the
obtained result was similar to the result obtained in the single
metal system whereby the KF value obtained for Cu(II) ions was
higher than the value obtained for Pb(II) ions.
3.6. Thermodynamic of the adsorption of Pb(II) and Cu(II) ions
The effect of different temperature on the adsorption of Pb(II) and
Cu(II) ions onto CTPP beads based on Langmuir isotherm were
shown in Table 2. It was found that the adsorption capacity (Q)
values increased as the temperature was increased, which was
similar to the work by Prasad and Saxena (2008). Due to the
dependence on temperature, b values were used to predict the Gibbs
20
18
3
2.5
14
12
10
8
Experimental data
(Lead (II))
Experimental data
(Copper (II))
ln b
16
1.5
1
Langmuir isotherm
Freundlich isotherm
2
0
0
50
100
150
Equilibrium concentration, Ce (mg/L)
200
Fig. 6. Non-linear Langmuir and Freundlich isotherm for the adsorption of Pb(II) and
Cu(II) ions onto CTPP beads in a binary metal species system.
0.5
Lead (II)
Copper (II)
0
0.0028
0.0029
0.003
0.0031
0.0032
0.0033
0.0034
-1
1/ T (K )
Fig. 7. Plot of ln b versus 1/T for estimation of thermodynamic parameters for the
adsorption of Pb(II) and Cu(II) ions onto CTPP beads.
964
Table 3
Kinetic parameters for the adsorption of Pb(II) and Cu(II) ions onto CTPP beads based
on the pseudo-rst and pseudo-second order kinetic and intraparticle diffusion
equations.
Pb(II) ions
Cu(II) ions
qe(exp.) (mg/g)
9.28
9.67
Pseudo-rst order
k1 (min1)
qe(theor.) (mg/g)
r
4.10 102
3.99
0.99
3.82 102
1.76
0.99
Pseudo-second order
k2 (g/mg min)
qe(theor.) (mg/g)
r
1.86 102
9.73
0.99
4.66 102
9.84
0.99
Intraparticle diffusion
kint,1 (mg/g min1/2)
r
kint,2 (mg/g1 min1/2)
r
0.35
0.98
0.11
0.95
0.30
0.97
0.04
0.98
DG RTlnb
DS
R
8
6
4
Lead (II)
Copper (II)
0
0
40
60
80
100
120
Fig. 9. Pseudo-second order plot for the adsorption of Pb(II) and Cu(II) ions onto CTPP
beads.
(7)
DH
20
t (min)
lnb
10
t / qt (min g/mg )
Kinetic equation
12
(8)
RT
logqe qt logqe
k1
t
2:303
(9)
where qe and qt are the amounts of Pb(II) or Cu(II) ions adsorbed onto
CTPP beads (mg/g) at equilibrium and at time t, respectively, and k1 is
the rate constant of pseudo-rst order kinetic model (min1). The
straight-line plots of log (qe qt) against t were used to determine
the k1 and correlation coefcient, r. The k1, qe(theor.) (calculated
equilibrium adsorption capacity value) and qe(exp.) (experimental
0.8
12
10
8
20
40
60
80
100
120
-0.4
qt (mg/g)
log ( qe - qt )
0.4
6
4
-0.8
Lead (II)
2
-1.2
Lead (II)
Copper (II)
Copper (II)
-1.6
t (min)
Fig. 8. Pseudo-rst order plot for the adsorption of Pb(II) and Cu(II) ions onto CTPP
beads.
1/2
(min
8
1/2
10
12
Fig. 10. Intraparticle diffusion kinetics for the adsorption of Pb(II) and Cu(II) ions onto
CTPP beads.
965
Table 4
Adsorption and desorption behaviors of Cu(II) and Pb(II) ions on CTPP beads.
Metal Ion
Desorption medium
Cycle 1
Cycle 2
Cycle 3
Uptake (mg/g)
Recovery (%)
Uptake (mg/g)
Recovery (%)
Uptake (mg/g)
Recovery (%)
Cu(II)
0.1 M EDTA
0.01 M EDTA
0.001 M EDTA
2.38
2.38
2.39
77.46
92.26
94.56
2.09
2.12
2.07
74.93
95.14
96.52
1.89
2.14
2.09
75.63
96.25
95.15
Pb(II)
0.1 M EDTA
0.01 M EDTA
0.001 M EDTA
2.42
2.42
2.43
98.67
97.60
92.35
2.41
2.39
2.16
97.09
95.75
92.56
2.24
2.15
97.49
95.81
t
1
t
qt
qe
k2 q2e
(10)
where qe and qt are the amounts of Pb(II) and Cu(II) ions adsorbed onto CTPP beads (mg/g) at equilibrium and at time t, and k2
A
CTPP beads
1415
1640
1314
1530 1384
1253
1152
%T
520
3449
1023
1090
1314
518
1250
1541 1384
3450
1152
1099 1023
1637
4000.0
3600
3200
2800
2400
2000
1800 -1 1600
cm
1400
1200
1000
800
600
400.0
B
CTPP beads
1415
1530
3449
1314
1253
1640
1152
%T
520
1384
1023
1090
518
1323
1544
3445
1384
1152
1400
1200
1638
4000.0
3600
3200
2800
2400
2000
1800 -1 1600
cm
1018
1074
1000
800
600
400.0
Fig. 11. FTIR spectrum of CTPP beads before and after the adsorption of Pb(II) ions (A) and Cu(II) ions (B).
966
CH2OH
CH2OH
O
H
H
H
H
H
OH
H
HO
NH2
NH3
OH
O P
O P
O P
O
O
M n+
O
O
O
O-
NH2
H
H
HO
H
O
H
H
O
CH2OH
HO
H
O
H
NH3
O
CH2OH
CTPP
CH2OH
CH2OH
O
H
H
H
OH
H
HO
NH2
NH3
O
H
O P
O
O
n+
-
O P
2 H+
O
O
M n+
O P
O
O-
H
HO
H
O
H
NH2
H
H
H
O
HO
H
NH3
CH2OH
CH2OH
CTPP +M
n+
Fig. 12. Binding mechanism for the adsorption of metal ions onto CTPP beads.
qt kint t 1=2
(11)
967
Rb=r
h
i
M2
h
i h i h i
i h
i
h
Na
K
H
Ca2 Mg2
2
2
2
(12)
Fig. 13. SEM-EDX spectra of CTPP beads (a) before adsorption, (b) after the adsorption of Pb(II) ions, (c) after the adsorption of Cu(II) ions and (d) after the adsorption of Pb(II) and
Cu(II) ions.
968
Fig. 14. SEM-EDX micrograph of the white particle found on the surface of CTPP beads after the adsorption of Pb(II) ions.
that the major changes in the FTIR spectrum after the adsorption of
Pb(II) and Cu(II) ions were quite similar. This indicated that the
mechanism for the adsorption of Pb(II) and Cu(II) ions onto the
beads were the same. The intensity of the broad band of the OH
stretching vibration at the wavenumber 3449 cm1 decreased due
to the Pb(II) and Cu(II) ions adsorption. Signicant changes in
the FTIR spectrum were also found at the wavenumber of 1314
and 1415 cm1 which can be assigned to CN stretching vibration
and NH deformation vibration in NH2. Both Pb(II) and Cu(II) ions
adsorption were found to affect the bonds related to nitrogen
atoms, indicating that nitrogen atoms could be the main adsorption
sites for both metal ions attachment. Apart from that, the intensity
at the wavenumber 1090 cm1 was reduced, suggesting that the
oxygen atom in the hydroxyl groups in the beads was also involved
in the adsorption of heavy metal ions ions (Jin and Bai, 2002; Li and
Bai, 2005a). These observations suggested that the adsorption of
Pb(II) and Cu(II) ions was probably through the formation of
complexes with the nitrogen atom of NH2 group (which were not
involved in the ionic-cross-linking process) and of the oxygen atom
of hydroxyl group (Fig. 12). Similarly, Lee et al. (2001), suggested
that the adsorption of Cu(II) ions onto CTPP beads was probably by
the chelation mechanism involving the nitrogen (from NH2
groups) and oxygen (from hydroxyl groups) atoms. The peak at
1640 cm1 showed signicant reduction in the transmittance
indicating the oxygen atom in the POH groups were involved in
the adsorption process. The formation of metal ions complexes
with the PO group (Fig. 12) occurred when the POH groups were
deprotonated. The release of the H ions in the solution explains
the reduction in the pH of the solution after the adsorption of Pb(II)
and Cu(II) ions. However, no signicant changes was observed at
1253 cm1, which represented the P]O stretching.
The SEM-EDX micrographs were shown in Fig. 13. The SEM
images for the CTPP beads before and after adsorption of Pb(II) and
Cu(II) ions in the single and in the binary metal system showed that
the surface morphology of the beads changed. Before adsorption,
the surface of CTPP beads (Fig. 13a) was smooth and there was less
cracking. The EDX spectra conrmed the existence of carbon,
oxygen, nitrogen and phosphorus in the beads. After Pb(II) ions
adsorption (Fig. 13b), the surface morphology drastically changed
whereby the surface was more in irregular form, but after Cu(II)
ions adsorption, the surface (Fig. 13c) was rough and more cracks
appeared on the surface. Once CTPP beads were introduced into the
binary metal system, the surface morphology (Fig. 13d) showed the
presence of white particles of Pb(II) ions on the surface of the beads.
Fig. 14 showed the EDX spectra obtained when the white particles
were analyzed. Due to the molecular weight of Pb(II) ions, it was
easily differentiated by SEM, but for Cu(II) ions the metal was not
clearly visible, but based on EDX spectra the presence for Cu(II) ions
was conrmed as well. The spectra showed that in binary metal
system, Pb(II) ions tend to cluster unevenly on CTPP beads but
Cu(II) ions was adsorbed more evenly on the surface of the beads.
4. Conclusions
Adsorption experiments showed that CTPP beads can be used as
an effective adsorbent for the removal of Pb(II) and Cu(II) ions. The
Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherms
were used, and all isotherms tted well with the adsorption equilibrium data obtained. The maximum adsorption capacity obtained
for Pb(II) and Cu(II) ions in the single metal system based on the
Langmuir isotherm model was 57.33 mg/g and 26.06 mg/g, respectively. Adsorption of Pb(II) and Cu(II) ions onto CTPP beads obeyed the
pseudo-second order kinetic model and also followed the intraparticle diffusion model, whereby intraparticle diffusion was not the
sole rate controlling step. Based on the thermodynamic studies, it was
found that the adsorption process was spontaneous and endothermic
in nature. Desorption study showed that Pb(II) and Cu(II) ions
adsorbed on the beads can be easily and effectively desorbed using
0.1, 0.01 and 0.001 M EDTA solution. FTIR analysis revealed that the
nitrogen and oxygen atoms found in the beads were the binding sites
for the metal ions. This work also showed that CTPP beads can be used
to treat wastewaters containing Pb(II) and Cu(II) ions.
Acknowledgement
The authors thank Universiti Sains Malaysia for the nancial
support under the Short Term Grant (Grant no. 304/229/PKIMIA/
638166) and the co-author would like to extend her gratitude to the
Universiti Sains Malaysia Fellowship for funding her studies.
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