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Journal of Environmental Management 91 (2010) 958969

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Journal of Environmental Management


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

Adsorption characterization of Pb(II) and Cu(II) ions onto


chitosan-tripolyphosphate beads: Kinetic, equilibrium and
thermodynamic studies
W.S. Wan Ngah*, S. Fatinathan
School of Chemical Sciences, Universiti Sains Malaysia, 11800 Penang, Malaysia

a r t i c l e i n f o

a b s t r a c t

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

* Corresponding author. Tel.: 60 4 6533888; fax: 60 4 6574854.


E-mail address: wsaime@usm.my (W.S.W. Ngah).
0301-4797/$ see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jenvman.2009.12.003

promising option in treating wastewater with low concentration of


heavy metal ions. A very promising natural material that can be
obtained in large quantities and cheap is chitosan, a nitrogenous
polysaccharide.
Chitosan, composed mainly of poly(b-1-4)-2-amino-2-deoxyD-glucopyranose, is obtained by alkaline deacetylation of chitin,
one of the most abundantly found biopolymers in nature. Chitosan
shows high afnity for metal ions due to the amine (NH2) and
hydroxyl (OH) groups. These groups function as the coordination
sites for heavy metal ions (Zhao et al., 2007). Although chitosan has
good adsorption capability, due to the low porosity and weak
mechanical property, its fullest capacities are not met. However,
physical or chemical modications can be carried out to overcome
these drawbacks. Physical and chemical modications can prevent
dissolution of chitosan in strong acids, improve the mechanical
strength and increase the adsorption capacities. Most commonly
used chemical modications are cross-linking, grafting of a new
functional group and acetylation (Sun and Wang, 2006). Crosslinking agents such as glutaraldehyde (GLA), epichlorohydrine
(ECH) and ethylene glycol diglycidyl ether (EGDE) are commonly
used but are not preferred due to their toxicity. Cross-linking agents
with less cytotoxic characteristics are given preferences nowadays.
Tripolyphosphate (TPP) is a non-toxic polyanion which interacts
with chitosan through electrostatic forces. The protonated amine

W.S.W. Ngah, S. Fatinathan / Journal of Environmental Management 91 (2010) 958969

Nomenclature

KF

DG
DH
DS
3

kint
M2

b
Ce

Co
CTPP
E
ho
ht
k
k1
k2

Gibbs free energy change (kJ/mol)


enthalpy change (kJ/mol)
entropy change (J/Kmol)
Polanyi potential, [RT ln (1 (1/Ce))]
the Langmuir constant related to the afnity of binding
sites (mL/mg)
nal concentration of Cu(II) or Pb(II) ions or
equilibrium concentration of remaining heavy metal
ions in the solution (mg/L)
initial concentration of Cu(II) or Pb(II) ions (mg/L)
chitosan-tripolyphosphate
the mean free energy (kJ/mol)
initial height of the beads (cm)
height of swollen beads (cm) at time t
constant related to the adsorption energy (mol2/kJ2)
rate constant of pseudo-rst order kinetic model
(min1)
the rate constant of pseudo-second order kinetic
model (g/mg min)

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

Freundlich constant indicating adsorption capacity


(mg/g)
the intraparticle diffusion rate constant (mg/g min1/2)
concentration of metal ions (Pb(II) or Cu(II) ions)
(mmol/L)
Freundlich constant indicating intensity
amount of heavy metal ions adsorbed (mg/g or mol/g)
the experimental value of adsorption capacity (mg/g)
calculated equilibrium adsorption capacity value (mg/g)
amount of metal ions adsorbed per mass unit of
adsorbent at equilibrium or adsorption capacity (mg/g)
the adsorption capacity (mol/g)
amount of metal ions adsorbed per mass unit of
adsorbent at time t (mg/g)
correlation coefcient
gas constant (8.314 J/K mol)
percentage of swelling (%)
temperature (K)
time (min)
volume of Cu(II) or Pb(II) ions solution (L)
weight of the CTPP beads (g) used

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

W.S.W. Ngah, S. Fatinathan / Journal of Environmental Management 91 (2010) 958969



ht  ho
 100
S
ho

concentration of Pb(II) and Cu(II) ions in the range of 20300 mg/L,


in the same solution.
The batch kinetic studies were carried out using 0.05 g adsorbent in 50 mL solution of 10 mg/L of Pb(II) or Cu(II) ions. The
adsorption time was varied from 10 to 180 min.
A series of desorption studies were also conducted using 0.20 g
CTPP beads loaded with either Pb(II) or Cu(II) ions under the
optimum conditions. The Pb(II) or Cu(II)-loaded CTPP beads were
then collected and washed with distilled water to remove any
unadsorbed Pb(II) or Cu(II) ions. The amount of Pb(II) or Cu(II) ions
adsorbed was determined. The dried CTPP beads were then
agitated with 50 mL EDTA solution of various concentrations for
60 min and the amount of desorbed Pb(II) or Cu(II) ions were
determined. This process was repeated for three times to observe
the reusability of CTPP beads. All experiments were carried out in
duplicates.

(1)

where S is the percentage of swelling, ht is the height of swollen


beads (cm) at time t and ho is the initial height of the beads (cm).
2.5. Batch adsorption experiments
Stock solutions of 1000 mg/L of Pb(II) and Cu (II) ions were
prepared using the analytical-reagent grade lead(II) nitrate salt and
copper metal, respectively. The stock solutions were diluted
accordingly to give the appropriate concentrations. The batch
adsorption experiments were conducted in 250 mL beakers with
50 mL of standard solutions and equilibrated at 400 rpm. All
experiments were conducted at 300 K, unless otherwise was stated.
The effect of initial pH on the adsorption of Pb(II) and Cu(II) ions
onto CTPP beads was studied in a pH range of 16. The initial pH of
the 10 mg/L Pb(II) or Cu(II) ions solution was adjusted using 0.10 M
HCl or NaOH solutions. A weight of 0.050 g CTPP beads was then
added into the solution and was stirred for 60 min. The effect of
agitation period was also studied under similar experimental
conditions. The effect of adsorbent dosage on the uptake of Cu(II)
and Pb(II) ions was conducted by varying the amount of adsorbent
from 0.025 to 1.00 g at a constant concentration of 10 mg/L of the
heavy metal ions solution under optimum pH and agitation period.
Adsorption equilibrium study in a single metal system was
conducted using 0.20 g of CTPP beads with a contact time of
100 min at different temperature ranging from 300 to 343 K. The
optimum pH used for Pb(II) and Cu(II) ions were pH 4.5 and the
concentration of heavy metal ions solution used were from 20 to
300 mg/L. The following equation was used to calculate the amount
of Pb(II) or Cu(II) ions adsorbed at equilibrium:

Adsorption capacityqe


Co  Ce
V
W

3. Results and discussion


3.1. Characterization of CTPP beads
The values of BET and Langmuir surface areas and average pore
diameter obtained for CTPP beads were 0.2667 m2/g, 0.4188 m2/g
and 12.67 nm, respectively. According to the IUPAC recommendation, total porosity can be classied into three groups which were
macropores (d > 50 nm), mesopores (2 < d < 50 nm) and micropores (d < 2 nm). Based on the average pore diameter value, CTPP
beads falls into the category of mesopores. The C, H and N
composition of CTPP beads 27.06, 5.42 and 4.68%, respectively.
Meanwhile, the C, H and N values obtained for chitosan beads were
37.51, 6.12 and 6.53%, respectively. It was observed that there was
a decrease in the percentage of free C, H and N atom after the crosslinking. The point of zero charge (pHpzc) of CTPP beads was found to
be at pH 4.00. pHpzc is the required pH value to give a zero net
surface charge on the beads (Chen et al., 2007). Based on this value,
the prepared adsorbent was acidic in nature.
The FTIR spectrum obtained for CTPP and chitosan beads were
compared (Fig. 1) to differentiate the functional groups existing
before and after the cross-linking. The major peaks for chitosan
beads were observed around 3420 cm1 which was assigned to the

(2)

where Co is the initial concentration of Pb(II) or Cu(II) ions (mg/L),


Ce is the nal concentration of Pb(II) or Cu(II) ions (mg/L), V is the
volume of the heavy metal ions solution (L) and W is the weight of
CTPP beads (g). The equilibrium adsorption study was also conducted in the binary metal system by varying the initial

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

Fig. 1. FTIR spectrum of chitosan beads and CTPP beads.

800

600

400.0

W.S.W. Ngah, S. Fatinathan / Journal of Environmental Management 91 (2010) 958969

stretching vibration of OH groups. The peaks at 1650 and


1594 cm1 were attributed to the secondary amide C]O bond of
the remaining acetamido groups and the NH bending vibration
of NH2 groups, respectively. The peak at 1420 cm1 can be
assigned to NH deformation vibration in NH2, while the peaks at
1319 and 1152 cm1 were due to the CN stretching vibration. The
remaining peaks at 1081 and 1029 cm1 were attributed to the CO
stretching vibration in COH (Li and Bai, 2005b).
After cross-linking, the spectra of CTPP beads showed some
changes. A new peak was observed at 1253 cm1 indicating the
presence of P]O stretching while the peak at 1640 cm1 were
assigned to P]O of the POH groups found in the tripolyphosphate molecule. The peak at 1529 cm1 can be attributed to NH
3
in CTPP beads. The intensity of the peaks at 1414, 1314 and
1
1153 cm were reduced after the cross-linking process. All of the
peaks related to N atoms were affected after the cross-linking
process. This indicated that that the gelation of CTPP beads was

through the complexation between NH
3 and OP (Lee et al.,
2001; Mi et al., 1999).
3.2. Swelling test of CTPP beads
The percentages of swelling of chitosan-tripolyphosphate beads
in 5% (v/v) acetic acid, distilled water and 0.10 M NaOH solution
were 168.5, 54.9 and 79.9%, respectively. The swelling ability of the
CTPP beads depended on the degree of cross-linking. It is well
known that the polymer chain in chitosan will fall apart and nally
will result in dissolution at lower pH due to the protonation of the
amine groups (Ngah and Fatinathan, 2008). However, CTPP beads
did not dissolve in the acidic solution due to the interchain linkages
in the well cross-linked CTPP network, which leads to less NH2
groups to be protonated (Mi et al., 2003).
3.3. Effect of initial pH, agitation period and adsorbent dosage
The adsorption of Pb(II) and Cu(II) ions was highly dependent on
the initial pH of heavy metal ions solution because pH inuences
the metal speciation and changes the charge in the adsorbent. In
this study, the adsorption experiments were conducted in the
initial pH range of 16. At pH > 6, both Pb(II) and Cu(II) ions
precipitate as an insoluble hydroxides (Gupta and Bhattacharyya,
2008; Khotimchenko et al., 2007; Ngah et al., 2002). This could lead
to inaccurate interpretation of the obtained results. Based on Fig. 2,
it was found that the adsorption capacities of Pb(II) and Cu(II) ions

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

W.S.W. Ngah, S. Fatinathan / Journal of Environmental Management 91 (2010) 958969

Freundlich and Dubinin-Raduskevich isotherm equations were


used in this study to describe the equilibrium of Pb(II) and Cu(II)
ions adsorption onto CTPP beads.
The non-linear form of Langmuir isotherm is expressed as:

(3)

where Ce is the equilibrium concentration of remaining heavy


metal ions in the solution (mg/L); qe is the amount of heavy metal
ions adsorbed per mass unit of adsorbent at equilibrium (mg/g);
Q is the amount of heavy metal ions at complete monolayer (mg/g)
and b, the Langmuir constant related to the afnity of binding sites
(mL/mg) and is a measure of the energy of adsorption. Langmuir
isotherm assumes that the adsorption occurs at specic homogeneous adsorption sites within the adsorbent. Furthermore, it
assumes monolayer adsorption and maximum adsorption occurs
when adsorbed molecules on the surface of the adsorbent form
a saturated layer. All adsorption sites involved are energetically
identical and the intermolecular force decreases as the distance
nlu and Ersoz, 2006; Uysal
from the adsorption surface increases (U
and Ar, 2007).
The Freundlich isotherm expresses adsorption at multilayer and
nlu
on energetically heterogeneous surface (Hasan et al., 2008; U
and Ersoz, 2006). It is an empirical equation suitable for high and
middle-concentration range. However, this isotherm is not suitable
for low concentration range, as the Henrys law is not met. The nonlinear Freundlich isotherm is given as:
1=n

qe KF Ce

(4)

where KF and n are Freundlich constants indicating adsorption


capacity (mg/g) and intensity, respectively.
Meanwhile, the Dubinin-Radushkevitch (D-R) isotherm describes
the adsorption on a single type of uniform pores and can be applied to
distinguish between physical and chemical adsorption. This isotherm
does not assume a homogeneous surface or a constant adsorption
potential. The non-linear D-R isotherm is expressed as:



Q Qm exp k32

(5)

where 3 (Polanyi potential) is [RT ln (1 (1/Ce))], Q is the amount of


solute adsorbed per unit weight of adsorbent (mol/g), k is
a constant related to the adsorption energy (mol2/kJ2) and Qm is the
adsorption capacity (mol/g). The mean free energy (E) of adsorption
per molecule of the adsorbate when it is transferred to the surface
of the solid from the solution was calculated based on the k value
using the equation below:

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

for Pb(II) than Cu(II) ions. Meanwhile, the Langmuir constant


(b) which is related to the afnity of binding sites, showed that the
binding sites had higher afnity for Cu(II) ions. This constant corresponded to the initial slope of the isotherm curve. A high value of
b was reected in the steep initial slope of the adsorption isotherm,
indicating high afnity for the adsorbate (Guibal et al., 1999). On the
contrary, during this study the initial slope was not steep for Cu(II)
ions, thus giving a low value of b. However, this b value was higher
than the value obtained for Pb(II) ions although the adsorption
capacity for Cu(II) ions was lower than the adsorption capacity
obtained for Pb(II) ions. This indicated that CTPP beads had higher
afnity for Cu(II) ions in low concentration of heavy metal ions, but
had the tendency to adsorb more lead (II) ions at higher concentration. According to Volesky (2003), a biosorbents adsorbs better
at low concentration may be inferior at higher concentration, and
vice versa.
Based on the Freundlich isotherm, the adsorption capacity, KF
obtained for Cu(II) ions was much higher than Pb(II) ions. But, for
both metal ions the n value which represented the favorability of the
adsorption, was more than one, indicating that the adsorption
intensity is good (or favorable) at high concentration. The parameter
-4

x 10
4

Experimental data
(Lead (II))

(6)

The E value is useful as can be used to estimate the type of


adsorption process. If the value falls in between 8 and 16 kJ/mol, the
adsorption process can be explained by ion-exchange mechanism.
Meanwhile, if the value is less than 8 kJ/mol, it shows that the
zcan et al., 2005; U
nlu
adsorption process is of a physical nature (O
and Ersoz, 2006).
Fig. 4 showed the plot based on Langmuir and Freundlich
isotherm models and the plot in Fig. 5 was based on the D-R
isotherm model for the adsorption of Pb(II) and Cu(II) ions in
a single metal system. The calculated values of Langmuir, Freundlich and D-R parameters were given in Table 1.
Based on the correlation coefcients, r, the adsorption of Pb(II)
and Cu(II) ions correlated well with all three isotherms studied. The
Q value which represented the maximum adsorption of metal ions
at monolayer based on the Langmuir isotherm, was much higher

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.

W.S.W. Ngah, S. Fatinathan / Journal of Environmental Management 91 (2010) 958969


Table 1
Isotherm constants for adsorption of Pb(II) and Cu(II) ions onto CTPP beads in
a single and binary metal species system.
Isotherm
equation

Single metal species system

Binary 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

3.5. Equilibrium adsorption isotherm (binary metal system)


Fig. 6 showed the non-linear plot for CTPP beads based on
Langmuir and Freundlich isotherm models for the competitive
adsorption in a binary metal system. The calculated values for
Langmuir and Freundlich parameters were summarized in Table 1.
Based on the Langmuir isotherm, the Q value obtained for Cu(II)
ions was almost similar to the value obtained (slightly lower) in the
single metal system. However, for Pb(II) ions, the results were in
contrast whereby the Q value obtained in the binary metal system
was three times lower than the Q value obtained in the single 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

n can be also represented as 1/n value which is related to the degree


of surface heterogeneity. A smaller 1/n value indicates more
heterogeneous surface whereas a value closer to or even one indicates the adsorbent has relatively more homogeneous binding sites
(Chen et al., 2007). The 1/n value obtained for Pb(II) and Cu(II) ions
were 0.56 and 0.31, respectively, indicating that for the adsorption of
Pb(II) and Cu(II) ions, the binding sites involved were more of
heterogeneous.
Alternatively, the mean free energy (E) obtained for Pb(II) and
Cu(II) ions based on the D-R isotherm, were less than 8 kJ/mol,
indicating that physical adsorption was also involved during the
adsorption process.

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

Adsorption capacity, qe (mg/g)

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

W.S.W. Ngah, S. Fatinathan / Journal of Environmental Management 91 (2010) 958969

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)

free energy change (DG ), enthalpy change (DH ) and entropy


change (DS ). These thermodynamic parameters were determined
zcan et al., 2005):
by using the following equation (Ho, 2006; O

lnb

10

t / qt (min g/mg )

Kinetic equation

12

observed in this study, implies greater driving force for adsorption


at high temperature. Meanwhile, the sign of DS indicated the
direction of adsorption system (Crini and Badot, 2008). The DS
obtained for Cu(II) and Pb(II) ions were positive indicating
adsorption. The thermodynamic parameters are actually helpful in
the practical application of the process.

(8)

RT

3.7. Adsorption kinetics

where R is the gas constant (8.314 J/K mol), T is the temperature in


Kelvin and b is the Langmuir constant related to the afnity of
binding sites (mol/L). The plot of ln b versus 1/T yields a straight line
(Fig. 7) from which DH and DS was calculated from the slope and
intercept, respectively. The correlation coefcient, r obtained for
Pb(II) and Cu(II) ions were the 0.98 and 0.99, respectively.
The calculated values of the thermodynamic parameters were
given in Table 2. The DH values found for the adsorption of Pb(II)
and Cu(II) ions were positive due to the endothermic nature of the
adsorption process. The value obtained for the adsorption Cu(II)
ions was much higher than the value obtained for Pb(II) ions.
A negative value of DG indicates the spontaneous nature of the
reaction, while the positive value for DS reects an increase in the
randomness at the solid/solution interface during the adsorption
process (Ngah and Hanaah, 2008). According to Crini and Badot
(2008), a more negative value of DG at higher temperatures, as was

Several adsorption kinetic models such as pseudo-rst and -second


order kinetic models had been used to understand the adsorption
kinetics and the rate limiting step during adsorption process. Some of
the rate determining steps includes diffusion control, chemical reactions and particle diffusion. The pseudo-rst order kinetic model of
Lagergren (Ho and McKay, 1998) is given as:

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.

W.S.W. Ngah, S. Fatinathan / Journal of Environmental Management 91 (2010) 958969

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

adsorption capacity value) obtained based on this model were given


in Table 3. As can be seen in Fig. 8, although the plot was linear, the
qe(theor.) and qe(exp.) values were not in agreement with each other
nlu and
indicating a poor pseudo-rst order kinetic model t (U
Ersoz, 2006). Moreover, this kinetic model does not t well to the
whole range of contact time. It would only be applicable over the
initial stage of the adsorption process (Crini and Badot, 2008).

The pseudo-second order kinetic model can be expressed as:

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

CTPP beads + Pb(II) ions

%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

CTPP beads + Cu(II) ions

%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

W.S.W. Ngah, S. Fatinathan / Journal of Environmental Management 91 (2010) 958969

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.

is the rate constant of pseudo-second order kinetic model (g/mg


min). The straight-line plots of t/qt against t (Fig. 9) were used to
determine the k2 and correlation coefcient, r. The pseudosecond order kinetic model was used to determine whether the
rate limiting step during the adsorption process was chemisorption. This model was more likely to predict the behavior over
whole range of contact time. Based on Table 3, the r values for the
pseudo-second order kinetic model was higher than 0.99.
Moreover, the calculated equilibrium adsorption capacity values,
qe(theor.) were very close to the experimental qe(exp.) values.
Therefore, it was reasonable to conclude that the rate limiting
step during the adsorption of Pb(II) and Cu(II) ions onto CTPP
beads was chemisorption which involved valence forces through
sharing or exchange of electrons between the metal ions and the
adsorbent (Hasan et al., 2008; Septhum et al., 2007).
The adsorption process on a porous adsorbent will generally
have multi-step process. These steps involve the transport of the
adsorbate from the bulk solution, lm diffusion, intraparticle
diffusion in the pores and in the solid phase and nally adsorption on the sites. It is likely that the intraparticle diffusion is
the rate controlling step in a well stirred batch system. The

intraparticle diffusion model is given by the equation (Varma


et al., 2004):

qt kint t 1=2

(11)

where qt is the amount of Pb(II) and Cu(II) ions adsorbed onto


chitosan-tripolyphosphate beads (mg/g) at time t, and kint is the
intraparticle diffusion rate constant (mg/g min1/2). The straightline plots of qt against t1/2 were used to determine the intraparticle diffusion rate, kint and correlation coefcient, r. Based on
Fig. 10, the plot showed multi-linearity correlation which indicated that two steps occurred during the adsorption process. The
rst initial linear portion was followed by a plateau. The initial
linear portion represented the intraparticle diffusion while the
plateau corresponds to equilibrium. The straight line did not pass
the origin indicating that the intraparticle diffusion is not the
zcan et al., 2006). The correlation
sole rate limiting process (O
coefcients obtained (Table 3) showed a good t for both
portions whereby the intraparticle diffusion rate constant, kint,1
represented the rst linear portion while the kint,2 represented
the equilibrium portion.

W.S.W. Ngah, S. Fatinathan / Journal of Environmental Management 91 (2010) 958969

3.8. Desorption study


Desorption of the loaded adsorbents was essential as the
adsorbent can be reused to adsorb heavy metal ions. Desorption
experiments were conducted using HNO3, H2SO4, EDTA and HCl
solutions. The 0.1 M, 0.01 M and 0.001 M EDTA solution gave better
desorption percentage compared with other solutions (HCl, HNO3
and H2SO4). The other three solutions can be used for desorption
experiment, but, the adsorbent either swelled in the medium used
or the adsorption capacity dropped after one cycle. Table 4 showed
the experimental results on the amount of Pb(II) and Cu(II) ions
adsorbed and the percentage of desorption in three consecutive
cycles. It was observed that the adsorption capacities of Pb(II) and
Cu(II) ions dropped slightly after each cycle. The results indicated
that the CTPP beads can be recovered for consecutive uses. CTPP
beads exhibited a good reusability.
3.9. FTIR, SEM-EDX analysis and adsorption mechanism of Pb(II)
and Cu(II) ions on chitosan-tripolyphosphate beads
To study the mechanism of the adsorption process, the changes
in the pH of the heavy metal ions solution was measured during the
adsorption process. It was found that the pH of the solution
decreased after the adsorption of Pb(II) and Cu(II) ions. The
decrease in the pH indicated an increase in the hydronium (H)
ions concentration in the heavy metal ions solution. This showed
that the adsorption of Pb(II) and Cu(II) ions onto CTPP beads could
be governed by ion-exchange mechanism (Prasad and Saxena,
2004). However, further analysis was required as H ions alone
were not enough to play the crucial role in the ion-exchange

967

process. To further evaluate the ion-exchange process, an analysis


was carried out using 0.20 g of CTPP beads mixed with 10 mg/L of
metal ions solution at pH 4.5. The net release of Ca2, Mg2, Na, K
(light metal ions) and H due to the adsorption process was
calculated by subtracting the amount of cations released from
blanks from the amount of cations measured in the efuent after
the adsorption of Pb(II) and Cu(II) ions. The ion-exchange mechanism is given by the Rb/r ratio (Sciban et al., 2006):

Rb=r

h
i
M2
h
i h i h i

i h
i
h
Na
K
H
Ca2 Mg2

2
2
2

(12)

where M2 represented the heavy metal ions in mmol/L and the


concentration of the cations also expressed in mmol/L. According to
Sciban et al. (2006) the Rb/r ratio should be unity if the adsorption
process involved predominantly ion-exchange mechanism while
higher Rb/r ratio means that the sum of cations released was smaller
than the amount of metal ions adsorbed. The Rb/r values obtained for
Pb(II) and Cu(II) ions were 0.3909 and 0.6191, respectively. The
amount of cations released was more than the amount of metal ions
adsorbed. This proved that ion-exchange did not play a predominant
role in the adsorption of Pb(II) and Cu(II) ions onto CTPP beads. In the
work by Lee et al. (2001), a different ion-exchange study was conducted, however, the ndings were almost similar to what had been
found in this work, whereby ion-exchange process was not the
predominant process involved in the adsorption process.
The FTIR spectrum of CTPP beads before and after adsorption
were obtained to identify the possible sites in the beads for the
bonding of Pb(II) and Cu(II) ions. Based on Fig. 11, it was observed

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

W.S.W. Ngah, S. Fatinathan / Journal of Environmental Management 91 (2010) 958969

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.

W.S.W. Ngah, S. Fatinathan / Journal of Environmental Management 91 (2010) 958969

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