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Abstract
The adsorption of Cu(II) ions from aqueous solution by chitosan and chitosan/PVA beads was studied in a batch adsorption system.
Chitosan solution was blended with poly(vinyl alcohol) (PVA) in order to obtain sorbents that are insoluble in aqueous acidic and
basic solution. The adsorption capacities and rates of Cu(II) ions onto chitosan and chitosan/PVA beads were evaluated. The Langmuir,
Freundlich and BET adsorption models were applied to describe the isotherms and isotherm constants. Adsorption isothermal data could
be well interpreted by the Langmuir model. The kinetic experimental data properly correlated with the second-order kinetic model, which
indicates that the chemical sorption is the rate-limiting step. The Cu(II) ions can be removed from the chitosan and chitosan/PVA beads
rapidly by treatment with an aqueous EDTA solution. Results also showed that chitosan and chitosan/PVA beads are favourable adsorbers.
2004 Elsevier B.V. All rights reserved.
Keywords: Chitosan beads; Chitosan/PVA beads; Adsorption capacities; Adsorption rates; Adsorption isotherm; Desorption
0141-8130/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.ijbiomac.2004.03.001
156 W.S. Wan Ngah et al. / International Journal of Biological Macromolecules 34 (2004) 155161
ical stability of the biosorbents in such acidic solutions pore structure (hereafter called chitosan beads). The beads
but cross-linking has been found decreases the adsorption were then ground by using a laboratory jar mill and sieved
capacity of chitosan [2]. to a constant size (<250 m) before use.
In recent years, polymer blending has become one of the
effective methods for providing new desirable polymeric 2.3. Preparation of chitosan/PVA beads
materials for practical applications. Chitosan blended with
poly(vinyl alcohol) (PVA) has been reported to have good An 8.0 g amount of chitosan flakes was dissolved in
mechanical and chemical properties [27]. PVA is a nontoxic, 100 ml of 5% (v/v) acetic acid solution. The chitosan solu-
water soluble, biocompatible and biodegradable synthetic tion was left 24 h at room temperature. PVA in an amount
polymer, which offers good tensile strength, flexibility and of 6.0 g was dissolved in 100 ml of distilled water in a
barrier properties to oxygen and aroma [28,29]. As a topic beaker and agitated on a magnetic stirrer at about 500 rpm
of great interest, PVA has widely been used in biomedi- at 70 C for 5 h. The two solutions were then blended to-
cal and biochemical applications [30,31]. Chitosan/PVA has gether with stirring on the magnetic stirrer at about 500 rpm
been used in the removal of lead ions from aqueous solution at 70 C for 2 h and followed by another 48 h under room
[27]. However, the adsorption properties and mechanisms of temperature to obtain a homogeneous gel blend. The gel
the chitosan/PVA blend for metal removal have been seldom blend was sprayed into a precipitation bath containing
studied. 500 ml of 0.5 M NaOH, which neutralized the acetic acid
In this study, the equilibria of adsorption Cu(II) ion onto within the chitosan gel and thereby coagulated the chitosan
chitosan and chitosan/PVA beads from water were inves- gel to spherical uniform chitosan gel beads. The aqueous
tigated in detail. The influence of experimental conditions NaOH solution was agitated at about 300 rpm. Freshly
such as pH, agitation period, agitation rate and initial con- prepared wet chitosan/PVA gel beads were filtered and in-
centration will be studied. The Langmuir, Freundlich and tensively washed and finally air-dried. The newly formed
BET equations were used to fit the equilibrium isotherm. The blended beads (hereafter called chitosan/PVA beads) were
adsorption rates were determined quantitatively and com- then ground by using a laboratory jar mill and sieved to
pared by the first- and second-order kinetic model. This in- a constant size (<250 m) before use. The chitosan/PVA
formation will be useful for further applications of system beads (as shown in Fig. 1) obtained were confirmed by a
design in the treatment of practical waste effluents. Perkin-Elmer FT-IR System 2000 Model spectrometer.
2.1. Materials Chitosan and chitosan/PVA beads were tested with regard
to their solubility in each of 5% (v/v) acetic acid, distilled
Samples of chitosan flakes with average molecular weight water and 0.1 M sodium hydroxide solution by adding 0.1 g
105 106 and with a deacetylation percentage of approxi- of chitosan and chitosan/PVA beads in each of the dilute
mately 55.9% (defined by an IR method), prepared from acid, distilled water and dilute alkaline solution for a period
shells of prawns were kindly donated from Chitin-Chitosan of 24 h with stirring at room temperature.
Research Centre, Universiti Kebangsaan Malaysia, Bangi. The swelling studies of chitosan and chitosan/PVA beads
PVA (98% hydrolysed, average molecular weight 22,000) were carried out in dilute acid, distilled water and dilute
purchased from BDH was analytical-reagent grade. All the alkaline solution at room temperature for a period of 24 h.
reagents used were of analytical-reagent grade. Doubly dis- The percentage of swelling of these beads were calculated
tilled water used to prepare all the solutions. by using the following equation:
Ws W
2.2. Preparation of chitosan beads percentage of swelling = 100 (1)
W
Chitosan beads were prepared according to the same pro- where Ws is the weight of swollen beads (g) and W is the
cedure described previously [2,6]. Chitosan solution was weight of dry beads (g).
prepared by dissolving 2.0 g of chitosan flakes into 60 ml
of 5% (v/v) acetic acid solution. The chitosan solution was 2.5. Batch adsorption experiments
sprayed into a precipitation bath containing 500 ml of 0.5 M
NaOH, which neutralized the acetic acid within the chitosan Stock solutions (1000 ppm) of Cu(II) ions was prepared
gel and thereby coagulated the chitosan gel to spherical uni- by using analytical-reagent grade Cu metal (BDH). The
form chitosan gel beads. A magnetic stirrer used to stir the stock solution was then diluted to give standard solutions of
aqueous NaOH solution. The wet chitosan gel beads were appropriate concentrations. Batch adsorption experiments
extensively rinsed with distilled water to remove any NaOH, were conducted in 250 ml beakers and equilibrated using a
filtered and finally air-dried to remove the water from the magnetic stirrer. Then 50 ml aliquots of these standard solu-
W.S. Wan Ngah et al. / International Journal of Biological Macromolecules 34 (2004) 155161 157
CH2 CH
n
O
H
Intermolecular
HOH2C
HOH2C O
O
O
O
O NH2
NH2 HO
HO
Intermolecular
H
Intramolecular
O
CH2 CH
n
tions were placed in 250 ml beakers and added with 0.01 g riod of 30 min and agitation rate was fixed at 500 rpm.
of chitosan or chitosan/PVA beads. After filtration, the con- Cu(II)-loaded chitosan and chitosan/PVA beads were col-
centration of Cu(II) ions in supernatant was analysed at lected, gently washed with distilled water to remove any
wavelength 325 nm using an atomic absorption spectropho- unadsorbed Cu(II). The amount of Cu(II) adsorbed per
tometer (Perkin-Elmer 3100 Model). The effect of Cu(II) gram of chitosan and chitosan/PVA were determined by
adsorption was studied in pH range 16. The pH of the using the supernatant Cu(II) concentration. The chitosan
initial solution was adjusted to the required pH value us- and chitosan/PVA beads were agitated with 50 ml of EDTA
ing either 0.1 M HCl or 0.1 M NaOH. Chitosan and chi- and HNO3 of various concentration (102 105 M) and the
tosan/PVA beads were equilibrated at the particular pH for percentage of desorption of Cu(II) was calculated from the
about 30 min at 500 rpm and at an initial Cu(II) concentra- following expression:
tion of 5 ppm. The effect of agitation period and agitation mr
percentage of desorption = 100% (3)
rate also studied to determined the optimum condition for m0
adsorption of Cu(II) ions.
where mr is the amount of Cu(II) ions desorbed (mg) and
Adsorption equilibrium studies were conducted at opti-
m0 is the amount of Cu(II) ions adsorbed (mg).
mum condition using a contact time of 50 min at pH 6 for
chitosan whereas for chitosan/PVA beads, a contact time of
70 min at pH 6. Isotherm studies were conducted with a
3. Results and discussion
constant chitosan and chitosan/PVA beads weight (0.01 g)
and varying initial concentration of Cu(II) in the range of
3.1. Solubility and swelling test of chitosan and
014 ppm. The amount of adsorption was calculated based
chitosan/PVA beads
on the difference of Cu(II) concentration in aqueous solu-
tions before and after adsorption, the volume of aqueous so-
It was shown that after blending with PVA, the blended
lution (50 ml) and the weight of the beads (0.01 g) according
chitosan was found to be insoluble in acidic and alkaline me-
to:
dia as well as distilled water (Table 1). It is well known that
(C0 Ce )V chitosan is soluble in dilute organic acid solutions. This due
adsorption capacity (qe ) = (2)
W to each of the accessible amine groups is protonated in acid
where C0 is the initial Cu(II) concentration (ppm), Ce is media. Table 2 reports the percentage of swelling behaviour
the final or equilibrium Cu(II) concentration (ppm), V is the of chitosan and chitosan/PVA beads. A convenient proof of
volume of the Cu(II) solution (ml) and W is the weight of blending is the swelling behaviour of the blended chitosan
the chitosan and chitosan/PVA beads (g). beads in dilute acetic acid. This may suggests that blending
For batch kinetic studies, 0.01 g chitosan and chi- treatment should be necessary to reinforce the chemical sta-
tosan/PVA beads were equilibrated at optimum condition
as mentioned earlier. The beads and Cu(II) solution (5 ppm) Table 1
were placed in 250 ml beakers and stirred by a magnetic Solubility effect of chitosan and chitosan/PVA beads
stirrer. Every time, after filtration the concentration of Cu(II) Beads Solubility effect
in supernatant were determined. 5% acetic acid Distilled water 0.10 M NaOH
For the desorption studies, 0.01 g of chitosan and chi-
tosan/PVA beads were loaded with Cu(II) using 50 ml Chitosan Soluble Insoluble Insoluble
Chitosan/PVA Insoluble Insoluble Insoluble
of 5 ppm Cu(II) solution at optimum pH, agitation pe-
158 W.S. Wan Ngah et al. / International Journal of Biological Macromolecules 34 (2004) 155161
Table 2 25
Swelling behaviour of chitosan and chitosan/PVA beads
Beads Swelling (%) 20
5% acetic acid Distilled water 0.10 M NaOH
qCu(II) (mg g )
-1
15
Chitosan Soluble 57.1 42.9 Chitosan/PVA
Chitosan/PVA 12.4 7.8 6.5 Chitosan
10
In this study, knowledge of pH is important because the Fig. 3. Effect of agitation period on the adsorption of Cu(II) on chitosan
pH of solution strongly affects the adsorption capacity of the and chitosan/PVA beads.
chitosan and chitosan/PVA beads. Fig. 2 shows the effect of
pH on the adsorption of Cu(II) by chitosan and chitosan/PVA chitosan/PVA beads. The adsorption of Cu(II) increases with
beads. The maximum adsorption of Cu(II) on chitosan and agitation period and attains equilibrium at about 50 min for
chitosan/PVA beads was found at pH 6.0, respectively. At chitosan and 70 min for chitosan/PVA beads for an initial
pH values higher than 7, Cu(II) precipitation occurred si- Cu(II) concentration of 5 ppm. It shows that the adsorption
multaneously. pH 6 was chosen for the adsorption of Cu(II) of Cu(II) remained constant, implying equilibrium has been
ions to avoid the formation of Cu(II) hydroxide which will reached.
affect the adsorption by the beads. The adsorption increases
(i.e., the difference in absorbance increases) with increasing 3.4. Effect of agitation rate
pH of the solution. This could be explained by the fact that
at low pH, more protons will available to protonate amine Fig. 4 shows the effect of agitation rate on the adsorp-
groups to form groups NH3 + , reducing the number of bind- tion of Cu(II) by chitosan and chitosan/PVA beads. The ad-
ing sites for the adsorption of Cu(II). While, at higher pH sorption of Cu(II) increases with agitation rate and attains a
adsorption of Cu(II) increases due to the inhibitory effect of constant value at about 500 rpm for both beads. The agita-
H+ decreased with the increase in pH. tion rate of 500 rpm was chosen because the agitation above
this has little effect on adsorption rate. Therefore, the opti-
3.3. Effect of agitation period mum agitation rate for adsorption of Cu(II) was 500 rpm for
chitosan and chitosan/PVA beads.
Fig. 3 shows the effect of agitation period on the adsorp-
tion of Cu(II) by chitosan and chitosan/PVA beads. The op- 3.5. Adsorption equilibrium
timum period for the adsorption of Cu(II) on chitosan and
chitosan/PVA can be observed by looking at the difference The equilibrium adsorption of Cu(II) on the chitosan and
in absorbance of Cu(II) solution after adding chitosan and chitosan/PVA beads as a function of the initial concentra-
30 25
25 20
qCu(II) (mg g )
qCu(II) (mg g )
20
-1
-1
15
Chitosan/PVA Chitosan/PVA
15
Chitosan Chitosan
10
10
5 5
0 0
0 2 4 6 8 0 200 400 600 800
pH Agitation Rate (rpm)
Fig. 2. Effect of pH on the adsorption of Cu(II) on chitosan and chi- Fig. 4. Effect of agitation rate on the adsorption of Cu(II) on chitosan
tosan/PVA beads. and chitosan/PVA beads.
W.S. Wan Ngah et al. / International Journal of Biological Macromolecules 34 (2004) 155161 159
50 Table 4
RL values based on the Langmuir equation
Chitosan Chitosan/PVA
qe (mg g )
-1
30
Chitosan/PVA 4 0.1007 0.1097
Chitosan 6 0.0695 0.0759
20
8 0.0530 0.0580
10 0.0429 0.0470
10 12 0.0360 0.0395
0
0 2 4 6 8 The BET equation is given by:
Ce 1 B1 Ce
Ce (ppm) = + (6)
(Ci Ce )(qe ) BQ BQ Ci
Fig. 5. Equilibrium adsorption of Cu(II) from aqueous solutions using
chitosan and chitosan/PVA beads. where Q is the maximum adsorption at monolayer (mg g1 ),
Ce is the equilibrium concentration of Cu(II) (ppm), Ci is
the saturation concentration of the solute (ppm), qe is the
tion of Cu(II) is shown in Fig. 5. There was a gradual in- amount of Cu(II) adsorbed per unit weight of chitosan and
crease of adsorption for both Cu(II) ions until an equilibrium chitosan/PVA beads at equilibrium concentration (mg g1 )
was attained. An equilibrium concentration of Cu(II) ions and B is the BET constant expressive of the energy of inter-
was reached at about 5 ppm for chitosan and chitosan/PVA action with surface.
beads. Adsorption isotherm is important to describe how The calculated results of the Langmuir, Freundlich and
solutes interact with adsorbent. The Langmuir, Freundlich BET isotherm constants are given in Table 3. It is found that
and BET models are often used to describe equilibrium the adsorption of Cu(II) on the chitosan and chitosan/PVA
sorption isotherms. The most widely used Langmuir equa- beads were correlated well (R > 0.99) with the Langmuir
tion, which is valid for monolayer sorption on to a sur- equation as compared to Freundlich and BET equation under
face with a finite number of identical sites and is given the concentration range studied.
by: The essential features of a Langmuir isotherm can be ex-
Ce Ce 1 pressed in terms of a dimensionless constant separation fac-
= + (4) tor or equilibrium parameter, RL that is used to predict if an
qe Q Qb
adsorption system is favourable or unfavourable. The
where Q is the maximum adsorption at monolayer (mg g1 ), separation factor, RL is defined by:
Ce is the equilibrium concentration of Cu(II) (ppm), qe is the 1
amount of Cu(II) adsorbed per unit weight of chitosan and RL = (7)
1 + bC0
chitosan/PVA beads at equilibrium concentration (mg g1 )
and b is the Langmuir constant related to the affinity of where C0 is the initial Cu(II) concentration (ppm) and b is
binding sites (ml mg1 ) and is a measure of the energy of the Langmuir adsorption equilibrium constant (ml mg1 ).
adsorption. A linearized plot of Ce /qe against Ce gives Q Table 4 lists the calculated results. Based on the effect of
and b. separation factor on isotherm shape, the RL values are in the
The widely used empirical Freundlich equation based on range of 0 < RL < 1, which indicates that the adsorption of
sorption on a heterogeneous surface is given by: Cu(II) on chitosan and chitosan/PVA beads are favourable.
Thus, chitosan and chitosan/PVA beads are favourable ad-
1
log qe = log KF + log Ce (5) sorbers. The mechanism of ion adsorption on porous adsor-
n bents may involve three steps: (i) diffusion of the ions to
where KF and n are Freundlich constants indicating sorption the external surface of adsorbent; (ii) diffusion of ions into
capacity (mg g1 ) and intensity, respectively. KF and n can the pores of adsorbents; (iii) adsorption of the ions on the
be determined from linear plot of log qe against log Ce . internal surface of adsorbent.
Table 3
Langmuir, Freundlich and BET isotherm constants and correlation coefficients
Beads Langmuir Freundlich BET
50 2.00
40 1.60
t/qt (min g mg )
-1
qt (mg g )
30 1.20
-1
Chitosan/PVA Chitosan/PVA
Chitosan Chitosan
20 0.80
10 0.40
0 0.00
0 20 40 60 0 20 40 60
t (min) t (min)
Fig. 6. Time profiles of Cu(II) adsorption using chitosan and chitosan/PVA Fig. 7. Test of second-order equation for adsorption of Cu(II) using
beads. chitosan and chitosan/PVA beads.
1.60
3.6. Kinetics of adsorption
1.20
Fig. 6 shows the time profiles of Cu(II) adsorption onto
log (qe - q t )
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