Abstract
Physico-chemical investigation on adsorption of congo red, an anionic azo dye by chitosan hydrobeads has been carried out. Adsorption process
has been found to be dependant on temperature with optimum activity at 30 ◦ C. Both ionic interaction as well as physical forces is responsible for
binding of congo red with chitosan. Theoretical correlation of the experimental equilibrium adsorption data for congo red–chitosan hydrobeads
system would be best explained by linearized form of Langmuir isotherm model. The kinetic results follow pseudo second-order rate equation. pH of
the experimental solution influenced congo red adsorption inversely, and ∼20.0% of the dye could be desorbed from the loaded beads by changing
the pH of the solution to alkaline range (∼pH 12.0). Both sodium chloride and sodium dodecyl sulfate significantly influenced the adsorption process.
© 2006 Elsevier B.V. All rights reserved.
Keywords: Chitosan hydrobeads; Congo red; Adsorption; Binding mechanism; Zeta potential
0927-7757/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2006.11.036
S. Chatterjee et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 299 (2007) 146–152 147
Objective of the present investigation is to study the efficacy were taken in a Hitachi model S-415A scanning electron micro-
of chitosan in the form of hydrobeads to remove congo red, scope after coating the beads with gold by elctro-deposition
a member of anionic azo dyes, from its aqueous solution and under vacuum.
to investigate the dye-chitosan interaction during adsorption in
single component system as well as in presence of different 2.5. Mesurement of zeta potential
industrial contaminants.
Dry powder of chitosan beads (0.2 g) was added to 200 ml
2. Materials and methods deionized water and pH of the suspension was adjusted with
0.1 N NaOH or HCl to the desired level. The mixture was
2.1. Chemicals stirred for 24 h and then allowed to settle for 12 h. Supernatant
containing some small particles was used for zeta potential mea-
Chitosan used in the present investigation was prepared from surements in zeta nano series instrument (Malvern Instruments).
shrimp shell by modified Hackmann procedure as described ear-
lier [30]. Average molecular weight and degree of deacetylation 2.6. Equilibrium studies
of this chitosan were 398 kDa and 90.8%, respectively. All other
chemicals were of analytical grade and procured from BDH, Fifty millilitres aqueous solution of congo red (pH ∼6.0, nat-
England. ural) with predetermined initial concentration (1–500 mg/l) was
taken in different 250-ml Erlenmeyer flasks. Swollen chitosan
2.2. Preparation of chitosan beads hydrobeads (1 g) having water content of 96.4% were added to
each flask. The flasks were agitated (50 rpm) at 30 ± 1 ◦ C for
Chitosan hydrobeads were prepared by drop-wise addition 48 h, which is expected to be far beyond the time required to
of 3% chitosan solution (w/v) in 7% AcOH (w/v) to an alka- reach equilibrium. At the end of incubation, beads were sepa-
line coagulating mixture (H2 O: MeOH:NaOH:: 4:5:1, w/w) as rated by filtration through glass wool and concentration of the
described by Mitani et al. [31]. The beads were spherical in dye in the solution was estimated spectrophtometrically. The
shape with an average diameter ∼2.5 mm as determined with same experiment was repeated at two different temperatures
electronic microvernier caliper. Before use, chitosan beads were (viz., 40 ◦ C and 50 ◦ C).
kept for 30 min in water of pH adjusted to that required for
different experimental conditions.
2.7. Adsorption dynamics
2.3. Preparation of congo red solution and analytical
The above experiment was repeated with 500-mg/l congo
measurements
red solution at 30 ◦ C and concentration of dye in the solution
was determined at different time intervals. Each data point was
Stock solution of congo red (1 g/l) was prepared in deion-
obtained from individual flask and therefore no correction was
ized water and desired concentrations of the dye were obtained
necessary due to withdrawal of sampling volume [32].
by diluting the same with water. Calibration curve of congo
red was prepared by measuring absorbance of different prede-
termined concentrations of the samples at λmax 497 nm using 2.8. Influence of pH
UV–vis spectrophotometer (Varian Carry 50). Concentration of
dye in the experimental solution was calculated from the linear Influence of pH on the adsorption process was studied over a
regression equation (OD = 0.046 × concentration of dye in mg/l) range 3.0 to 12.0. Other conditions were the same as described
of the calibration curve. Adsorption of dye by 1 g of chitosan in in kinetic study, and dye concentration was measured after 10 h.
the form of hydrobeads was determined by the following mass
balance equation. 2.9. Influence of sodium chloride, sodium dodecyl sulphate
and desorption studies
(Ci − Cf ) × V
q=
1000 × W Influence of sodium chloride and sodium dodecyl sulphate
where q represents the amount of dye adsorbed, Ci and Cf are the on dye adsorption was studied in similar way as described in pH
initial and final concentration (mg/ml) of dye after adsorption. V experiment. Congo red solution contained either sodium chlo-
is the volume (ml) of experimental solution and W is the weight ride (0.5 M and 1 M) or sodium dodecyl sulfate (1% and 2%,
(g) of chitosan in form of hydrobeads. w/v); pH of the solution was maintained at 6.0.
After kinetic experiment, dye-loaded chitosan hydrobeads
2.4. Scanning electron micrograph (SEM) studies (1 g) obtained by filtration and washing with water through glass
wool were taken in different 250-ml Erlenmeyer flasks. Fifty
Chitosan beads before and after adsorption of congo red were millilitres water having pH adjusted to 8–12 or 50 ml ethanol,
dried initially at 70 ◦ C for 48 h and finally for 24 h after increas- methanol, propanol, ether, acetone was added to each flask. The
ing the temperature to 105 ◦ C. Beads were kept in a desiccator flasks were agitated (50 rpm) for 24 h at 30 ◦ C and concentration
until use. The scanning electron microscope (SEM) photographs of the dye in the supernatant was estimated.
148 S. Chatterjee et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 299 (2007) 146–152
Adsorption of congo red from its aqueous solution by chi- Adsorption isotherm model describes how adsorbate interacts
tosan hydrobeads at different temperature is presented in Fig. 2. with adsorbents, and comprehensive understanding of the nature
S. Chatterjee et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 299 (2007) 146–152 149
Table 2 Table 3
Constants of Freundlich’s and Langmuir’s equation Constants of different rate models
Temperature (◦ C) Constant Region of the Freundlich’s curve Experimental
Co (mg/l) 200.0
Lower Middle Higher Ce (mg/l) 133.34
Freundlich’s equation qe (exp) (mg/g) 92.59
KF 7.79 11.39 66.69 First-order
20
1/n 0.734 0.75 0.06 R 0.974
KF 10.26 16.64 72.18 k1 7.5 × 10−3
30 qe (cal) (mg/g) 65.77
1/n 0.600 0.703 0.045
KF 5.13 8.15 66.27 Second-order
40 R 0.998
1/n 0.732 1.23 0.903
k2 1.64 × 10−4
KF 3.75 4.42 58.56 qe (cal) (mg/g) 99.0
50
1/n 0.832 0.873 0.048
Fig. 6. Cogo red–chitosan interaction: (i) ionic interaction (involves when pH of experimental solution is below 6.4), (ii) hydrogen bonding between hydroxyl group
of chitosan and electronegative residues in the dye molecule, and (iii) Yosida H- bonding between hydroxyl group of chitosan and aromatic residue in dye.
8.0 15.4
10.0 18.0
3.6. Effect of additives on adsorption and pH on desorption
11.0 19.0
phenomena 12.0 21.2
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