Removal of Cationic Dyes by Poly (Acrylamide-Co-Acrylic Acid) Hydrogels in Aqueous Solutions
Removal of Cationic Dyes by Poly (Acrylamide-Co-Acrylic Acid) Hydrogels in Aqueous Solutions
Removal of Cationic Dyes by Poly (Acrylamide-Co-Acrylic Acid) Hydrogels in Aqueous Solutions
Abstract
Poly(acrylamide-co-acrylic acid (poly(AAm-co-AAc)) hydrogels prepared by irradiating with g-radiation were used in experiments on
swelling, diffusion, and uptake of some cationic dyes such as Safranine-O (SO) and Magenta (M). Poly(AAm-co-AAc) hydrogels
irradiated at 8.0 kGy have been used for swelling and diffusion studies in water and cationic dye solutions. The maximum swellings in
water, and SO, and M solutions observed are 2700%, 3500%, and 4000%, respectively. Diffusions of water and cationic dyes within
hydrogels have been found to be non-Fickian in character. Adsorption of the cationic dyes onto poly(AAm-co-AAc) hydrogels is studied
by the batch adsorption technique. The adsorption type was found Langmuir type in the Giles classification system. The moles of
adsorbed dye for SO and M per repeating unit in hydrogel (binding ratio, r) have been calculated as 3834 106 and 1323 106,
respectively. These results show that poly(AAm-co-AAc) hydrogels can be used as adsorbent for water pollutants such as cationic dyes.
r 2007 Elsevier Ltd. All rights reserved.
Keywords: Hydrogel; Gamma-irradiation; Poly(acrylamide-co-acrylic acid); Swelling; Adsorption; Diffusion; Cationic dyes.
0969-806X/$ - see front matter r 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.radphyschem.2007.08.006
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effect of poly(AAm-co-AAc) hydrogels on cationic dyes from the absorbance of the solutions. Swollen hydrogels
indicates the very good potential of this procedure in removed from the water bath at regular intervals were
achieving the desired objective. dried superficially with filter paper, weighed, and placed in
the same bath again. The measurements were continued
2. Experimental until a constant weight was reached for each sample.
2.1. Materials
2.4. Adsorption studies
Acrylamide (AAm) and acrylic acid (AAc) monomers
Adsorption of the dyes from aqueous solutions was
used in this study were obtained from BDH. Safranine-O
investigated in continuous adsorption equilibrium experi-
(SO) and Basic Magenta (M) dyes were supplied from
ments. Effects of initial concentration and content of AAc
Allied Chemical. Some properties of monomers and dyes
in AAm/AAc monomer mixtures to prepare hydrogels on
are listed in Table 1.
adsorption rate and capacity were studied. The cationic dye
solutions were prepared in the concentration ranges of
2.2. Preparation of hydrogels
5–60 mg dm3 for SO and M. Approximately 0.05 mg of
poly(AAm-co-AAc)1–3 hydrogels, which are of different
The solutions of monomers of AAm and AAc were
compositions, were transferred into 50 mL of dye solutions
prepared in three different compositions (AAm/AAc mole
at 0.1 ionic strength and agitated magnetically at moderate
ratios, 30/70, 20/80, and 15/85). These solutions were
rpm and allowed to be in equilibrium for 48 h at 25 1C.
placed in polyvinylchloride straws of 3 mm diameter and
After adsorption, the poly(AAm-co-AAc) hydrogels were
irradiated in air at ambient temperature in a Gammacell-
removed from the adsorption medium. The concentration
220 type g-irradiator. The percent conversion was deter-
of the dyes in aqueous phases were measured by a
mined gravimetrically. Dose of 8.0 kGy was applied at a
UV–visible spectrophotometer after the desired treatment
fixed dose rate of 0.16 kGy h1. Hydrogels obtained in long
period.
cylindirical shapes were cut, washed with distilled water for
removal of unreacted monomers, and dried in air and in
vacuum, and stored for later evaluations. Poly(AAm-co- 3. Results and discussion
AAc)1, poly(AAm-co-AAc)2, and poly(AAm-co-AAc)3
were prepared using three different compositions of 3.1. Swelling and diffusion
poly(AAm-co-AAc) hydrogels, which were obtained by
using AAm/AAc monomer mixtures at three different mole The swelling of poly(AAm-co-AAc) hydrogels in water
percents, which are 30/70, 20/80, and 15/85, respectively. and in aqueous solutions of 50 mg dm3 SO and M was
calculated from the following relation (Buckley and Berger,
2.3. Swelling and diffusion studies 1962; Güven and S- en, 1990):
% Swelling ¼ ½ðmt m0 Þ=m0 100, (1)
Dried poly(AAm-co-AAc)1–3 hydrogels irradiated at
8.0 kGy were left to swell in distilled water ionic strength where mt is the mass of swollen gel at time t, and m0 is the
I ¼ 0.1, 50 mg dm3 of SO and M solutions each at 25 1C initial mass of the dry gel. The swelling curves of
to measure the parameters of diffusion and swelling. The poly(AAm-co-AAc)3 hydrogel in distilled water and
concentrations of dyes in the solutions were determined solutions of SO and M are shown in Fig. 1. Fig. 1 shows
Table 1
Chemical formula of monomers and dyes
+
NH2
H H H3C N CH3 Cl-
C C
H CONH2
Acrylamide
H2N N+ NH2
Cl- C
H H
C C
H COOH H2N NH2
Acrylic Acid Safranine-O Basic Magenta
-1 -1
Molar mass (gmol ): 350 Molar mass (gmol ): 338
max(nm): 517 max(nm): 539
Color Index (CI):50240 Color Index (CI): 42500
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that maximum swellings occur with water (2700%), SO In this equation, F denotes the amount of solvent
(3500%), M (4000%). fraction at time t. k is a constant incorporating character-
The following equation was used to determine the nature istics of the macromolecular network system and the
of diffusion of water and aqueous solutions of dyes into penetrant, and n is the diffusional exponent, which is
poly(AAm-co-AAc) hydrogels (Buckley and Berger, 1962): indicative of the transport mechanism. This equation was
applied to the initial stages of swelling, and plots of ln(F)
F ¼ ktn . (2) versus ln(t) are presented in Fig. 2. The exponents (n) and k
were calculated from the slope and intercept of the lines
and the results are given in Table 2.
4000 For hydrogel characterization, the diffusion coefficient
can be calculated by various methods. The short time
approximation method is used for calculation of diffusion
3000 coefficients of poly(AAm-co-AAc) hydrogels. The short
% Swelling
-1.5 0.15
-2.0
-2.5 0.10
lnF
-3.0
H 2O
-3.5 H2O 0.05 Magenta
Magenta Safranine-O
Safranine-O
-4.0
-4.5 0.00
2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 2 4 6 8 10 12
lnt t1/2
Fig. 2. Plots of lnF versus lnt of poly(AAm-co-AAc)3 hydrogels in water Fig. 3. Plots of F versus t 12 of poly(AAm-co-AAc)3 hydrogels in water
and in 50 mg dm3 Safranine-O and Magenta solutions at pH 7.0 and and in 50 mg dm3 Safranine-O and Magenta solutions at pH 7.0 and
25 1C. 25 1C.
Table 2
Swelling and diffusion parameters of poly(AAm-co-AAc) hydrogels in water and Safranine-O and Magenta solutions at pH 7.0 and 25 1C
Water 0.35 0.76 2.48 0.40 0.70 2.22 0.39 0.70 3.05
SO 0.32 0.83 2.95 0.24 0.85 2.44 0.35 0.85 3.13
M 0.36 0.79 2.98 0.33 0.88 2.89 0.38 0.87 3.63
D: cm2 min1.
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of the lines of F versus t 1/2 give the diffusion coefficients In an adsorption system at equilibrium, the total solute
that are listed for three different hydrogels in Table 2. concentration (Ct, mol dm3) is
Diffusion coefficients are important parameters for the
Ct ¼ Cb þ Ce, (5)
penetration of some chemical species into polymeric
systems. The n values in this table range between where Cb is the equilibrium mole number of the solute on
0.70 and 0.87. The diffusion of aqueous solutions of the adsorbent per dm3 solution (bound solute concentra-
dyes into poly(AAm-co-AAc) hydrogels was taken as a tion) and Ce is the equilibrium concentration of the solute
non-Fickian character. Penetration of solvent into hydro- in the solution in mol dm3 (free solute concentration). The
gel is more easy in aqueous solutions of SO and M, since value of the bound concentration may be obtained by using
there is a hydrophilic interaction with these dyes and Eq. (5). For a fixed free solute concentration, Cb is
hydrogel. proportional to the polymer concentration on the binding
The equilibrium swelling of hydrogels is high system; the amount bound can therefore be conveniently
(3500–4000%) in aqueous solutions of SO and M, which expressed as the binding ratio, r, defined by
are cationic dyes, but low (2700%) in water. The dyes r ¼ C b =P. (6)
contain unpaired electrons of N. These atoms behave like a 3
hydrophilic group and hydrogen bonds with water. Thus, Thus, with Cb in mol dm and P in base mol (moles of
the swelling of poly(AAm-co-AAc) hydrogels increases as monomer units) per dm3 solution, r represents the average
the dyes bring water into the gels. At the end of these number of molecules of solute bound to each monomer
evaluations, the hydrogels in the aqueous solutions were unit at that free solute concentration (Karadağ and
swollen in the following order: M4SO4water. The Saraydın, 1996).
number that determines the type of diffusion n was found
to be over 0.70 in the aqueous dye solutions. Hence, the 3.3. Effect of concentration of dye solution on adsorption
diffusion of water is not easier than the other molecules.
Non-Fickian transport is observed as the pH of the To determine the effect of concentration of dye solution
surrounding fluid increases above pKa (Ende and Peppas, on adsorption, plots of the binding ratio (r) against the free
1996). For cylindirical hydrogels, in Non-Fickian type concentrations of the dyes in solutions (C, m mol dye dm3)
diffusion, n is between 0.45 and 1.00. Hence, the diffusion are shown in Figs. 4 and 5 for SO and M at pH 7 and 25 1C
into poly(AAm-co-AAc) hydrogels was taken to be as a and 0.1 ionic strength, respectively. These figures show
non-Fickian. It can be said that for higher swelling values that adsorptions of dyes within different compositions
of the hydrogels, the transport of water into the hydrogels of poly(AAm-co-AAc) hydrogels correspond to type-S
becomes more non-Fickian. This is generally explained as a adsorption isotherms in the Giles classification system
consequence of the slow relaxation rate of the polymer for adsorption of a solute from its solution (Giles et al.,
matrix. The cationic dye molecules interact with the 1960).
carboxyl groups of acrylic acid in poly(AAm-co-AAc) In the S curves, the initial direction of curvature shows
hydrogel, so the hydrophilic groups of the poly(AAm-co- that adsorption becomes stronger as concentration in-
AAc) are not bonded with water. Thus, the swelling of the creases. In practice, the S curve usually appears when
hydrogel increased in the aqueous solutions of cationic three conditions are fulfilled: the solute molecule (a) is
dyes.
rx106 (mol dye/repeating unit in hydrogel)
4000
3000
To observe the adsorption of SO and M, poly(AAm-co-
AAc)3 hydrogels were placed in aqueous solutions of 2500
cationic dyes such as SO and M. The amount of adsorption
2000
per unit mass of the poly(AAm/AAc) hydrogels was
evaluated by using the following equation: 1500
500 Safranine-O
where, qe is the amount of dye adsorbed on unit dry mass
of the poly(AAm/AAc) hydrogels (mg g1), C0 and Ce are 0
0 5 10 15 20 25 30 35 40
the concentrations of the dyes in the initial solution and the
Cex106 (mol dye dm-3)
aqueous phase after treatment for a certain period of time,
respectively (mg dm3), V is the volume of the aqueous Fig. 4. The variations of binding ratio (r) of poly(AAm-co-AAc)3
phase (L) and W is the amount of dry poly(AAm/AAc) hydrogel–dye systems with the equilibrium concentration in Safranine-O
hydrogels (g). solutions at pH 7.0 and 25 1C.
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4000
maximum % swelling in distilled water.
3500 Diffusion of water and dye solutions within hydrogels
Magenta was found to be of a non-Fickian character.
3000 Safranine-O Diffusion coefficients were calculated for poly(AAm-co-
2500 AAc) hydrogel in water, SO, and M solutions.
Initial swelling rate increased with increased pH and
2000
AAc content in hydrogel.
1500 Adsorption capacity of poly(AAm-co-AAc) hydrogels
was changed with amount of AAc, and adsorption
1000
isotherms of poly(AAm-co-AAc) hydrogels were S type.
500
0
0 20 40 60 80
% AAc References
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