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International Journal of Chemical and Environmental Engineering
Abstract
Novel terpolymer resin involving phthalic acid and urea with formaldehyde (PUF) was synthesized by condensation
polymerization in glacial acetic acid medium and proved to be a selective chelation ion-exchange terpolymer for certain
metals. The resin was characterized by FTIR and 1H NMR spectroscopy. Based on the spectral data, the structure of the
resin was proposed. The average molecular weight of the terpolymer resin was determined by gel permeation
chromatography (GPC). The morphology of the terpolymer was established by scanning electron microscopy (SEM). In
addition, the physicochemical parameters were also determined for the terpolymer resin. A batch equilibrium method
was employed to study the selectivity and sorption capacity of the resin towards certain divalent metal ions such as
Pb2+, Zn2+, Cu2+, Ni2+, Ba2+, Co2+ and Mn2+ in various electrolyte concentrations, wide pH ranges and different
time intervals. Hence the resin can be used to recover certain metal ions from waste solutions and used for the purpose of
purification of waste water and removal of iron from boiler water. The ion-exchange capacity of the metal ions has also
been compared with other commercial resins.
COOH
its chelation ion-exchange properties by batch equilibrium NH2
method for Pb2+, Zn2+, Cu2+, Mg2+ and Ba2+ ions [13]. + + CH2 O
In this research article, the synthesis of terpolymer C
H 2N O
involving phthalic acid and urea with formaldehyde is COOH
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Metal Sorption Studies of a Novel Terpolymer Resin
2.6 Evaluation of the Distribution of Metal Ions at Table I. Phyicochemical Properties of PUF resin
Different pH Properties Value (SD)
The distribution of each of the metal ions at various
pH ranging from 3 to 5.5 between the polymer phase and Moisture (%) 4.1 ± 0.25
the aqueous phase were determined in the presence of 1 Solid (%) 95.9 ± 0.45
M KNO3 at 25 ºC. The distribution ratio KD, may be True density (dry resin) g/cm3 1.47 ± 0.03
defined as Void volume fraction 0.887 ± 0.015
Sodium exchange capacity ( mmol/g 9.19 ± 0.25
KD = Weight (in mg) of metal ions taken up by 1 g of the dry resin)
resin sample / Weight (in mg) of metal ions present in 1
mL of the solution
2.7 Evaluation of Rate of Metal Ion Uptake
The time required for attaining the state of
equilibrium under the experimental conditions was
evaluated by a series of experiments carried out to
determine the amount of metal ion adsorbed by the
terpolymer at specific time intervals. 25 mg of the
polymer sample was mechanically stirred with 25 mL of 1
M KNO3 to allow the polymer to swell. The pH of the
suspension was adjusted to the required value by adding
either 0.1 M HCl or 0.1 M NaOH. It was observed that
under the given experimental conditions the state of
equilibrium established within 24 h at 25 ºC. The rate of
metal ion uptake is expressed as the percentage of the Figure 1. FTIR spectrum of PUF terpolymer resin
metal ion uptake after the specific time related to the state 3.3 1H
NMR Spectral Analysis
of equilibrium. It is given as, The 1H NMR spectrum of the PUF terpolymer is
Metal ion uptake = Amount of metal ion adsorbed / shown in Fig. 2. The signal at 8.85 ppm is assigned to the
Amount of metal ion adsorbed at equilibrium × 100 -OH of Ar-COOH and this downfield shift is due to the
1. Results and Discussion: intermolecular hydrogen bonding [10]. The signals in the
region of 6.5– 7.6 ppm are assigned to all the protons of
3.1 Physicochemical Analysis the aromatic ring [10]. The signals appeared in the region
The PUF terpolymer resin was soluble in solvents of 1.1 to 4.21 ppm is due to the methylene proton of Ar-
like N,N-dimethylformamide (DMF), tetrahydrofuran CH2 bridge [15]. The signal appeared in the region of 6.4
(THF), dimethylsulphoxide (DMSO), aqueous sodium ppm is due to the –NH bridge present in the terpolymer
and potassium hydroxide solutions and insoluble in [18].
alcohol, chloroform and carbon tetrachloride. The
physicochemical parameters such as moisture content, 3.4 Morphology and Molecular Weight Measurements
solid percentage, void volume fraction, true density and The SEM image of the terpolymer at 5000× is shown
sodium exchange capacity of the terpolymer resin are in Fig. 3. The image of the resin was found to be less
shown in Table 1. close packed with high porosity over the surface of the
terpolymer. The micrograph of the resin also shows a
3.2 Infra-Red Spectral Analysis fringed micelle model having deep and shallow voids on
FTIR spectrum of PUF is depicted in Fig. 1. A band the surface of the polymer indicates the presence of
appeared in the region of 3442.7 cm-1 is assigned to the amorphous structure. Presence of voids and cavities of
hydroxyl group of –COOH present in the aromatic ring specific size can adsorb metal ions on their surface. This
which is involved in an intramolecular hydrogen bonding is evident from the higher ion-exchange capacity of the
[15]. A peak appeared at 2807.5 cm-1 is assigned to terpolymer also. The GPC data for the terpolymer is
aromatic ring stretching modes [15]. The 1,2,3,5 tetra presented in Table 2. The average molecular weight of the
substitution of aromatic benzene ring was confirmed by PUF resin is found to be around 2060 by GPC. The
sharp, medium/weak absorption bands appeared between polydispersity index for the resin is 1.016.
1200 cm-1 and 800 cm-1 [16]. The band appeared at
1679.8 cm-1 is due to –C=O stretching vibrations. A weak Table 2.Average molecular weight of PUF resin
band appeared in the region 2901.5 cm-1 is attributed to –
CH2 linkage present in the terpolymer [17]. The band Sample Mn Mw Mz Polydispersity
appeared in the region of 3347.9 cm-1 is assigned to the – ( Mw / Mn )
NH bridge present in the terpolymer resin [18]. PUF Resin 2055 2089 2056 1.016
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Metal Sorption Studies of a Novel Terpolymer Resin
26
Metal Sorption Studies of a Novel Terpolymer Resin
3.7 Evaluation of Rate of Metal Ion Uptake found to be 6.0 mmol/g for Co2+ ion. This shows that the
The rate refers to the change in the concentration of PUF resin has higher uptake capacity for the ion-
the metal ions in the aqueous solution, which is in contact exchange process than commercial phenolic and
with the terpolymer. The metal ion uptake by the polymer polystyrene ion-exchange resins (Table 6) for cobalt ion.
increases with the increase in shaking time. Perusal of the Further the ion-exchange capacity is comparable to the
Table 5 reveals that the time taken for the uptake of the other metal ion also with the commercial resins.
different metal ions depends on the nature of the resin
3.9 Recycling of the resin
under the given conditions. Among the seven metal ions
The advantage of the PUF chelating resin is their
taken for the study, Co2+ and Cu2+ ion require about 5 h
reusability after the exchange process. The resin, once
(shortest time), whereas Mn2+, Zn2+ and Ni2+ require
used, can be
about 6 h for the establishment of the equilibrium. Ba2+
and Pb2+ ions require 7 h to reach the state of equilibrium.
The rate of the metal ion uptake depends upon the Table 6 Comparative study with commercial reins
hydrated ionic radii of the metal ions. Hence, the order of Ion-Exchange
rate of metal ion uptake is Co2+ > Cu2+ > Mn2+ > Zn2+ > Trade Name Polymer Matrix capacity
Ni2+ > Ba2+ > Pb2+ for the PUF resin. (mmol/g)
Table 4. Evaluation of distribution ratio KD, at different pH Amber lite IR-120 Polystryrene 5.0-5.2
Duolite C-3 Phenolic 2.8-3.0
Distribution ratio(KD) of the metal ions Amber lite IRC-50 Meth acrylic 9.5
Metal Duolite ES-63 Polystyrene 6.6
ions pH of the medium Dowex - 1 Polystyrene 3.5
Amberlite IRA-45 Polystyrene 5.6
3 3.5 4 4.5 5 5.5
Dowex – 3 Polystryrene 5.8
Cu2+ 150.22 190.85 280.75 394.45 501.27 610.01 PUF Resin Carboxylic and Urea 6.0
Ni2+ 100.01 140.81 230.23 320.98 410.66 508.93
recovered back to its original form by desorption of the
Zn2+ 91.23 155.28 290.17 380.03 450.82 499.25 chelated metal ions using concentrated nitric acid. The
metal free resin can be reused after repeated washing with
Co2+ 160.41 279.51 394.29 480.33 572.34 630.80 water. The recycling of the purified resin with the
addition of chosen metal ion solution results in the uptake
Ba2+ 70.12 120.63 190.25 250.36 312.27 378.98 of almost the same amount as it was initially adsorbed.
The retention of metal ion uptake capacity, even after few
Mn2+ 130.45 240.96 350.74 430.19 520.37 600.98
cycles of repeated exchanges, suggests that the resin can
Pb2+ 45.66 115.52 208.71 246.11 286.49 320.01 be used as an ion-exchanger.
2. Conclusion
M2+(NO3)2 = 0.1 M; volume = 2 mL; KNO3 = 1 M; volume = 25 mL;
weight of resin = 25 mg; time = 24 h; temperature = 25 ºC PUF terpolymer was synthesized by solution
condensation technique in acid medium. The structure of
Table 5 Evaluation of rate metal ion uptake by PUF resin the resin was confirmed by spectral studies. The
Metal Equilibrium attainment (%) morphology of the resin illustrated the high porosity and
ions Time (h) deep pits on the surface which is an additional evidence
1 2 3 4 5 6 7 for the higher ion-exchange capacity of the terpolymer.
Cu2+ 60 71 79 85 92 - - From the batch equilibrium studies, the resin has good
binding capacity with the selective metal ions and proved
Ni2+ 49 56 64 76 88 94 - as an excellent ion-exchanger.
Zn2+ 48 55 66 78 89 95 - Acknowledgment
Co 2+
61 70 79 88 97 - - The authors thank the Management & Principal
of Jamal Mohamed College (Autonomous),
Ba2+ 21 33 41 52 68 75 83
Tiruchirappalli, Tamil Nadu, India for their support
Mn2+ 46 58 60 71 85 92 - and encouragement.
2+
Pb 16 24 32 42 56 65 80 References
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Metal Sorption Studies of a Novel Terpolymer Resin
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