Beruflich Dokumente
Kultur Dokumente
1
International Journal of Chemical and Environmental Engineering
Abstract
-Resorcinol and ethylene diamine with formaldehyde (REF) terpolymer has been synthesized by polycondensation technique in 2M
HCl medium and used as a chelating resin for the removal of few divalent toxic metal ions. The physico-chemical parameters such as
moisture, solid percentage, void volume, true density and sodium exchange capacity were calculated for the resin. Fourier transform
infrared and nuclear magnetic resonance spectroscopic methods were used to elucidate the structure of the resin. Average molecular
weight of the resin was determined by viscometry. Scanning electron microscopy (SEM) was used to determine the surface features
of the resin. The chelation ion-exchange property of the resin showed an effective binding capacity for few divalent cations. A batch
equilibration method was employed to study the selectivity of the metal ion uptake over a wide range of concentrations, pH ranges and
at different time intervals.
Keywords: Chelating Resin; Polycondensation; Sorption; Physicochemical Parameters; Molecular Weight.
1. Introduction
In the recent past, accurate analysis of metal ions determined by batch equilibrium method for Cu2+, Ni2+,
especially at trace level is one of the most difficult and Co2+, Pb2+ and Fe3+ metal ions. This copolymer showed a
complicated analytical tasks, since it requires versatility, higher selectivity for the Fe3+ ions compared to the other
specificity and sensitivity in the analysis. Terpolymer metal ions [10]. An eco-friendly technique was affected to
plays a major role in fulfilling the task as chelation ion- synthesize a terpolymer resin and it was used as an ion-
exchange resin [1-4]. Ion-exchange resin derived from p- exchanger for few metal ions [11].
hydroxybenzaldehyde with resorcinol and formaldehyde In this research paper, we report the synthesis of a
was reported for its ion-exchange capacity for selective chelating resin involving resorcinol and ethylene diamine
metal ions such as copper, nickel, zinc, cobalt and iron with formaldehyde in 2M HCl medium. The synthesized
[5]. The quantitative separation of metal ions from binary chelating resin was characterized by FTIR, and 13C NMR,
[cadmium (II)-lead (II)] and ternary [zinc (II)-copper (II)- viscometric technique and scanning electron microscopy.
nickel (II)] synthetic mixtures were done by column Further, the terpolymer was used as a chelating ion-
chromatography for salicylic acid based chelating resin exchange resin for the removal of few metal ions by batch
[6]. The chelation behavior of the phenolic-formaldehyde equilibration method. The chelation ion-exchange
polymers toward the trivalent lanthanide metal-ions like capacity of the terpolymer was determined over a wide
La3+, Nd3+, Sm3+, Gd3+, and Tb3+ was studied by a static range of concentrations, pH ranges and at different time
batch equilibration technique at 25°C as a function of intervals.
contact time, pH and counter ion. The study revealed that
the polymer have higher metal-ion uptake capacity [7]. 2. Materials and Method
Orthonitro phenol – thiourea – paraformaldehyde and 2.1 Synthesis of REF Resin
anthranilic acid – thiourea – paraformaldehyde The REF resin was synthesized by the
terpolymers found to be a good cation exchanger for polycondensation of resorcinol and ethylene diamine with
selective transition metal ions [8, 9]. 8-hydroxyquinoline- formaldehyde in 1:1:2 mole ratio in presence of 2M HCl
5-sulfonic acid–thiourea–formaldehyde copolymer resin catalyst at 180 ± 2 °C in an oil bath for 8 h [9, 10]. The
was synthesized and its ion-exchange properties were also separated product was then cooled, poured into crushed
Synthesis and Analytical Applications of a Chelating Resin
ice with constant stirring and left overnight. The brick red ions like Zn2+, Mn2+, Cu2+, Ba2+ and Mg2+ in the form of
colored resin obtained was separated and washed with their aqueous metal nitrate solutions. The ion-exchange
warm water, ethanol, ether and air dried. The route for the capacity for the resin was studied as a function of various
synthesis of REF resin is shown in Scheme 1. electrolytes in different concentrations, pH ranges, and
OH time intervals.
NH2 2.6 Determination of metal ion uptake in various
+
H 2C
+ CH2 O electrolytes at different concentrations
CH 2 NaCl, NaNO3, NaClO4 and Na2SO4 electrolytes in
OH different concentrations viz. 0.01, 0.1 and 0.5 M was
NH 2 taken in a separate pre-cleaned glass bottles. 25 mg of the
Resorcinol Ethylene diamine Formaldehyde
REF resin was added to it. The pH of the suspension was
adjusted to the required value either by adding 0.1 M HCl
2M HCl 180 °C
or 0.1 M NaOH as the case may be and mechanically
stirred to swell the resin for 24 h at room temperature.
Then exactly 0.1 M of the metal ion solution (2 mL) was
HO OH HO OH
added and the stirring was continued for 24 h at the same
H2 H2
temperature. The mixture was then filtered off and
H H
N C C N washed with distilled water. The filtrate and the washings
C C
H2 H2 were collected and then the amount of metal ion was
estimated by titrating against standard Na2EDTA solution.
REF Resin The amount of metal ion taken up by the polymer in the
Scheme 1: Synthetic route for the preparation of resin
presence of a given electrolyte can be calculated from the
difference between the actual value and that of from the
2.2 Regeneration of the Resin blank experiment carried out along with the regular
The dried resin was dissolved in 8% NaOH and titration. The mechanism of the chelation proposed for
regenerated in 1:1(v/v) HCl/water to remove the the resin is as follows.
impurities. The resin was then filtered off and cured at 60 (Res.A-)B+ + C+ (solution) ↔ (Res.A-) C+ + B+(solution)
°C for 24 h in an air oven. The yield of the resin was
found to be 80%. The dried resin sample was finely where, Res., A-, B+, and C+ represents the polymeric
grounded and sieved to obtain uniform particle of 80 resin, the anion attached to the polymeric framework, the
mesh size and stored in a polyethylene container. active or mobile cation, and the metal ion respectively.
2.3 Physicochemical and Spectral Analysis 2.7 Determination of the distribution of metal Ions at
The physicochemical parameters such as moisture different pH
content, solid percentage, void volume fraction, true The distribution of each of the metal ion at various
density and sodium exchange capacity were calculated for pH ranging from 3 to 5.5 between the polymer phase and
the resin as per the reported procedure [12]. The FTIR the aqueous phase were determined in the presence of 1
spectrum of the synthesized resin sample had been M NaNO3 at 25 ºC. The distribution ratio KD, may be
scanned in KBr pellets on a Bruker (Model Tensor 27) defined as
spectrophotometer to identify the functional groups. The KD = Weight (in mg) of metal ions taken up by 1 g of the
13
C NMR spectrum of the resin was recorded in DMSO-d6 resin sample / Weight (in mg) of metal ions present in 1
solvent using Bruker 100 MHz. mL of the solution
2.4 SEM and Molecular Weight Measurements 2.8 Determination of rate of metal ion uptake
The surface analysis of the REF resin was examined The rate of uptake of metal ion under the
by Hitachi (Model S-3000H) scanning electron experimental conditions was evaluated by a series of
microscope. The viscosity-average molecular weight of experiments carried out at specific time intervals. 25 mg
the resin was determined using Brooke Field viscometer of the polymer sample was mechanically stirred to swell
in DMSO solvent. By selecting the appropriate spindle the terpolymer with 25 mL of 1 M NaNO3. 0.1 M HCl or
and adjusting the spindle speed, the viscosity-average 0.1 M NaOH were added to adjust the pH depending on
molecular weight of the resin can be calculated by the acidity or basicity of the suspension. The rate of
multiplying the value obtained in the viscometer reading metal ion uptake is usually expressed in terms of the
and its spindle number. The experiment was repeated to percentage of the metal ion uptake after a specific time
confirm the average molecular weight of the resin. related to the state of equilibrium which was perceived as
24 h at 25 ºC. It is given as,
2.5 Ion-Exchange Properties Metal ion uptake = Amount of metal ion adsorbed /
The ion-exchange properties of REF resin was Amount of metal ion adsorbed at equilibrium × 100
evaluated by batch equilibrium method for specific metal
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Synthesis and Analytical Applications of a Chelating Resin
3. Results and Discussion The 13C NMR spectrum provides useful information
about the nature of the carbon present in the resin. The
The REF resin was soluble in DMF, THF, DMSO, observed chemical shifts are assigned on the basis of the
aqueous NaOH, and KOH. However the resin was literature [10, 17]. The spectrum shows the corresponding
insoluble in solvents like ethanol and chloroform. The peaks at 118.4, 157.3, 130.1, 137.4, 128.2, and 127.8 ppm
results of the physicochemical parameters such as with respect to C1 to C6 of the aromatic ring. The peak
moisture content, solid percentage, void volume fraction, appeared at 42.12 ppm is assigned to the Ar–CH2 in the
true density and sodium exchange capacity of the resin resin. The appeared shift at 22.54 ppm is assigned to –
are shown in Table 1. CH2 – CH2 –linkage in the resin.
Table I Physicochemical Parameters of REF resin
Properties Value (SD)
Moisture (%) 3.4 ± 0.65
Solid (%) 96.6 ± 0.35
True density (dry resin) g/cm3 2.21 ± 0.21
Void volume fraction 0.1 ± 0.035
Sodium exchange capacity ( mmol/g dry 08.12 ± 0.95
resin)
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Synthesis and Analytical Applications of a Chelating Resin
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Synthesis and Analytical Applications of a Chelating Resin
Acknowledgement
The authors thank the Management & Principal of
Jamal Mohamed College, Tiruchirappalli, and Dr. D.
Jeyakumar, Scientist, Central Electrochemical Research
Institute, Karaikudi, Tamil Nadu for their support and
encouragement.
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33
Synthesis and Analytical Applications of a Chelating Resin
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