July 2010, Volume 1, No.

1
International Journal of Chemical and Environmental Engineering

Synthesis and Analytical Applications of a

Chelating Resin
A. Burkanudeen1*, R. Azarudeen1, M. Riswan Ahamed1, P. Ramesh2, N. Vijayan3
1
PG &Research Department of Chemistry, Jamal Mohamed College, Tamil Nadu, India
2
Materials Laboratory, Engineering Centre, Lucas-TVS Ltd., Padi, Chennai – 600 050, Tamil Nadu, India
3
Department of Chemistry, Raja College of Engineering and Technology, Madurai – 625 001, Tamil Nadu,
India
*
Corresponding author: a_deen@rediffmail.com

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
especially at trace level is one of the most difficult and
complicated analytical tasks, since it requires versatility,
specificity and sensitivity in the analysis. Terpolymer
plays a major role in fulfilling the task as chelation ion-
exchange resin [1-4]. Ion-exchange resin derived from p-
hydroxybenzaldehyde with resorcinol and formaldehyde
was reported for its ion-exchange capacity for selective
metal ions such as copper, nickel, zinc, cobalt and iron
[5]. The quantitative separation of metal ions from binary
[cadmium (II)-lead (II)] and ternary [zinc (II)-copper (II)-
nickel (II)] synthetic mixtures were done by column
chromatography for salicylic acid based chelating resin
[6]. The chelation behavior of the phenolic-formaldehyde
polymers toward the trivalent lanthanide metal-ions like
La3+, Nd3+, Sm3+, Gd3+, and Tb3+ was studied by a static
batch equilibration technique at 25°C as a function of
contact time, pH and counter ion. The study revealed that
the polymer have higher metal-ion uptake capacity [7].
Orthonitro phenol – thiourea – paraformaldehyde and
anthranilic acid – thiourea – paraformaldehyde
terpolymers found to be a good cation exchanger for
selective transition metal ions [8, 9]. 8-hydroxyquinoline-
5-sulfonic acid–thiourea–formaldehyde copolymer resin
was synthesized and its ion-exchange properties were also
determined by batch equilibrium method for Cu2+, Ni2+,
Co2+, Pb2+ and Fe3+ metal ions. This copolymer showed a
higher selectivity for the Fe3+ ions compared to the other
metal ions [10]. An eco-friendly technique was affected to
synthesize a terpolymer resin and it was used as an ion-
exchanger for few metal ions [11].
In this research paper, we report the synthesis of a
chelating resin involving resorcinol and ethylene diamine
with formaldehyde in 2M HCl medium. The synthesized
chelating resin was characterized by FTIR, and 13C NMR,
viscometric technique and scanning electron microscopy.
Further, the terpolymer was used as a chelating ion-
exchange resin for the removal of few metal ions by batch
equilibration method. The chelation ion-exchange
capacity of the terpolymer was determined over a wide
range of concentrations, pH ranges and at different time
intervals.
2. Materials and Method
2.1 Synthesis of REF Resin
The REF resin was synthesized by the
polycondensation of resorcinol and ethylene diamine with
formaldehyde in 1:1:2 mole ratio in presence of 2M HCl
catalyst at 180 ± 2 °C in an oil bath for 8 h [9, 10]. The
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
colored resin obtained was separated and washed with
warm water, ethanol, ether and air dried. The route for the
synthesis of REF resin is shown in Scheme 1.
OH
NH2
+
H 2C
+ CH2 O
CH 2
OH
NH 2
Resorcinol Ethylene diamine
2M HCl 180 °C
HO OH HO
H2 H2
H H
N C C N
C C
H2 H2
REF Resin
Scheme 1: Synthetic route for the preparation of resin
2.2 Regeneration of the Resin
The dried resin was dissolved in 8% NaOH and
regenerated in 1:1(v/v) HCl/water to remove the
impurities. The resin was then filtered off and cured at 60
°C for 24 h in an air oven. The yield of the resin was
found to be 80%. The dried resin sample was finely
grounded and sieved to obtain uniform particle of 80
mesh size and stored in a polyethylene container.
2.3 Physicochemical and Spectral Analysis
The physicochemical parameters such as moisture
content, solid percentage, void volume fraction, true
density and sodium exchange capacity were calculated for
the resin as per the reported procedure [12]. The FTIR
spectrum of the synthesized resin sample had been
scanned in KBr pellets on a Bruker (Model Tensor 27)
spectrophotometer to identify the functional groups. The
13
C NMR spectrum of the resin was recorded in DMSO-d6
solvent using Bruker 100 MHz.
2.4 SEM and Molecular Weight Measurements
The surface analysis of the REF resin was examined
by Hitachi (Model S-3000H) scanning electron
microscope. The viscosity-average molecular weight of
the resin was determined using Brooke Field viscometer
in DMSO solvent. By selecting the appropriate spindle
and adjusting the spindle speed, the viscosity-average
molecular weight of the resin can be calculated by
multiplying the value obtained in the viscometer reading
and its spindle number. The experiment was repeated to
confirm the average molecular weight of the resin.
2.5 Ion-Exchange Properties
The ion-exchange properties of REF resin was
evaluated by batch equilibrium method for specific metal
ions like Zn2+, Mn2+, Cu2+, Ba2+ and Mg2+ in the form of
their aqueous metal nitrate solutions. The ion-exchange
capacity for the resin was studied as a function of various
electrolytes in different concentrations, pH ranges, and
time intervals.
2.6 Determination of metal ion uptake in various
electrolytes at different concentrations
NaCl, NaNO3, NaClO4 and Na2SO4 electrolytes in
different concentrations viz. 0.01, 0.1 and 0.5 M was
taken in a separate pre-cleaned glass bottles. 25 mg of the
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
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
OH
added and the stirring was continued for 24 h at the same
temperature. The mixture was then filtered off and
washed with distilled water. The filtrate and the washings
were collected and then the amount of metal ion was
estimated by titrating against standard Na2EDTA solution.
The amount of metal ion taken up by the polymer in the
presence of a given electrolyte can be calculated from the
difference between the actual value and that of from the
blank experiment carried out along with the regular
titration. The mechanism of the chelation proposed for
the resin is as follows.
(Res.A-)B+ + C+ (solution) ↔ (Res.A-) C+ + B+(solution)
where, Res., A-, B+, and C+ represents the polymeric
resin, the anion attached to the polymeric framework, the
active or mobile cation, and the metal ion respectively.
2.7 Determination of the distribution of metal Ions at
different pH
The distribution of each of the metal ion at various
pH ranging from 3 to 5.5 between the polymer phase and
the aqueous phase were determined in the presence of 1
M NaNO3 at 25 ºC. The distribution ratio KD, may be
defined as
KD = Weight (in mg) of metal ions taken up by 1 g of the
resin sample / Weight (in mg) of metal ions present in 1
mL of the solution
2.8 Determination of rate of metal ion uptake
The rate of uptake of metal ion under the
experimental conditions was evaluated by a series of
experiments carried out at specific time intervals. 25 mg
of the polymer sample was mechanically stirred to swell
the terpolymer with 25 mL of 1 M NaNO3. 0.1 M HCl or
0.1 M NaOH were added to adjust the pH depending on
the acidity or basicity of the suspension. The rate of
metal ion uptake is usually expressed in terms of the
percentage of the metal ion uptake after a specific time
related to the state of equilibrium which was perceived as
24 h at 25 ºC. It is given as,
Metal ion uptake = Amount of metal ion adsorbed /
Amount of metal ion adsorbed at equilibrium × 100
30
 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)

Fig. 2 13C NMR spectrum of REF resin

3.2 Determination of metal ion uptake at different
electrolytes
Fig 1. FTIR spectrum of REF resin
Batch equilibrium method was adopted to study the
3.1 FTIR Spectrum chelation ion-exchange property of the REF resin using
The FTIR spectrum provides useful information Zn2+, Mn2+, Cu2+, Ba2+ and Mg2+ ions in various
about the linkages and the functional group present in the electrolyte medium viz. NaCl, NaNO3, NaClO4, and
terpolymer. FTIR of REF resin is shown in Fig. 1. The Na2SO4 in 0.01, 0.1 and 0.5 M concentrations of the
band appeared in the region of 3253.1 cm-1 is assigned to electrolytes. The results are presented in Table 3. The
the –OH group present in the aromatic ring [13]. A peak data reveals that the amount of metal ion uptake for a
appeared at 2885.3 cm-1 is assigned to aromatic ring given amount of resin depends on the nature and
stretching modes [13]. The 1,2,3,5 tetra substitution of concentrations of the electrolyte. As the concentration of
aromatic benzene ring by sharp, medium/weak absorption the electrolyte increases, the uptake of metal ion also
bands appeared between 1200 cm-1 and 800 cm-1 [14]. A increases. This can be explained on the basis of the
weak band appeared in the region 2641.1 cm-1 is stability constants of the resin which is higher at higher
attributed to –CH2 linkage present in the terpolymer [15]. concentrations of the electrolyte. The amount of uptake
The band appeared in the region of 3253.1 cm-1 is of Cu2+ and Zn2+ ions by the resin in all the four
assigned to the –NH bridge present in the resin [16]. This electrolytes is found to be higher than that of the other
band seems to be merged with the band appeared for the – metal ions like Ba2+, Mg2+ and Mn2+. This is due to the
OH in the –COOH group of the resin. The spectral data formation of stronger complexes by the anions of the
for the resin is given in Table 2. electrolytes with Cu2+ and Zn2+ ions. The strong
complexing ability of Cu2+ and Zn2+ ions may be the
Table 2 FTIR Spectral data of REF resin
reason behind the higher uptake of metal ion by the resin
at higher concentration of the electrolytes. Further the
Vibration Mode Frequency (cm-1) amount of metal ion taken up by the resin in Na2SO4
electrolyte decreases on increasing concentration of the
Expected Observed electrolyte. This is due to the formation of strong chelates
by the sulphate ions compared to other anions in the
-OH group of Ar-OH 3500-3200 3253.1
-CH2- stretching 3000-2600 2641.1 solution medium. The amount of metal ion taken up by
1,2,3,5 substituted 1200-800 1212.5 & 894.3 the REF resin is found to be good and comparable to
benzene ring other terpolymer resins of similar nature [7, 13].
Aromatic ring 2700-3000 2885.3
stretching (CH) 3500-3200 3253.1 3.3 Determination of Distribution of Metal Ions at
-NH bridge Different pH

31
 Synthesis and Analytical Applications of a Chelating Resin

The distribution of metal ions between polymer phase

and the aqueous phase was determined at room be the reason behind the decreased uptake of the
temperature in the presence of 1 M NaNO3 at various pH metal ions. The order of distribution of metal ions are
ranges from 3 to 5.5. Perusal of the Table 4 reveals that, Cu2+ > Zn2+ > Mg2+ > Mn2+ > Ba2+ for the pH ranges from
the relative amount of the metal ion taken up by the resin 3 to 5.5.
at equilibrium increases with increasing pH. It is also
3.4 Determination of rate of metal ion uptake
observed that Cu2+ ion is more effectively taken up than
The metal ion taken up by the polymer increases with
the other ions under study at all pH. Among the other
the increase in contact time. Table V reveals that the time
ions, Zn2+ and Mg2+ shows moderate uptake
taken for the uptake of the different metal ions. From the
Table 3 Determination of the uptake of metal ions study, Cu2+ and Zn2+ ions require about 5 h, whereas Mn2+
and Mg2+ require about 6 h for the establishment of the
Metal Concentration Weight of metal ion uptake in
equilibrium. However, Ba2+ ion require 7 h to reach the
ions of presence of electrolytes (mg) state of equilibrium. This is due to the hydrated ionic radii
electrolytes Nalco NaNO3 Na2SO4 NaClO4 of the metal ions. It is observed that bigger the size of the
cation lower will be rate of metal ion uptake. Hence, the
(mol/L)
order of rate of metal ion uptake is Cu2+ > Zn2+ > Mg2+ >
Cu2+ 0.01 07.54 08.55 03.56 06.57 Mn2+ > Ba2+ for the REF resin.
0.10 08.96 09.01 03.01 07.41 3.5 SEM and molecular weight measurements
0.50 09.78 10.45 02.54 07.92 A surface characteristic of the REF resin is shown in
Zn2+ 0.01 06.69 07.59 03.08 05.12 Fig. 3 at 7200× magnification. As seen from the image,
the resin is in the intermediate state between amorphous
0.10 07.45 08.03 02.85 05.98
and crystalline nature. Moreover, the photograph also
0.50 08.11 08.89 01.98 06.21 shows that the terpolymer has deep shallow pits with
Ba 2+
0.01 03.28 04.02 01.05 03.54 more amorphous character and less close packed surface.
There are pores and voids on the surface of the terpolymer
0.10 03.97 04.65 00.65 04.12
which would be the reason behind the effective adsorption
0.50 04.39 04.99 00.34 04.85 of metal ions of suitable size. Hence, these kinds of
Mn 2+
0.01 05.69 06.11 01.12 01.96 polymers can act as effective ion-exchangers. The
0.10 06.25 06.74 00.75 02.33
viscosity-average molecular weight of the resin is 2250 as
determined by viscometric measurements.
0.50 06.95 07.29 00.45 02.99
3.6 Reusability of the resin
Mg2+ 0.01 06.01 07.96 04.58 05.45
The terpolymer can be used again and again
0.10 06.87 08.51 03.91 05.97 repeatedly. The resin is recovered back to its original
0.50 07.45 08.87 03.28 06.23 form by desorption process in concentrated nitric acid.
M2+(NO3)2 = 0.1 M; volume = 2 mL; volume of electrolyte = 25 mL; After the repeated cycling in concentrated HNO3 the resin
weight of resin = 25 mg; time = 24 h; temperature = 25 ºC is washed and dried. It is now ready for the reuse. It is
of the metal ions at more acidic pH values. This may estimated that the amount of metal ion taken up by the
be due to the steric hindrance of macromolecules at recycled polymer is no way inferior to the freshly
higher acidic conditions. In the case of Ba2+ and Mn2+ prepared resin.
ions, it is observed that the distribution ratio is very low at Table 5.Determination of rate of metal ion uptake
pH ranges from 3 to 5.5. The weak stabilization energy of
the metal complex will Equilibrium attainment (%)
Metal
Table 4 Distribution ratios KD, at various pH ions Time (h)

Distribution ratio(KD) of the metal ions 1 2 3 4 5 6 7

Metal pH of the medium Cu2+ 65 74 80 89 96 - -
ions 3 3.5 4 4.5 5 5.5
Zn2+ 56 67 74 88 94 - -
Cu2+ 147.21 220.54 295.29 370.12 460.08 550.32
2+
Zn2+ 101.02 135.69 220.78 300.85 386.22 480.98 Ba 23 34 42 58 66 79 -

Ba2+ 65.14 101.24 150.48 201.28 245.98 286.96 Mn2+ 51 60 68 75 84 90 -

2+
Mn 85.27 132.85 190.65 245.39 298.57 360.78
Mg2+ 54 62 71 80 88 95 -
Mg2+ 95.86 125.84 170.19 244.61 312.27 401.23
M2+(NO3)2 = 0.1 M; volume = 2 mL; NaNO3 = 1 M; volume = 25 mL; 2+
M (NO3)2 = 0.1 M; volume = 2 mL; NaNO3 = 1 M; volume = 25 mL;
weight of resin = 25 mg; time = 24 h; temperature = 25 ºC weight of resin = 25 mg; temperature = 25 ºC

32
 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.

References
[1] R.K. Sharma, “Design, synthesis, and application of chelating
polymers for separation and determination of trace and toxic metal
ions. A green analytical method,” Pure Appl. Chem., vol. 73(1),
pp. 181-186, 2001.
[2] R.J. Qu, C.N. Ji, Y.Z. Sun, Z.F. Li, G.X. Cheng, and R.F. Song,
“Syntheses and adsorption properties of phenol formaldehyde type
chelating resins bearing the functional group of tartaric acid,”
Fig 3. SEM image of REF resin at 7200× magnification Chinese J Polym Sci., vol. 22(5), pp. 469-475, 2004.
[3] S. Das, R.R. Samal, S. Sahoo, and S. Acharya, “Chelating resins V:
These results clearly establish that the polymer can be Synthesis and characterization of chelating resins of formaldehyde-
reused again and again. condensed phenolic schiff bases derived from 4,4'-
diaminodiphenyl sulphone with hydroxy benzaldehydes,” Polym.
3.7 Comparative study for resin Int., vol. 44, pp. 41-48, 1997.
The ion-exchange capacity of the various commercial
[4] T. Kaliappan, S.C. Murugavel, and P. Kannan, “Studies on various
resins was reported to be between 2.8-6.6 mmol/g for divalent metal complexes of poly(2-hydroxy-4-
different metal ions (Table 6). The ion-exchange capacity acryloyloxybenzophenone) in aqueous medium,” Polym. Int., vol.
of the REF terpolymer resin for the chosen metal ions is 45, pp. 278-284, 1998.
found to be 2.0-4.3 mmol/g. Hence it is proposed that the [5] V.V. Hiwase, A.B. Kalambe, K.M. Khedkar, and S.D. Deosarkar,
terpolymer can be a better replacement for the “Ion-exchange properties of resins derived from p-
commercially available resin. This shows that the REF hydroxybenzaldehyde, resorcinol and formaldehyde,” E. J. Chem.,
resin has higher uptake capacity for the ion-exchange vol. 7(1), pp. 287-294, 2010.
process than commercial phenolic and polystyrene ion- [6] B.A. Shah, A.V. Shah, and R.R. Bhatt, “Studies of chelation ion-
exchange resins. exchange properties of copolymer resin derived from salicylic acid
and its analytical applications,” Iran. Polym. J., vol. 16(3), pp.
Table 6.Comparative study of the various Ion-Exchange resins 173-184, 2007.
[7] F.A. Rimawi, A. Ahmad, F.I. Khalili, and M.S. Mubarak, “Chelation
Trade Name Polymer Matrix Ion-Exchange properties of some phenolic-formaldehyde polymers toward some
capacity trivalent lanthanide ions,” Solv. Extr. Ion Exch., vol. 22(4), pp.
(mmol/g) 721-735, 2004.
Amberlite IR-120 Polystryrene 5.0-5.2 [8] A.Burkanudeen, and M. Karunakaran, “Chelation ion-exchange
Duolite C-3 Phenolic 2.8-3.0 properties of ortho nitrophenol-thiourea-paraformaldehyde
Duolite ES-63 Polystyrene 6.6 terpolymer,” Orient. J. Chem., vol. 18, pp. 65-68, 2002.
Dowex – 1 Polystyrene 3.5
Amberlite IRA-45 Polystyrene 5.6 [9] M.Karunakaran, and A. Burkanudeen, “Synthesis and ion-exchange
REF Resin Phenolic 4.3 characteristics of anthranilic acid-thiourea-paraformaldehyde
resins,” Orient. J. Chem., vol. 19, pp. 225-228, 2003.
4. Conclusion [10] V.D. Mane, N.J. Wahane, and W.B. Gurnule, “Copolymer resin.
VII. 8-hydroxyquinoline-5-sulfonic acid–thiourea–formaldehyde
In conclusion, the chelating resin derived from copolymer resins and their ion-exchange properties,” J. Appl.
resorcinol and ethylene diamine with formaldehyde was Polym. Sci., vol. 111, pp. 3039-3049, 2009.
useful cation exchanger for divalent metal ions. The [11] R.S. Azarudeen, M.A. Riswan Ahamed, D. Jeyakumar, and A.R.
spectroscopic results clearly confirm the structure of the Burkanudeen, “An eco-friendly synthesis of a terpolymer resin:
resin. Viscometric measurement provides that the characterization and chelation ion-exchange property,” Iran.
Polym. J., vol. 18(10), pp. 821-832, 2009.
viscosity-average molecular weight of the resin as 2250.
A SEM image of the resin establishes the amorphous [12] A. Vogel, Text Book of Quantitative Chemical Analysis, 5th ed.,
nature of the resin which helps for the higher metal ion Longman group, UK, 1989.
uptake. From the study, Cu2+ and Zn2+ were taken up [13] B.A. Shah, A.V. Shah, N.B. Patel, “A benign approach of
more effectively by the resin compared to the other metal microwave assisted synthesis of copolymeric resin with improved
thermal, spectral and ion-exchange properties,” Iran. Polym. J.,
ions. The ion-exchange of the REF terpolymer is vol. 17, pp. 3-17, 2008.
comparable to the commercially available resins. Hence
toxic metals of similar divalent nature from industrial [14] R.M. Silverstein, and F.X. Webster, Spectrometric Identification of
Organic Compounds, 6th ed., John Wiley, New York, 1998.
wastes can also be removed by the resin effectively.

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 Synthesis and Analytical Applications of a Chelating Resin

[15] J.A. Raj, C. Vedhi, A. Burkanudeen, P. Arumugam, and P.
Manisankar, “Synthesis and characterization of novel nano-size
polyreactive yellow 107,” Ionics, vol. 16, pp. 171-175, 2010.
[16] S.S. Kattamwar, A.B. Zade, S.S. Rahangdale, and W.B. Gurnule,
“Terpolymer resin–III: synthesis and characterization of 8-
hydroxyquinoline–dithiooxamide–formaldehyde terpolymer
resins,” J. Appl. Polym. Sci., vol. 113, pp. 3330-3335, 2009.
[17] E. Pretsch, P. Buhlmann, and C. Afflolter, Structure Determination
of Organic Compounds, Springer, New York, 2000.
[18] W.B. Gurnule, and D.B. Patle, “Study of chelation ion-exchange
properties of new copolymer resin derived from o-aminophenol,
urea and formaldehyde,” Arch. Appl. Sci. Res., vol. 2(1), pp. 261-276, 2010.

34