Reactive & Functional Polymers 68 (2008) 1346–1354

Contents lists available at ScienceDirect

Reactive & Functional Polymers

journal homepage: www.elsevier.com/locate/react

Heavy metals adsorption on some iminodiacetate chelating resins as a

function of the adsorption parameters
Maria Valentina Dinu, Ecaterina Stela Dragan *
‘‘Petru Poni’’ Institute of Macromolecular Chemistry, Aleea Grigore Ghica 41A, 700487 Iasi, Romania

a r t i c l e i n f o a b s t r a c t

Article history: The adsorption properties of some novel chelating resins (CRs) bearing iminodiacetate
Received 7 May 2008 groups for removal of heavy metal ions like: Cu(II), Co(II) and Ni(II) from aqueous solutions
Received in revised form 4 June 2008 comparative with the commercial resin Amberlite IRC-748 have been studied in this work
Accepted 14 June 2008
by a batch equilibrium technique. Quantitative analysis for adsorption was conducted
Available online 21 June 2008
using UV–vis spectroscopy to investigate the kinetics, adsorption isotherm and thermody-
namics of the removal process considering equilibration time, pH, metal ion concentration
and temperature as controlling parameters. The metal adsorption capacities, at pH 5, were
Keywords:
Iminodiacetate chelating resins
in the order Cu(II) > Ni(II) > Co(II), for both the CR with 10 wt.% DVB (CR-10) and the com-
Adsorption mercial resin Amberlite IRC-748. The adsorption capacities on CR-10 were higher for Ni(II)
Copper and Co(II) ions, but lower for Cu(II) ions compared with Amberlite IRC-748. Both Freundlich
Cobalt and Langmuir isotherms well fitted on the adsorption results of Cu(II), Ni(II) and Co(II) ions
Nickel on all iminodiacetate resins.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction moreover, these processes have high reagent and energy

Environmental contamination with heavy metals
gained lately more concern because of their high persis-
tence, and the nervous system damage, and even cancer,
caused by their accumulation at certain levels. A difficult
problem encountered in the removal of the metal ions is
that the target species are usually in low concentration
and in complex mixtures. Numerous variables must be
considered in practice, such as: salinity, pH, temperature
and the presence of organic substances [1].
Among various methods of heavy metal removal such
as liquid–liquid extraction, precipitation, electrolytic con-
centration, membrane filtration, ion exchange and adsorp-
tion, the last is generally preferred because of its high
efficiency, ease of handling, and availability of different
sorbents. While using methods such as chemical precipita-
tion and reverse osmosis for the removal of metal ions
from waste waters, metal removal is incomplete, and
* Corresponding author. Tel.: +40 232 217454; fax: +40 232 211299.
E-mail address: sdragan@icmpp.ro (E.S. Dragan).
requirement, the toxic sludge produced requiring careful
disposal. Therefore, the most promising technique for
removal of metal cations is their adsorption on organic
sorbents containing chelating functional groups [2–9]. An
organic chelating sorbent consists in two main parts:
chelating functional group(s) and the polymer matrix or
support. The structure of polymer matrix and of the chelat-
ing groups, on the one side, and the interaction mode
between the support and functional group, on the other
side, determine the specific applications of the chelating
sorbents. Organic chelating sorbents, by their high selectiv-
ity in binding metal ions and metal complex ions have a
major implication in concentration control (preconcentra-
tion of the trace elements from solutions so dilute that
no analytical determinations are possible), and in inorganic
analytical chemistry.
One central task is the removal and recovery of non-fer-
rous metals, a selective process being required for this pur-
pose. The selectivity of a certain chelating sorbent is
attributed to the differences in the stability constants of
the complexes formed with the chelating groups of the

1381-5148/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.reactfunctpolym.2008.06.011
 M.V. Dinu, E.S. Dragan / Reactive & Functional Polymers 68 (2008) 1346–1354
resin [10,11]. The selectivity can be modified by changing
the environment characteristics (pH, temperature, ionic
strength) or by the addition of different complexing agents.
Numerous studies and reviews concerning the synthesis
and characterization of the selective chelating sorbents,
and the wide applicability of these resins in the removal
of toxic metals and complex ions from industrial effluents,
as well as in selective metal ion recovery processes, have
been recently published [12–25]. This demonstrates the
constant interest in finding new chelating materials with
increased performances.
Therefore, the adsorption properties of some novel
chelating resins (CR) bearing iminodiacetate groups de-
rived from acrylonitrile – divinylbenzene (AN-DVB)
copolymers for the removal of heavy metal ions like:
Cu(II), Co(II) and Ni(II) from aqueous solutions were inves-
tigated in this work. The difference between the commer-
cial CRs bearing iminodiacetate groups and the CRs
synthesized in this work is the higher mobility of the
functional groups caused by the presence of a longer
spacer between the matrix and the iminodiacetate groups.
It is expected as this longer linker to have a positive influ-
ence on the sorption behavior of these resins. The effects
of different controlling parameters like: solution initial
pH, temperature, metal ions initial concentration and
equilibration time on the adsorption capacity of the CRs
for Cu(II), Co(II) and Ni (II) was examined by UV–vis spec-
troscopy. The influence of the regeneration level on the
heavy metal adsorption was also considered. The adsorp-
tion data of the novel CRs were compared with those of a
commercial resin (Amberlite IRC-748) based on a macro-
porous styrene-DVB matrix bearing iminodiacetate chelat-
ing groups attached on the styrene nuclei by one
methylene group.
2. Experimental
2.1. Materials
DVB, technical grade (64% o-DVB, m-DVB, p-DVB and
36% ethylstyrene, by gas chromatography), purchased from
Purolite (Victoria, Romania), was distilled at 400 Pa, at a
temperature of 50 °C, before use, to remove the polymeri-
zation inhibitor. Benzoyl peroxide (BPO) purchased from
Fluka, was employed as a radical polymerization initiator
after two times recrystallization from methanol. Acryloni-
trile (AN), purchased from Sigma–Aldrich was distilled at
76–77 °C, 101.3  103 Pa. 1,2-Diaminoethane (EDA), pur-
chased from Sigma–Aldrich, has been distilled before use
at 118 °C. Sodium monochloroacetate (NaMCA) was ob-
tained by the neutralization reaction between the mono-
chloroacetic acid and NaOH, both purchased from Sigma–
Aldrich, in ethanol. The metal salts used were copper (II)
sulphate pentahydrated, cobalt (II) chloride hexahydrated
and nickel (II) acetate tetrahydrated (all from Aldrich).
Hydrochloric acid from Chimopar, Romania, potassium
chloride, citric acid and dibasic sodium phosphate
(Na2HPO4  12 H2O), analytical grade, all from Sigma–Al-
drich were used for preparation of HCl–KCl and citrate–
phosphate buffer solutions.
1347
Amberlite resin IRC-748 was purchased from Rohn and
Haas International Ltd. The main physical and chemical
features of this resin are as follows: ionic form: Na+; oper-
ating pH: 1-14; maximum operating temperature: 90 °C
(Na+ form), 70 °C (H+ form).
2.2. Methods
AN-DVB copolymers were prepared in the presence of
toluene as porogen, by suspension polymerization tech-
nique, according to the method previously presented
[26]. Typically, 14.1 g DVB (15.4 mL) and 75,9 g AN
(93.61 mL) were used to prepare 90 g copolymer having a
nominal crosslinking degree of 10%; for 90 g of copolymer
having a nominal crosslinking degree of 15%, 21.1 g DVB
(23.1 mL) and 68.9 g AN (84.95 mL) were used. BPO
(1 wt% relative to monomers) was added to monomers
and then the corresponding amount of porogen to form
the organic phase. Dilution of the monomer mixture, D,
was calculated as the ratio between the volume of toluene
and the volume of the whole organic phase [D = Vtoluene/
(Vm + Vtoluene)]. The organic phase was then added in a vol-
ume ratio of 1/2 to the aqueous phase which contained
1.8 wt% ammonium salt of styrene-maleic acid copolymer,
0.2 wt% food grade gelatine, prepared in a four-necked
reaction reactor (1000 mL) fitted with a mechanical stirrer,
condenser and thermometer. The stirrer speed was kept at
around 200 rpm in order to obtain at least 95 wt% beads
with the diameter within the range 0.3–1.0 mm. The poly-
merization was allowed to proceed 10 h, in three stages of
temperature: 2 h at 60 °C, 3 h at 70 °C and 5 h at 85 °C. This
thermal regime allowed as about 98 wt% of monomers to
be converted in copolymer.
The copolymer fraction with bead sizes in the range
0.3–1.0 mm was selected, porogen was removed by extrac-
tion with methanol and polyacrylonitrile (PAN) likely to be
formed in the copolymerization process was extracted
with dimethylformamide (DMF). Finally, the selected
beads were washed with methanol and dried at room tem-
perature, 24 h and in vacuum at 50 °C, 48 h. Anion
exchangers with primary amine groups were obtained by
the aminolysis-hydrolysis reaction of the nitrile groups
with EDA, 8 h at 118–120 °C, at a molar ratio CN: EDA:
H2O of 1:10:2 as shown elsewhere [26,27]. The excess of
EDA was recovered by distillation at 118 °C, and finally
the beads were filtered and washed with distilled water
up to the neutral pH. To prepare an iminodiacetate chelat-
ing resin, the ion exchanger with primary amine groups
was reacted with NaMCA, in aqueous medium, at 70 °C
and a pH of 7.5–8.0, with NaI as catalyst [27]. All resins
have been treated first with 1 M NaOH and after that with
1 M HCl before the first metal ion adsorption test. Determi-
nation of cation exchange capacity was performed by
H3O+/Na+ ion exchange as previously shown [26]. Thus,
about 15 mL CR was put into a glass column fitted with a
fritted glass disk at the bottom. An aqueous solution of
4 wt% HCl was passed through the column followed by
washing with distilled water until a neutral pH value was
reached. With this procedure the iminodiacetate groups
were transformed into iminodiacetic groups. A measured
amount of 1 M NaOH (V1, mL) was passed through the col-
1348 M.V. Dinu, E.S. Dragan / Reactive & Functional Polymers 68 (2008) 1346–1354
umn and the eluent was titrated with 1 M HCl (V2, mL).
After that, the CR was quantitatively removed from the col-
umn in a graded cylinder and its volume was measured (Va,
mL). The cation exchange capacity per volume (Csv) was
calculated as follows:
C sv ¼ ðV 1  V 2 Þ=V a ðmeq=mLÞ
The wet CR was dried at constant weight (m, g). The cation
exchange capacity per dry resin (Csg) was then calculated
C sg ¼ ðV 1  V 2 Þ=m ðmeq=gÞÞ
For the structural and morphological characterization in
dry state, the CRs were rinsed several times with anhy-
drous methanol, dried in air at room temperature for
24 h and at 40 °C under reduced pressure for three days.
Morphological characterization of the AN-DVB copolymers
and CRs was performed as previously shown [27]. Briefly,
the following measurements were performed: the water
uptake, Qw, was determined by centrifuging the samples
after an immersion for 48 h in distilled water, according
to Pepper et al. [28]. The apparent density (qap) was deter-
mined using a mercury pycnometer at 1.333  102 Pa
[29]. The real density (qr) was measured in n-heptane.
The specific surface area (Ssp) was determined by the nitro-
gen adsorption at the boiling temperature of liquid nitro-
gen, by the Haul-Dümbgen method on a Ströhlein Area
Meter apparatus [30]. The average pore radius was calcu-
lated using the following equation, cylindrical shape of
pores being assumed:
r p ¼ ð2V p =Ssp Þ  103 ðnmÞ
where Vp = (1/qap)  (1/qr), pore total volume, cm /g. 3 morphological characteristics of the AN-DVB copolymers,
Study of the metal ion retention properties of the CRs
and Amberlite IRC 748 was carried out using a batch
equilibrium procedure. Thus, 0.5 g of dry CRs was placed
in a flask and contacted with 50 mL of the aqueous solution
of each metal ion: Cu(II), Co(II), Ni(II), at different temper-
atures and pH. The kinetic of the metal ion retention was
studied by placing 0.5 g of dry CRs in 50 mL of aqueous
solution of metal ion with a concentration of 0.07 mol/L,
at 25 °C, the equilibrium concentration of the metal being
measured at different contact durations. The contact time
ranged between 2 and 24 h. The influence of pH on Cu(II),
Co(II) and Ni(II) metal ions retention was studied for each
resin and the pH of the metal-ion solution was adjusted
before equilibration over a range of 1.2–2 with a HCl–KCl
buffer solution, and over a range of 2.5–6 with a citrate–
phosphate buffer solution. The effect of different concen-
trations of the Cu(II), Co(II) and Ni(II) metal ion solutions
was also examined. The resin was filtered off, and the
residual concentration of the metal cation remained in
the filtrate was measured by the UV–vis spectroscopy at
510 nm for Co(II), 720 nm for Ni(II) and 775 nm for Cu(II)
(these were the maximum absorption wavelengths of
CoCl2  6H2O, Ni(OCOCH3)2  4H2O and CuSO4  5H2O). UV–
vis spectroscopy was performed on a UV–vis Specord
M42 Carl Zeiss Jena, Germany.
The amount of metal ion bound on the resin was calcu-
lated with Eq. (4)
Metal ion bound ¼ ½ðS0  SÞV=ðW  1000Þ mg=g
where S0 and S are the concentrations of the metal ion in
aqueous solution (mg/L) before and after the interaction
with chelating resin, respectively, V is the volume of the
aqueous phase (mL) and W is the amount of the dry resin
(g).
The Cu(II) loaded on the resins was recovered with 1 M
ð1Þ
H2SO4 solution. The regeneration of the resins loaded with
a known amount of Co(II) or Ni(II) was performed with 1 M
HCl solution. After heavy metal ions were recovered from
the resins, the resins were washed with enough distilled
ð2Þ
water and then were regenerated with 1 M HCl solution.
These regenerated resins were used again for the retention
of Cu(II) (regenerated and reused at least three times).
3. Results and discussion
The general structure of the CRs obtained by the postde-
rivatization of the primary amine groups by the reaction
with NaMCA is presented in Scheme 1.
As Scheme 1 shows, the CRs synthesized in this work
have a higher mobility of the functional groups compared
with the commercial resins, caused by the presence of a
longer spacer between the matrix and the iminodiacetate
groups.
3.1. Characterization of the CRs
As it was presented in subsection 2.2, AN-DVB copoly-
mers were prepared in the presence of toluene as porogen
ð3Þ by the suspension polymerization method. Structural and
prepared at the same dilution (D = 0.47 mL/mL), were col-
lected in Table 1. Sample name includes: AN from acryloni-
trile; the numbers mean the nominal crosslinking degree,
which is the content of DVB wt% in the monomer mixture.
As Table 1 shows, the specific surface area, the pore to-
tal volume and the average pore radius, are higher for AN-
15C than for AN-10C.
Table 2 summarizes the characteristics of CRs with imi-
nodiacetate groups and of the Amberlite IRC-748 ion
exchanger.
The morphological characteristics of CR resins show
first that the specific surface area and the average pore ra-
dius decreased comparative with the starting copolymers
(Table 2 compared with Table 1). This decrease could be
correlated with the synthesis steps of CRs presented in
Scheme 1, the intermediary step for the generation of the
primary amine groups by the aminolysis-hydrolysis reac-
tion taking place at a temperature of around 118 °C. On
the other hand, Table 2 shows that the two resins are dif-
ferent, CR-10 being characterized by smaller specific sur-
face area and pore total volume than CR-15, the values of
the cation exchange capacity being in a reversed order, as
expected. Even if the matrix structure of CR-10 and Amber-
lite IRC-748 is different, the values of their cation exchange
capacity per volume are almost identical and will decide
on the retention of metal cations, as will be shown later.
The difference between the values of Csg characteristic for
CR-10 and Amberlite IRC-748 are generated by the differ-
ð4Þ ences between the matrices of the two resins, as follows:
 M.V. Dinu, E.S. Dragan / Reactive & Functional Polymers 68 (2008) 1346–1354 1349

+ 2 ClCH2COONa CH ) ( CH2 CH ) + 2 NaCl

( CH2 CH ) ( CH2 CH ) ( CH2 CH ) ( CH2 CH ) ( CH2
pH = 7. 5 8. 0
C=O
C=O
NH
NH
CH CH2 CH
CH2 C2H5 CH2
C2H5 CH2
CH2
CH2 CH2COONa
N
NH2 CH2COONa

Scheme 1.

Table 1
Some characteristics of the starting AN-DVB copolymers

Sample DVB (wt.%) Ethyl styrenea (wt%) AN (wt.%) qapc (g/cm3) Sapd (m2/g) Vpe (cm3/g) r
p
f
(nm)
Calcd. Foundb
AN-10C 10 5.64 84.36 84 0.919 27.76 0.188 13
AN-15C 15 7.59 77.41 75.95 0.541 41.27 0.948 46
a
The content of ethyl styrene corresponding to the composition of technical DVB.
b
Determined from nitrogen content of copolymers.
c
Apparent density.
d
Specific surface area.
e
Pore total volume V p ¼ q1  q1 , where qr is the real density and was equal to 1.11 g/cm3.
ap r
2V p
f
Average pore radius r 
p ¼ Ssp  103 ðnmÞ.

Table 2
Morphological and functional characteristics of CRs and Amberlite IRC–748

Sample qap (g/cm3) qr (g/cm3) Ssp (m2/g) Vp (cm3/g) r

p (nm) Csva (meq/ml) Csgb (meq/g) Qwc, (g/g)
CR-10 1.1605 1.1847 5.67 0.02 7.058 1.86 4.885 0.567
CR-15 0.903 1.1847 17.1 0.263 30.81 1.106 2.907 0.714
Amberlite IRC-748 0.7561 1.1564 29.04 0.458 31.53 1.845 7.488 0.9148
a
Cation exchange capacity per volume.
b
Cation exchange capacity per dry resin.
c
Water uptake.

a lower nominal crosslinking degree in the case of Amber- 1.0

lite IRC-748 (about 8 wt% DVB) compared with CR-10 0.9 pH = 2
(10 wt%), i.e., a higher density of the functional groups
0.8
per mass unit. The presence of ethyl styrene as the third
comonomer in the case of CR-10 also diminished the num- 0.7
ber of chelating groups per mass unit. On the other hand,
Ct/Ci

0.6
the lower water uptake of CR-10 (Qw = 0.567 g/g, Table 2)
than of Amberlite IRC-748 (Qw = 0.9148 g/g, Table 2) ex- 0.5
pH = 5
plains the similarity between the values of Csv of both res- 0.4
ins, i.e., about the same number of functional groups per CR - 10
unit volume. 0.3
CR - 15
0.2
3.2. Adsorption properties of CRs for Cu2+
0.1
0 2 4 6 8 10 12 14 16 18 20 22 24
3.2.1. Effect of contact duration on Cu(II) retention capacity of
duration, h
CRs
The effect of the contact duration on the Cu(II) retention Fig. 1. Cu(II) retention, as the ratio between the metal concentration at a
capacity of the CRs is shown in Fig. 1. The contact duration given moment (Ct) and initial metal concentration (Ci), as a function of
varied in the range 2–24 h, the initial metal concentration contact duration of CRs, initial metal concentration of 0.07 mol/L.
was fixed at 0.07 mol/L.
As Fig. 1 shows, the time required to achieve the equi- experiments the contact duration was kept constant at 8 h.
librium at pH 2 was 8 h. Therefore, for the next adsorption Concerning the influence of pH on the retention efficiency
1350 M.V. Dinu, E.S. Dragan / Reactive & Functional Polymers 68 (2008) 1346–1354

of the CRs, the first information are given by Fig. 1, which 5.0
shows that more than 80% of the metal ion remained in

/g resin)
the effluent after passing on CR-10 compared with about
29.7% on the same resin, at pH 5. On the CR-15 resin the 4.5

2+
amount of metal ion remained in effluent was higher

Metal ion retention (mmol Cu

(about 84% at pH 2 compared with about 35% at pH 5).
3.2.2. Effect of pH on Cu(II) retention capacity of CRs
Solution pH can influence the metal ion retention by the
modification of both metal ion concentration and the ratio
between acid form (COOH) and basic form (COO) of the
carboxylic groups. The values of distribution coefficient
KC, calculated with Eq. (5) [9,31], for Cu(II), were plotted
in Fig. 2 as a function of pH
K C ¼ X e =ðC i  X e Þ
where Xe is the concentration of solute adsorbed on the re-
sin at equilibrium, mmol/L, Ci is the initial ion concentra-
tion, mmol/L.
The pH values ranged from 1.2 to 6. From Fig. 2, it can
be observed that Cu(II) could hardly be adsorbed by CRs
when pH < 3. With the increasing pH value, the Cu(II)
retention increased gradually as expected, the optimum
adsorption pH of Cu(II) being located at 5. At pH > 5 the
Cu(II) retention decreased because small amount of Cu(II)
started to deposit as Cu(OH)2, the pH corresponding to
the deposition of Cu(OH)2, calculated on the basis of Ks
(solubility product of Cu(OH)2) (2.5  1019) and the initial
concentration of Cu(II) (0.07 mol/L), being 5.27.
The influence of the adsorption/desorption cycles on
the metal retention capacity is shown in Fig. 3.
An increase of the adsorption capacity of the resins up
to three adsorption/desorption cycles was observed, this
being a positive aspect of these novel resins, a decrease
of the metal adsorption capacity being usually observed
for chelating resins [7]. It seems that, after some regenera-
tion steps, the accessibility of metal ions to the iminodiac-
etate groups increased. This result could be assigned to the
increase of the chain flexibility in the whole matrix.
4.0
3.5
CR - 10
CR - 15
3.0
ð5Þ 2.5
0 1 2 3 4 5
Cycles
Fig. 3. Cu(II) retention as a function of loading cycles at pH 5, temper-
ature 25 °C, 0.07 mol/L metal ions, contact duration 8 h.
3.2.3. Equilibrium adsorption isotherms
In the adsorption process of a solute from solution onto
a solid surface, the solute adsorbed on the solid surface is
in a dynamic equilibrium with the solute remained in
solution. A plot of the solute concentration adsorbed on
the solid surface (mg g1) as a function of the solute con-
centration in the solution at equilibrium (mg L1), at con-
stant temperature, gives an adsorption isotherm, which
can be described by some adsorption models. Fig. 4 shows
that the retention capacity of CRs for Cu(II) ions increased
with the increase of the equilibrium metal concentration
resulting in a concave curve, i.e., a type L isotherm accord-
ing to the classification of Limousin et al. [32], for both res-
ins. The experimental data included in Fig. 4 resulted from
the average of three measurements at least.
The experimental data obtained for the adsorption of
Cu(II) ions onto CRs were fitted in the Freundlich, Eq. (6),
and Langmuir, Eq. (7), models [19,25,32], Figs. 5 and 6,
respectively.

2.0
CR - 10 5.0
1.8 CR - 10
CR - 15
Amberlite IRC - 748
4.5 CR - 15
1.6
4.0
1.4
qe mmol Cu(II)/g resin

3.5
1.2
3.0
KC

1.0
2.5
0.8
2.0
0.6
1.5
0.4
1.0
0.2
0.5
0.0
0 2 4 6 8 0.0
0.00 0.01 0.02 0.03 0.04 0.05 0.06
pH
Ce (mol/L)
Fig. 2. Distribution coefficient for the adsorption of Cu(II) on CRs as a
function of pH, at an initial concentration of 0.07 mol/L and temperature Fig. 4. Cu(II) retention as a function of the equilibrium metal concentra-
25 °C. tion for the CRs at pH 4, temperature 25 °C, contact duration 8 h.
 M.V. Dinu, E.S. Dragan / Reactive & Functional Polymers 68 (2008) 1346–1354 1351

0.60 Table 3
Adsorption isotherm constants of Freundlich and Langmuir models for the
0.55 2 sorption of Cu(II) on CRs
CR - 10; R =0.98
2
CR - 15; R =0.99
0.50 Adsorption model CR-10 CR-15

0.45 Freundlich
KF (mmol g1) 1.48 1.35
log qe

0.40 N 0.211 0.195

0.35 R2 0.98 0.99
Langmuir
0.30
KL (mmol/L) 0.43 0.26
0.25 B (mmol/g) 3.257 3.04
R2 0.999 0.997
0.20
0.15
0.25 0.50 0.75 1.00 1.25 1.50 1.75 As Table 3 shows, the correlation factors are high for
log Ce both models and therefore it is difficult to decide which
model is the best for the adsorption process of Cu(II) ions
Fig. 5. Freundlich adsorption isotherm for Cu(II) at pH 4. onto CRs. The values of N parameter fulfil the condition
of favouring the adsorption process (0 < N < 1) [9,33].

0.8 3.3. Adsorption properties of CRs for Co2+and Ni2+

CR - 10; R2=0.999
0.7 CR - 15; R 2 = 0.997 The values of distribution coefficient KC, calculated with
Eq. (5), for Co(II) and Ni(II), as a function of pH, were plot-
0.6 ted in Figs. 7 and 8, respectively.
1/q (g/mmol)

With the increasing pH value, the retention of both

Co(II) and Ni(II) increased gradually, the optimum adsorp-
0.5
tion pH being located at 5, as already observed for Cu(II). At
e

pH > 5 the metal retention decreased because the metals

0.4
started to deposit as M(OH)2. It was also observed that
the resin CR-10 had a higher retention capacity than the
0.3
commercial resin, irrespective of pH.
The adsorption isotherms illustrated in Fig. 9 for the
0.2 adsorption of Co(II) and Ni(II) on the resins CR-10 and
0.0 0.1 0.2 0.3 0.4 0.5
CR-15 show that the retention capacity of CRs for both ions
1/C (L/mmol)
e increased with the increase of the equilibrium metal con-
centration according to a type L isotherm.
Fig. 6. Langmuir adsorption isotherm for Cu(II) at pH 4.
The experimental data obtained for the adsorption of
Co(II) and Ni(II) ions onto CR resins were fitted in the
qe ¼ K F C Ne or log qe ¼ log K F þ N log C e ð6Þ Freundlich, Eq. (6), and Langmuir, Eq. (7), models, the
where qe is the amount of metal ion adsorbed in mg/g, Ce is
the concentration (mg/L) of metal ion in the solution at
equilibrium; KF, Freundlich constant which predicts the 2.0
quantity of metal ion per gram of resin at the unit equilib-
1.8
rium concentration; N, a measure of the nature and
strength of the adsorption process and of the distribution 1.6
CR - 10
of active sites. If N < 1, bond energies increase with the sur- 1.4 CR - 15
face density; if N > 1, bond energies decrease with the sur- Amberlite IRC-748
1.2
face density, and when N = 1, all surface sites are
1.0
equivalent [33]
KC

0.8
K L bC e 1 1 1
qe ¼ or ¼ þ ð7Þ 0.6
1 þ K LCe qe b K L bC e
0.4
where qe is the amount of metal ion adsorbed in mg/g, Ce is
0.2
the concentration (mg/L) of metal ion in the solution at
equilibrium and the Langmuir constants KL and b represent 0.0
0 1 2 3 4 5 6 7
adsorption equilibrium constant and saturated monolayer
adsorption capacity, respectively. pH
The constants corresponding to the adsorption models Fig. 7. Distribution coefficient for the adsorption of Co(II) on CRs as a
were calculated from Figs. 5 and 6 and were collected in function of pH, at an initial concentration of 0.07 mol/L and temperature
Table 3. 25 °C.
1352 M.V. Dinu, E.S. Dragan / Reactive & Functional Polymers 68 (2008) 1346–1354

1.8 Table 4
CR - 10 Adsorption isotherm constants of Freundlich and Langmuir models for the
1.6 CR - 15 sorption of Co(II) and Ni(II) on CRs
Amberlite IRC-748
1.4 Adsorption model CR-10 CR-15
Co(II)
1.2
Freundlich
1.0 KF (mmol g1) 0.5188 0.4
KC

N 0.354 0.373
0.8 R2 0.996 0.94

0.6 Langmuir
KL (mmol/L) 0.087 0.037
0.4 B (mmol/g) 2.512 2.6
R2 0.985 0.981
0.2 Ni(II)
Freundlich
0.0
KF (mmol g1) 1.43 0.81
0 1 2 3 4 5 6 7
N 0.174 0.27
pH R2 0.999 0.997

Fig. 8. Distribution coefficient for the adsorption of Ni(II) on CRs as a Langmuir

function of pH, at an initial concentration of 0.07 mol/L and temperature KL (mmol/L) 0.38 0.164
25 °C. B (mmol/g) 2.809 2.57
R2 0.982 0.995

4.0
CR -10_ Co(II)
3.5 CR -15_Co(II) 1.0
CR-10_Ni(II) CR - 10; R2 = 0.994
3.0 CR-15_Ni(II) CR - 15; R2 = 0.996
qe mmol M(II)/g resin

0.8
2.5 Amberlite IRC - 748; R2 = 0.996

2.0 0.6
ln KC

1.5
0.4
1.0

0.5
0.2
0.0
0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08
0.0
Ce (mol/L) 0.0030 0.0031 0.0032 0.0033 0.0034
1/T
Fig. 9. Co(II) and Ni (II) retention as a function of the equilibrium
concentration of the metal solution for the CRs at pH 4, temperature
Fig. 10. Plot of ln KC as a function of reciprocal of temperature (1/T) for
25 °C, contact duration 8 h.
the adsorption of Cu(II) on CRs.

constants corresponding to the adsorption models being

collected in Table 4. The Eq. (9), allows to evaluate the thermodynamic param-
The values of N parameter fulfil the condition of favour- eters of the adsorption by plotting ln KC versus 1/T.
ing the adsorption process (0 < N < 1). ln K C ¼ DSo =R  DHo =RT ð9Þ

3.4. Temperature effect on the metal retention capacity of CRs
To evaluate the thermodynamic parameters of the me-
tal cation adsorption on the chelating resins under study,
the adsorption experiments were performed at different
temperatures. Fifty milliliters of the cation metal solution
with a concentration of 0.07 mol/L was allowed to equili-
brate with 0.5 g of resin. The distribution coefficient KC,
calculated with Eq. (5), was evaluated at four temperatures
for each metal cation.
To calculate the free energy of the adsorption (DG0), the
following equation was employed:
DGo ¼ RTlnK C
where R (8.314 J/mol K) is the gas constant.
The values of the slope – DH0/R and the intercept DS0/R
from Figs. 10–12 give DH0 and DS0 for the adsorption of
Cu(II), Ni(II) and Co(II), respectively, on three chelating
resins.
The values of DH0, DS0 and DG0 were collected in Table
5.
The adsorption free energy (DG0) has negative values
for all ions under all conditions which reflect the spontane-
ity of the process. The negative enthalpy means a chemical
exothermic process and has been found also by other
authors [9,19]. In such situations, as Baraka et al. men-
tioned, the chelation mechanism may dominate over the
ð8Þ ion exchange mechanism [9].
 M.V. Dinu, E.S. Dragan / Reactive & Functional Polymers 68 (2008) 1346–1354 1353

Metal ion retention (mmol M(II)/g resin)

0.6 5.0
CR - 10; R2 = 0.997 CR - 10
4.5
0.5 CR - 15; R2 = 0.989 CR - 15
4.0 Amberlite IRC-748
Amberlite IRC - 748; R2 = 0.995
0.4 3.5
3.0
ln KC

0.3 2.5
2.0
0.2
1.5
0.1 1.0
0.5
0.0
0.0
0.0030 0.0031 0.0032 0.0033 0.0034
Cu(II) Ni(II) Co(II)
1/ T
Fig. 13. The effect of the structure of the CRs on the metal ion retention at
Fig. 11. Plot of ln KC as a function of reciprocal of temperature (1/T) for pH 5, temperature 25 °C, 0.07 mol/L metal ions, contact duration 8 h.
the adsorption of Co(II) on CRs.

Ni(II) > Co(II), at pH 5 and 0.07 mol/L metal ions. This order
0.8
is similar with that given by Rohm and Haas for Amberlite
CR - 10; R2 = 0.995 IRC-748 and can be correlated, qualitatively at least, with
CR - 15; R2 = 0.994
the hydrated cation radius.
0.6 With increasing the nominal crosslinking degree (CR-
Amberlite IRC - 748; R2 = 0.997
15), the metal adsorption capacity decreased for all metal
cations. Even if the retention capacity of Amberlite IRC-
ln KC

0.4 748 for Co(II) and Ni(II) was almost identical with that of
CR-15, being significant lower than that of CR-10, the affin-
ity for Cu(II) of the commercial resin was much higher
0.2 comparative with both CRs.
The adsorption results of further metal cations (Cd(II),
Zn(II) and Pb(II)) on CR-10 and CR-15 are the subject of a
0.0 forthcoming article.
0.0030 0.0031 0.0032 0.0033 0.0034
1/ T 4. Conclusions
Fig. 12. Plot of ln KC as a function of reciprocal of temperature (1/T) for
the adsorption of Ni(II) on CRs. The adsorption of Cu(II), Co(II) and Ni(II) on two novel
iminodiacetate chelating resins (CR-10 and CR-15) com-
parative with the commercial resin Amberlite IRC-748
3.5. Metal ion retention on CRs as a function of cation was reported in this work. The influence of different
parameters like: pH, contact time, temperature, metal ion
As Fig. 13 shows, the CRs showed a good retention abil- concentration on the adsorption capacity of the resins for
ity for the metal ions in the following order: Cu(II) > the selected heavy metals was examined; the optimum

Table 5
Thermodynamic parameters for the adsorption of Cu(II), Co(II) and Ni(II) on CRs

Sample DH0 kJ/mol DS0 J/mol K DG0 kJ/mol

298 K 308 K 318 K 328 K
Cu(II)
CR-10 10.6 37.16 21.67 22.04 22.41 22.77
CR-15 10.692 36.5 21.57 21.93 22.29 22.66
Amberlite IRC-748 9.19 33.59 19.2 19.54 19.87 20.21
Co(II)
CR-10 3.483 12.47 7.2 7.32 7.45 7.57
CR-15 3.783 14.009 7.96 8.09 8.23 8.37
Amberlite IRC-748 4.148 14.21 8.38 8.52 8.67 8.81
Ni(II)
CR-10 7.574 26.93 15.44 15.87 16.14 16.41
CR-15 7.376 25.27 14.9 15.16 15.41 15.66
Amberlite IRC-748 7.00 24.52 14.36 14.55 14.8 15.04
1354 M.V. Dinu, E.S. Dragan / Reactive & Functional Polymers 68 (2008) 1346–1354
adsorption pH of metal ions was located at 5 and the con-
tact time required to achieve the equilibrium was 8 h. A
monotonous increase of the adsorption capacity of the res-
ins for Cu(II) ions up to three adsorption/desorption cycles
was observed, this being a positive aspect of these novel
resins. Compared with the commercial resins based on a
styrene-DVB matrix, the CRs synthesized in this work are
characterized by a higher mobility of the functional groups,
caused by the presence of a linker of four atoms between
the matrix and the iminodiacetate groups. The experimen-
tal data obtained for the adsorption of all metal ions onto
CRs well fitted in both the Freundlich and Langmuir mod-
els. This shows that the adsorption energy is the same for
all sites and the ions are adsorbed on definite sites (imino-
diacetate groups), i.e., monolayer adsorption (coordination
of ions by three donor atoms 1 N and 2 O). The retention
capacity for the metal ions on CRs showed the following
order: Cu(II) > Ni(II) > Co(II), i.e., increased with the de-
crease of the hydrated cation radius. The adsorption pro-
cess is spontaneous (DG0 < 0) and exothermic (DH0 < 0).
Exothermic adsorption suggests chelation of ions to imino-
diacetate moieties to be the principle mechanism of
adsorption.
Acknowledgement
The authors gratefully acknowledge the financial sup-
port of this research from the Project CEEX-MATNANTECH
50/2006.
References
[1] R.L. Alberti, M. Casciola, U. Constantino, Encyclopedia of Analytical
Chemistry, vol. 4, Academic Press, London, 1995. p. 2298.
[2] B.L. Rivas, B. Quilodran, E. Quiroz, J. Appl. Polym. Sci. 92 (2004) 2908.
[3] W.D. Henry, D. Zhao, A.K. SenGupta, C. Lange, React. Funct. Polym. 60
(2004) 109.
[4] H. Leinonen, J. Lehto, React. Funct. Polym. 43 (2000) 1.
[5] V. Neagu, I. Bunia, C. Luca, Macromol. Symp. 235 (2006) 136.
[6] A. Denizli, N. Sanli, B. Garipcan, S. Patir, G. Alsancak, Ind. Eng. Chem.
Res. 43 (2004) 6095.
[7] A. Nastasovic, S. Jovanovic, D. Dordevic, A. Onjia, D. Jakovljevic, T.
Novakovic, React. Funct. Polym. 58 (2004) 139.
[8] M.J. Zohuriaan-Mehr, A. Pourjavadi, M. Salehi-Rad, React. Funct.
Polym. 61 (2004) 23.
[9] A. Baraka, P.J. Hall, M.J. Heslop, React. Funct. Polym. 67 (2007) 585.
[10] H. Helfferich, Ion Exchange, McGraw-Hill, New York, 1962.
[11] G. Schmuckler, in: H.F. Mark (Ed.), Encyclopedia of Polymer Science
and Technology, Suppl. vol. 2, John Wiley and Sons, New York, 1977,
p. 197.
[12] I.-H. Park, J.M. Suh, Angew. Makromol. Chem. 239 (1996) 121.
[13] C. Luca, Encyclopedia of Separation Science, vol. 4, Academic Press,
London, 2000, p. 1617.
[14] A.A. Atia, A.M. Donia, K.Z. Elwakeel, React. Funct. Polym. 65 (2005)
267.
[15] B.L. Rivas, M. Jara, E.D. Pereira, J. Appl. Polym. Sci. 89 (2003) 2852.
[16] B.L. Rivas, E. Pereira, M. Jara, C. Esparza, J. Appl. Polym. Sci. 99 (2006)
706.
[17] H. Bulbul Sonmez, B.F. Senkal, N. Bicak, J. Polym. Sci.: Part A: Polym.
Chem. 40 (2002) 3068.
[18] N. Bicak, D.C. Sherrington, S. Sungar, N. Tan, React. Funct. Polym. 54
(2003) 141.
[19] S.P. Ramnani, S. Sabharwal, React. Funct. Polym. 66 (2006) 902.
[20] C.C. Wang, C.C. Wang, React. Funct. Polym. 66 (2006) 343.
[21] Y.C. Chang, S.W. Chang, D.H. Chen, React. Funct. Polym. 66 (2006)
335.
[22] P.A. Kavakli, O. Güven, J. Appl. Polym. Sci. 93 (2004) 1705.
[23] P.K. Roy, A.S. Rawat, V. Choudhary, P.K. Rai, J. Appl. Polym. Sci. 94
(2004) 1771.
[24] A. Kałedkowski, A.W. Trochimczuk, React. Funct. Polym. 66 (2006)
957.
[25] T.C. Coelho, R. Laus, A.S. Mangrich, V.T. de Favere, M.C.M. Laranjeira,
React. Funct. Polym. 67 (2007) 468.
[26] S. Dragan, G. Grigoriu, Angew. Makromol. Chem. 200 (1992) 27.
[27] E.S. Dragan, E. Avram, M.V. Dinu, Polym. Adv. Technol. 17 (2006)
571.
[28] K.W. Pepper, D. Reichenberg, D.K. Hale, J. Chem. Soc. (1952) 3129.
[29] E. Bortel, Przem. Chem. 44 (1965) 255.
[30] R. Haul, G. Dümbgen, Chem. Ing. Technol. 32 (1960) 349.
[31] K.K. Singh, R. Rastogi, S.H. Hasan, J. Colloid Interf. Sci. 290 (2005) 61.
[32] G. Limousin, J.-P. Gaudet, L. Charlet, S. Szenknect, V. Barthe‘s, M.
Krimissa, Appl. Geochem. 22 (2007) 249.
[33] B.E. Reed, M.R. Matsumoto, Sep. Sci. Technol. 28 (1993) 2179.