Talanta 73 (2007) 195201

Review

A chelating resin with bis[2-(2-benzothiazolylthioethyl)sulfoxide]:

Synthesis, characterization and properties for the removal
of trace heavy metal ion in water samples
Chunnuan Ji, Rongjun Qu , Chunhua Wang, Hou Chen, Changmei Sun,
Qiang Xu, Yanzhi Sun, Chao Wei
School of Chemistry & Materials Science, Ludong University, Yantai 264025, China
Received 22 October 2006; received in revised form 20 March 2007; accepted 22 March 2007
Available online 27 March 2007

Abstract
A new chelating resin containing bis[2-(2-benzothiazolylthioethyl)sulfoxide] was synthesized using chloromethylated polystyrene as material
and characterized by elemental analysis and infrared spectra. The adsorption capacities of the newly formed resin for Hg2+ , Ag+ , Cu2+ , Zn2+ , Pb2+ ,
Mn2+ , Ni2+ , Cd2+ and Fe3+ were investigated over the pH range 1.06.0. The resin exhibited no affinity for alkali or alkaline earth metal ions.
The maximum adsorption capacities of the resin for Hg2+ , Ag+ , Cu2+ , Zn2+ , Pb2+ , Mn2+ , Ni2+ , Cd2+ and Fe3+ were 1.49, 0.96, 0.58, 0.11, 0.37, 0,
0.24, 0.36 and 0.25 mmol g1 , respectively. In column operation it had been observed that Hg2+ and Ag+ in trace quantity could be separated from
different binary mixtures and Hg2+ could be effectively removed from industrial wastewater and the natural water spiked with Hg2+ at usual pH.
2007 Published by Elsevier B.V.
Keywords: Chelating resin; Bis[2-(2-benzothiazolylthioethyl)sulfoxide]; Recovery; Metal ions

Contents
1.
2.

3.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1. Apparatus and reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2. Preparation of the resin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3. Water regain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4. Resin stability test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.5. Batch experiment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.6. Adsorption kinetic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.7. Effect of diverse metal ions on adsorption capacities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.8. Separation of Hg2+ and Ag+ from several binary mixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.9. Removal of Hg2+ from river and ground water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.10. Removal of Hg2+ from industrial wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1. Characterization of the resin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2. Adsorption capacities for metal ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3. Separation of Hg2+ and Ag+ from alkali and alkaline earth metal ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.4. Separation of Hg2+ and Ag+ from binary mixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.5. Removal of Hg2+ from natural waters and industrial wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Corresponding author.
E-mail addresses: rongjunqu@sohu.com, qurongjun@eyou.com (R. Qu).

0039-9140/$ see front matter 2007 Published by Elsevier B.V.

doi:10.1016/j.talanta.2007.03.043

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C. Ji et al. / Talanta 73 (2007) 195201

Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1. Introduction
Much attention has been drawn to the synthesis of chelating resins and to the investigation of their adsorption behavior
for the selective and quantitative separation of specific metal
ions from various matrices, because both their adsorption ability
and adsorption selectivity are superior to those of ion exchangers in a trace or ultra concentration range [13]. In general,
the adsorption selectivity of chelating resins has been reported
to be dependent mainly on the chelate forming properties of
functional groups chemically bonded on the supports such as
silica gel, cellulose and macroporous copolymers [4]. Chelating resins containing heterocyclic functional groups receive a
great deal of attention since they display high affinity towards
heavy and noble metal ions [5]. Many chelating resins obtained
by immobilization of heterocyclic functional groups on solid
supports have been practically applied in separation of trace metals from a variety of matrices [6,7]. Several heterocycles such
as pyridine [8,9], imidazole [10], imidazolylazo [11], benzimidazolylazo [12], quinoline [13] and 2-mercaptobenzothiazole
(MBZ) [1417] have been immobilized on a resin bed for this
purpose. Among the above-mentioned chelating resins, the ones
containing 2-mercaptobenzothiazole exhibit high affinity for
heavy and noble metal ions, especially for mercury [16]. In Ref.
[18], the separation properties of the resin containing sulphur and
MBZ for Hg2+ and Ag+ has been studied. The results obtained
show that the resin can separate Hg2+ and Ag+ quantitatively in
aqueous solution.
Recently, the synthesis of chelating resins with N,N substituted diamides of malonic acid [19,20] and N,N -dialkyl
aliphatic amides [21] has been reported. These resins are proved
to have good adsorption properties for metal ions owing to the
close proximity of donor atoms, which can increase the probability of formation of stronger complexes [22].
Considering the above we have designed a new chelating
resin containing bis[2-(2-benzothiazolylthioethyl)sulfoxide] as
functional group. The present report describes the synthesis and
characterization of the resin. Its adsorption capacity for Hg2+ ,
Ag+ , Cu2+ , Zn2+ , Pb2+ , Mn2+ , Ni2+ , Fe3+ and Cd2+ was investigated. The recovery of Hg2+ and Ag+ from several binary
mixtures and the recovery of Hg2+ from natural waters spiked
with Hg2+ and industrial wastewater were also studied.
2. Experimental
2.1. Apparatus and reagents
A flame atomic absorption spectrophotometer (Model 932A,
made in Australia) was used for metal ion determination. The
operating condition was presented in Table 1. The infrared
spectra were recorded on a Nicolet MAGNA-IR550 (series

200
200
200

II) spectrometer (made in American); test condition: potassium bromide pellets, scanning 32 times, resolution 4 cm1 .
The elemental analysis was carried out using an Elementar Analysensysteme Gmbh Varioel (made in Germany).
Semi-automatic sequential injection hydride generation doublechannel atomic fluorescence spectrometer (Model AFS-920,
made in China) was used to determine the content of Hg2+
in river water and ground water. The BET surface area was
determined by ASAP-2020 Surface Area and Porosity Analyzer (made in American). The adjustment of pH was done
with microprocessor pH meter (Model HANNA pH211, made in
Portugal).
Chloromethylated polystyrene (PS-Cl, crosslinked with 10%
DVB, 5.49 mmol g1 Cl, 3040 mesh, BET surface area
31.85 m2 g1 ) was purchased from Chemical Factory of Nankai
University of China. 2-Mercaptoethanol, 30% hydrogen peroxide solution, urotropine, 2-mercaptobenzothiazole (MBZ),
benzenesulfonyl chloride (BsCl), and other reagents, solvents
were of analytical reagent grade and were used without further
purification.
Stock solutions of the metal ions (1 mg ml1 each) were prepared by dissolving appropriate amounts of analytical grade
nitrates in distilled water, and further diluted prior to use. The
buffer solutions were prepared by addition of dilute NH4 OH or
HNO3 to 0.1 M ammonium acetate solution.
2.2. Preparation of the resin
The target chelating resin was synthesized as follows
(Scheme 1).
Resin I was obtained according to the similar procedure
described in literature [23]: 30.0 g of PS-Cl was reacted with
urotropine (96.0 g) in a mixture of ethanol and water (34:20,
v/v) at 90 C for 36 h. Then 250 ml of hydrochloric acid was
added and the mixture was stirred at 90 C for 9 h. After filtration, the residue was washed with distilled water and ethanol
and dried under vacuum at 50 C. 32.9 g of resin I was obtained.
Elemental analysis (%): N, 3.58.
Table 1
Operating parameters used for recording AAS for different metal ionsa
Metal ion

Lamp current (mA)

Slit width (nm)

Wavelength (nm)

Ag+

4.0
3.0
3.0
3.0
5.0
5.0
4.0
7.0

0.5
0.5
0.2
0.5
0.2
0.5
0.2
0.2

338.1
228.8
217.9
253.7
279.8
283.3
232.0
248.3

Cd2+
Cu2+
Hg2+
Mn2+
Pb2+
Ni2+
Fe3+
a

The flame type of AAS used in this paper was air-acetylene (oxidizing).

C. Ji et al. / Talanta 73 (2007) 195201

197

Scheme 1. Synthetic route of the resin.

Resin I (32 g) was reacted with 2-mercaptoethanol in a mixture of ethanol and hydrochloric acid (2:1, v/v) at 50 C for 72 h.
Then the product was filtered off and washed with distilled water
and ethanol. After drying under vacuum at 50 C, 37.0 g of resin
II was obtained. Elemental analysis (%): N, 2.94; S, 15.33.
Resins III and IV were synthesized according to the same
reaction condition described in literature [24]. 5.5 g of resin
II were swollen in 100 ml of acetone for 30 min, then 11.2 g
of hydrogen peroxide was added dropwise within 10 min. The
mixture was stirred mechanically for 6 h. Then the reaction was
heated to reflux for 2 h. Finally, the product was filtered off and
washed with distilled water and ethanol and then was dried under
vacuum at 50 C. 6.1 g of resin III was obtained. Elemental
analysis (%): N, 2.55; S, 14.12.
A mixture of 6.0 g of resin III and 100 ml of pyridine was
cooled in an ice-water bath, and 20.6 ml of BsCl was added
dropwise. The mixture was stirred at room temperature for 24 h.
Then the reaction were filtered and washed with distilled water
and ethanol and then was dried under vacuum at 50 C. 6.7 g
of resin IV was obtained. Elemental analysis (%): N, 2.52; S,
13.94.
At the last step, resin IV (6.5 g), 2-mercaptobenzothiazole
(14.7 g) and K2 CO3 (4.1 g) were suspended in DMF (150 ml),
the mixture was stirred at 85 C for 24 h. Then the reaction was
filtered off and washed with distilled water, ethanol and dried
under vacuum at 50 C. 5.7 g of resin V was obtained. Elemental
analysis (%): N, 3.16; S, 13.47.
2.3. Water regain
Water regain was defined as the amount of water absorbed by
1 g of polymer [20]. It was measured according to the method:
approximately 1 g of the resin was stirred in double distilled
water for 48 h, then filtered off by suction, weighted, dried
at 80 C for 48 h. After cooling in a desiccator, the resin was
reweighed. The water regain was calculated as (mw md )/md ,
where mw was the weight of water swollen polymer and md was
the dry weight.
2.4. Resin stability test
Fifty milligrams of the resin was shaken continuously with
25 ml of 15 M hydrochloric acid or alkaline solutions, respec-

tively for 7 days, then filtered off and washed with distilled water
until neutral. After drying, the adsorption capacity of the resin
for Hg2+ was measured by batch method.
2.5. Batch experiment
Thirty milligrams of the resin was added to 20 ml of metal ion
solution (5 103 M) adjusted to the desired pH and the mixture
was shaken for 24 h at 25 C. The mixture was filtered off and
the concentration of the solution was determined by FAAS. The
adsorption capacities were calculated according to the following
equation:
Q=

(C0 C)V
W

where Q is the adsorption amount (mmol g1 ); C0 and C are

the initial concentration and the concentration of metal ion in
solution when the adsorbent is separated (mmol ml1 ); V is the
volume (ml); W is the dry weight of resins (in g).
2.6. Adsorption kinetic
The adsorption kinetics was determined according to the following procedure: 20 ml of metal ion solution (5 103 M) was
shaken with 30 mg of the resin at room temperature. At predetermined intervals, aliquots of 1 ml solution were withdrawn for
analysis and the concentration of metal ion was determined by
FAAS. The loading half time t1/2 , i.e. the time required to reach
50% of the resin total loading capacity was estimated from the
resulting isotherm.
2.7. Effect of diverse metal ions on adsorption capacities
One hundred milligrams of the resin was shaken with 20 ml
of standard solutions of Hg2+ , Ag+ (10 g ml1 each) and
25 ml of diverse metal ion solutions containing the alkali and
alkaline earth metal ions (80 g ml1 each). After 24 h, the
resin sorbed metal ions was separated and completely eluted,
the concentration of metal ion in the eluent was measured
by FAAS.

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C. Ji et al. / Talanta 73 (2007) 195201

2.8. Separation of Hg2+ and Ag+ from several binary

mixtures
Separation of Hg2+ and Ag+ from several binary mixtures was
performed by batch and column operation. The batch experiment
was same as described above except for the amount of the resin
was 200 mg instead of 100 mg. In column operation, a column of
length 5 cm and 0.4 cm inner diameter was packed with 300 mg
of the resin. The resin column was equilibrated by passing 30 ml
of 0.1 M acetate buffer solution of an appropriate pH. In batch
operation, a 40 ml solution containing 250 g of Ag+ or Hg2+
and the interfering ions (500 g each) was shaken for 24 h with
200 mg resin. In column operation, solutions of same amount of
binary mixtures were passed through the resin at a flow rate of
0.25 ml min1 . After eluting the metal ion sorbed on the resin
with 10 ml of 5% thiourea in 0.1 M HNO3 , the concentration of
metal ion in eluent was determined by FAAS.
2.9. Removal of Hg2+ from river and ground water
River and ground water were employed for the removal of
Hg2+ in this experiment. To river water or ground water Hg2+
solution was added to make a solution of the concentration
of mercury of 2 g ml1 . This solution was passed through
the glass column having 300 mg of the resin at a flow rate of
0.25 ml min1 . The metal ion sorbed on the resin was eluted
with eluting agents, and then the amount of metal ion in eluent
was determined by FAAS.
2.10. Removal of Hg2+ from industrial wastewater
The industrial wastewater was collected in pre-washed
polyethylene bottles from Goldentide Battery Co. Ltd. (Yantai,

China). The sample was immediately filtered through a Millipore cellulose nitrate membrane (45 m), acidified to pH 2.0
with 2.0 mol l1 HNO3 and neutralized and then buffered to
the desired pH. The content of the sample was determined by
FAAS. For separation, 100 ml of the sample was passed through
the column containing 300 mg of the resin. Hg2+ was subsequently eluted with 10 ml of 5% thiourea in 0.1 M HNO3 , the
concentration of Hg2+ in eluent was determined by FAAS.

3. Results and discussion

3.1. Characterization of the resin
Fig. 1 showed the infrared spectra of PS-Cl and resins IV.
By comparison with the curve of PS-Cl, the characteristic peak
of 1265 and 675 cm1 almost disappeared in the curve of resin
I, and a new strong band appeared at 1697 cm1 , which was the
characteristic absorbance of C O group [23], indicating that the
aldehyde group had been introduced into the polymeric matrix
successfully. The data of elemental analysis indicated that the
nitrogen contents in resins IIV were 3.58, 2.94, 2.55 and 2.52%,
respectively. The existence of nitrogen could be ascribed to the
incomplete conversion of the intermediate (a) in the formation
of resin I (shown as Scheme 2). Resin II was characterized by
the absence of the absorbance of C O and the presence of a
band at 1046 cm1 corresponding to C OH group. The sulphur
content found by elemental analysis in resin II (4.79 mmol g1 )
indicated that more than 43.6% of the chloromethyl groups were
functionalized. In the spectrum of resin III, a strong absorption
peak at 1039 cm1 belonging to the characteristic absorbance of
S O was observed [25], which indicated that the sulphide had
been oxidized into sulfoxide. Resin IV was confirmed by the
presence of two bands at 1187 and 614 cm1 belonging to the

Fig. 1. FTIR spectra of PS-Cl and resins IV.

C. Ji et al. / Talanta 73 (2007) 195201

199

Table 2
Adsorption capacity of the resin for different metal ions vs. pH (mmol g1 )

Scheme 2. The formation mechanism of resin I.

characteristic absorbance of benzenesulfonate. In the spectrum

of resin V, the absorption bands at 1455 and 1424 cm1 due to
the skeletal vibration of the benzothiazole group were observed
[18]. Sulphur content for resin V was 13.47%, which meant the
functional group of MBZ was 1.40 mmol g1 .
The chemical stability was evaluated by measuring the
change of adsorption capacity of the resin for Hg2+ after successive contact of the resin with acid or alkali solutions in the various
concentration ranges. No obvious decrease in the adsorption
capacity of Hg2+ was observed. These experimental results indicated that the resin was sufficiently stable in acidic and alkaline
solutions.
The adsorption kinetic of the resin for Hg2+ and Ag+ was
determined at the corresponding pH of maximum adsorption.
The results were shown in Fig. 2. The t1/2 of the resin for Hg2+
and Ag+ was 30 and 35 min, respectively. The water regain value
of the resin was 35.6 mmol g1 . All these data showed that the
resin was quite suitable for column operation at a low flow rate.
3.2. Adsorption capacities for metal ions
The adsorption capacities of the resin for different metal
ions were determined by batch method at various pH values. The results were tabulated in Table 2. From Table 2,
it could be noted that the adsorption capacities of the
resin for the metal ions decreased in the following order:
Hg2+ > Ag+ > Cu2+ > Pb2+ > Cd2+ > Fe3+ > Ni2+ > Zn2+ > Mn2+ .

pH

Ag+

Cu2+

Hg2+

Zn2+

Pb2+

Ni2+

Cd2+

Fe3+

Mn2+

1.0
2.0
3.0
4.0
5.0
6.0

0.71
0.66
0.71
0.77
0.95
0.96

0.58
0.54
0.51
0.39
0.47
0.46

1.49
1.36
1.23
1.31
1.28
1.35

0.09
0.07
0.05
0.07
0.08
0.11

0.13
0.31
0.27
0.35
0.25
0.37

0.11
0.14
0.07
0.09
0.19
0.24

0.15
0.18
0.24
0.16
0.35
0.36

0.18
0.13
0.17
0.16
0.21
0.25

0
0
0
0
0
0

The highest adsorption capacities for Hg2+ and Ag+ were

1.49 and 0.96 mmol g1 , respectively. These results could be
interpreted as follows: according to the theory of soft and
hard acids and bases (SHAB), ligands with soft type donors
prefer interactions with soft, i.e. large and more easily
polarizable, acceptors such as noble and heavy metal ions [26].
The functional groups of sulfoxide and MBZ presented in
the investigated resin belong to soft bases, thus the resin had
higher adsorption capacities for Hg2+ and Ag+ than that for
Cu2+ , Pb2+ , Cd2+ , Fe3+ , Ni2+ , Zn2+ and Mn2+ , which were base
metal ions. One could observe that, Mn2+ was not recognized
by the resin. The reason for this could be ascribe to the low
accepting ability of Mn2+ with chelating group described by
Irving-Williams series [27].
As could be seen in Table 2, the pH values had a slight effect
on the adsorption capacities of the resin for the metal ions. The
maximum adsorption capacities of the metal ions were obtained
under the optimal pH 1.0 for Hg2+ and Cu2+ , 6.0 for Ag+ , Pb2+ ,
Cd2+ , Ni2+ , Zn2+ and Fe3+ in this paper.
3.3. Separation of Hg2+ and Ag+ from alkali and alkaline
earth metal ions
Separation of Hg2+ and Ag+ from several binary mixtures
with alkali and alkaline earth metal ions at their corresponding
maximum pH was carried out. The recovery of Hg2+ and Ag+
were 100% and 96+%, respectively. As could be expected that,
the presence of large excess of alkali and alkaline earth metal
ions did not affect the recovery of Hg2+ and Ag+ from the solution, which meant that the resin could be used for removal of
trace mercury and silver from natural samples.
3.4. Separation of Hg2+ and Ag+ from binary mixtures

Fig. 2. Adsorption rate curve of the resin for Hg2+ and Ag+ .

The ability to remove particular metal ions selectively from

aqueous solution under competitive condition is of utmost
importance in designing a resin for environmental remediation
applications. The recovery of Hg2+ and Ag+ by the resin in
the presence of diverse metal ions such as Cu2+ , Zn2+ , Pb2+ ,
Ni2+ , Cd2+ , Fe3+ and Mn2+ was determined by batch and column method. The results were shown in Table 3. From Table 3, it
could be seen that the recovery of the resin for Hg2+ and Ag+ was
96.3+%, 94.5+%, respectively. The experimental results showed
that the resin could remove Hg2+ and Ag+ from aqueous solution quantitatively, even in the presence of two-fold excess of
competing metal ions.

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C. Ji et al. / Talanta 73 (2007) 195201

Table 3
Separation of Hg2+ and Ag+ from binary mixtures at corresponding pH of maximum adsorptiona
Metal ion

Recovery (%)
Ag(I)

Hg(II)

Batch method
Cu2+
Zn2+
Pb2+
Ni2+
Cd2+
Mn2+
Fe3+

95.7
98.3
95.4
98.8
98.9
97.1
95.3

1.5
1.4
1.1
2.3
3.5
2.3
1.6

Column method
97.0
98.6
100
98.7
97.6
98.3
94.5

2.3
2.7
2.6
3.1
2.5
1.4
2.0

Batch method
97.5
98.8
100
98.7
98.5
99.2
96.3

1.3
2.9
1.5
4.2
2.3
1.8
3.3

Column method
98.6
99.0
99.6
99.4
98.6
100
97.8

1.4
3.4
2.3
2.7
3.4
5.6
4.3

The amount of Hg2+ and Ag+ in binary mixture was 250 g and the amount of interferences such as Cu2+ , Zn2+ , Pb2+ , Ni2+ , Cd2+ , Fe3+ and Mn2+ was 500 g,
respectively.
a

Table 4
Recovery of Hg2+ from natural waters and industrial wastewater
Sample

Measured value (g l1 )

Amount spiked (g)

Amount recovered (g)

River water
River water
Ground water
Ground water
Wastewater

0.1
0.1
0.05
0.05
538.4

50.0
100.0
50.0
100.0

49.6
98.5
50.0
99.1
50.0

3.5. Removal of Hg2+ from natural waters and industrial

wastewater
Experiments on the recovery of Hg2+ were carried out
using column method. Before the natural waters and industrial
wastewater were used, the contents of Hg2+ were determined by
using Semi-automatic sequential injection hydride generation
double-channel atomic fluorescence spectrometer and FAAS.
From Table 4, it could be seen that the recovery of Hg2+ was
92.9+%, which meant the trance amount of Hg2+ could be
recovered quantitatively with the resin from natural waters and
industrial wastewater.
4. Conclusions
A new chelating resin containing bis[2-(2-mercaptobenzothiazolylethyl)sulfoxide] was synthesized and characterized. It
was stable in acidic and alkaline medium. The resin had high
affinity for Hg2+ and Ag+ . The presence of alkali or alkaline
earth metal ions such as Na+ , Mg2+ , Ca2+ and Ba2+ had no
effect on the recovery of Hg2+ and Ag+ . This resin could efficiently remove Hg2+ and Ag+ from binary mixtures in batch
and column method. The recovery of the resin for Hg2+ and
Ag+ were 96.3+% and 94.5+%, respectively. The recovery of
Hg2+ from spiked natural waters and industrial wastewater was
92.9+%.
Acknowledgements
The authors are grateful for the financial support by
the Nature Science Foundation of Shandong Province (No.

3.9
1.5
1.8
1.9
2.3

Recovery (%)
99.2
98.5
100.0
99.1
92.9

7.8
1.5
3.6
1.9
2.3

Y2005F11), the Postdoctoral Science Foundation of China (No.

2003034330), the Nature Science Foundation of Ludong University (Nos. 032912, 20052901, 042920).
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