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Abstract
Composite materials formed by the combination of inorganic ion exchangers of multivalent metal acid salts and organic
conducting polymers (polyaniline, polypyrrole, polythiophene, etc.), providing a new class of organicinorganic hybrid ion
exchangers with better mechanical and granulometric properties, good ion-exchange capacity, higher stability, reproducibility
and selectivity for heavy metals. Such a type of ion exchanger polyaniline Sn(IV) tungstoarsenate was developed by
mixing polyaniline into inorganic precipitate of Sn(IV) tungstoarsenate. This material was characterized using atomic
absorption spectrometry, elemental analysis, Fourier transform infrared spectroscopy, simultaneous thermogravimetry
differential thermogravimetry, X-ray and scanning electron microscopy studies. Ion-exchange capacity, pH-titrations, elution
and distribution behavior were also carried out to characterize the material. On the basis of distribution studies, the material
was found to be highly selective for Cd(II) and its selectivity was tested by achieving some important binary separations like
Cd(II)Zn(II), Cd(II)Pb(II), Cd(II)Hg(II), Cd(II)Cu(II), etc., on its column. Using this composite cation exchanger as
electroactive material, a new heterogeneous precipitate based selective ion-sensitive membrane electrode was developed for
the determination of Cd(II) ions in solutions. The membrane electrode is mechanically stable, with a quick response time,
and can be operated within a wide pH range. The selectivity coefficients for different cations determined by mixed solution
method were found to be less than unity. The electrode was also found to be satisfactory in electrometric titrations.
2003 Elsevier Science B.V. All rights reserved.
Keywords: Organicinorganic composite material; Cation exchanger; Polyaniline Sn(IV) tungstoarsenate; Cd(II) ion-selective membrane
electrode
1. Introduction
Exploration of inorganic ion exchangers is
always of interest because of their applications
*Corresponding author. Fax: 191-571-270-1260.
E-mail address: mezbah@rediffmail.com (A.A. Khan).
1381-5148 / 03 / $ see front matter 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016 / S1381-5148(03)00018-X
278
2. Experimental
other reagents and chemicals were of analyticalreagent grade. A digital pH-meter (Elico LI-10,
India), Fourier transform infrared (FT-IR) spectrophotometer (Nicolet 400D, USA), an automatic thermal analyzer (V2.2A DuPont 9900),
an elemental analyzer (Carlo-Erba 1180), a
double beam atomic absorption spectrophotometer (GBC 902, Australia), an electron
microscope (LEO 435 VP) with attached imaging device, a digital flame photometer (Elico CL
22D, India), a UVVis spectrophotometer (Elico
EI 301E, India), a temperature controlled shaker
and a digital potentiometer (Equiptronics EQ
609, India) with a saturated calomel electrode as
reference electrode were used.
Sample
S-1
279
W
(0.1 M)
As
(0.1 M)
pH of the
inorganic
precipitate
K2S2O8
(0.1 M)
Aniline
(10%)
1.0
Appearance
of beads
after drying
Na 1
ion-exchange
capacity
(mequiv. g 21 )
Greenish
granular
1.67
280
2.5. pH-titration
pH-titrations were performed by the method
of Topp and Pepper [15]. A total of 500 mg
portions of the cation exchanger was placed in
each of the several 250-ml conical flasks,
After dissolving in hot concentrated hydrochloric acid, the sample S-1 was analyzed for
tin and arsenic by AAS and tungsten by a
standard spectrophotometric method. Carbon,
281
Table 1
The solubility of polyaniline Sn(IV) tungstoarsenate in various solvent systems
Solvent
(20 ml)
Sn
(mg / 20 ml)
W
(mg / 20 ml)
As
(mg / 20 ml)
4 M HNO 3
4 M HCl
4 M H 2 SO 4
0.1 M NaOH
0.1 M KOH
1 M NH 3
1 M NH 4 NO 3
1 M CH 3 COOH
1 M CH 3 COONa
1 M Citric acid
1 M Oxalic acid
1 M Formic Acid
Dimethyl sulfide (DMS)
n-Butanol
Acetone
DMW
2.13
5.99
2.03
16.31
24.59
13.84
0.13
0.69
0.51
7.02
13.96
0.21
0.23
0.48
0.07
0.05
0.25
1.03
0.65
13.30
35.86
1.15
0.53
1.28
1.13
1.10
4.40
0.86
0.08
0.19
0.63
0.15
1.27
3.52
1.31
22.07
36.41
6.87
1.80
1.21
2.20
0.94
8.31
3.64
1.48
2.17
0.51
0.45
282
External reference
Uelectrode
(SCE)
that the values of the H 1 -adsorption and H 1 liberation capacities are in close agreement. The
ion-exchange capacity of the composite cation
exchanger for alkali metal ions (except Na 1 )
and alkaline earth metal ions increased according to the decrease in their hydrated ionic radii.
The column elution experiments indicated a
dependence of the concentration of the eluent
on the rate of elution, which is a usual behavior
for such materials. The minimum molar concentration of NaNO 3 as eluent was 1 M for the
maximum release of H 1 ions from 1 g of the
cation exchanger. The elution was appreciably
fast as only 140 ml of the effluent was sufficient
for almost complete elution of the H 1 ions from
its column within 5 h. This material possessed a
better Na 1 ion-exchange capacity (1.67 mequiv.
g 21 ) as compared to simple Sn(IV) tungstoarsenate (1.12 mequiv. g 21 ) and some other similar
materials, i.e., double salts of tetravalent metals,
prepared earlier (Table 2).
The pH-titration curves obtained under
equilibrium conditions for LiOH / LiCl, NaOH /
NaCl and KOH / KCl systems indicated bifunctional behavior of the material as shown in Fig.
1. It appears to be a strong cation exchanger as
indicated by a low pH (|2.5) of the solution
when no OH 2 ions were added to the system.
The rate of H 1 Na 1 exchange was faster than
those of H 1 K 1 and H 1 Li 1 exchanges. The
theoretical ion-exchange capacity for these ions
was found to be |3.2 mequiv. g 21 .
The solubility experiments showed that the
material has reasonably good chemical stability.
As the results indicated that the material was
resistant to 4 M HNO 3 and 4 M H 2 SO 4 with
higher solubility in NH 3 and in alkaline media
and slightly higher solubility in HCl, citric acid
and oxalic acid. The chemical dissolution in
DMW, acetone, DMS, n-butanol, formic acid,
CH 3 COOH, CH 3 COONa, NH 4 NO 3 was almost
negligible. This chemical stability may be due
to the presence of binding polymer, which can
prevent the dissolution of heteropolyacid salt or
leaching of any constituent elements into the
solution. On heating at different temperatures
283
284
Ion-exchange materials
Reagents
Mixing ratio
pH of the
inorganic
precipitates
Na 1 -exchange
capacity
(mequiv. g 21 )
1:1:1:1:1
1.0
1.67
Sn(IV) tungstoarsenate
[18]
2:1:1
1.0
1.06
Sn(IV) tungstoarsenate
(as prepared)
1:1:1
1.0
1.55
1:1:1:1:1
1.0
1.58
2:1:2:1:2
1.02.0
1.46
1:1:1:1
1.0
0.75
1:1:1:1
1.0
0.87
Polyaniline
(as prepared)
10% Aniline10.1 M K 2 S 2 O 8
1:1
0.17
Table 2
Comparison of the preparation and properties of polyaniline Sn(IV) tungstoarsenate with those of other cation exchangers
285
(DTA). The DTA curve indicates two exothermic peaks with maxima at 84.46 and 480.20 8C
that confirm the removal of external water
molecules and structural transformations, respectively.
The FT-IR spectrum of the exchanger in the
H 1 -form indicated the presence of external
water molecules in addition to the OH groups
and metal oxides present internally in the material. In the spectrum two weak broad bands
around 3500 cm 21 are found, which can be
attributed to OH stretching frequency. A
medium band around 1600 cm 21 can be attributed to HOH bending band, being also representative of the strongly bonded OH groups in
the matrix [21]. The OH stretching bands
merge together and are shifted to lower frequency in the spectrum of the exchanger. This is
due to the possibility of H-bonding. The sharp
peak around 1300 cm 21 may represent the
presence of [AsO 4 ] 32 group in the material. The
additional band at about 1400 cm 21 can be
ascribed to stretching vibration of CN [22].
This indicates that the material contains a
considerable amount of aniline. It was also
observed that there is no difference in the FT-IR
spectra between the H 1 -form, Na 1 -form and
original form of the sample S-1 dried at 50 8C.
The molar ratio of Sn, W, As, C, H and N in
the
material
was
estimated
to
be
NH 2) 2 ] ?
nH 2 O
and its structure can be written as:
Assuming that only the external water molecules are lost, at 198 8C the |7.0% weight loss
of mass represented by the TGA curve must be
due to the loss of nH 2 O from the above
structure. The value of n, the external water
molecules, can be calculated using Albertis
equation [23]:
18n 5 X(M 1 18n) / 100
286
A. A. Khan, M.M. Alam / Reactive & Functional Polymers 55 (2003) 277290
Fig. 3. Scanning electron microphotographs of chemically prepared Sn(IV) tungstoarsenate at the magnifications of 1003 and 50003 (a, a9) and polyaniline Sn(IV)
tungstoarsenate at the magnifications of 1003 and 25003 (b, b9).
287
Table 3
Kd -values of some metal ions on polyaniline Sn(IV) tungstoarsenate in different solvent systems
Metal
ion
DMW
1310 23 M
HNO 3 ,
pH 3
1310 22 M
HNO 3 ,
pH 2
1310 21 M
HNO 3 ,
pH 1
0.1 M CH 3 COOH1
0.1 M CH 3 COONa
(1:2)
0.1 M CH 3 COOH1
0.1 M CH 3 COONa
(2:1)
0.1 M HNO 3 1
0.1 M NH 4 NO 3
(1:1)
Na 1
K1
Mg 21
Ca 21
Sr 21
Ba 21
Cu 21
Ni 21
Pb 21
Cd 21
Mn 21
Zn 21
Hg 21
Co 21
Bi 21
Cr 31
Al 31
Fe 31
La 31
Th 41
Ce 41
Ag 1
UO 21
2
1
Tl
36
446
33
117
198
440
180
400
203
2920
233
263
133
300
1000
767
86
100
225
340
122
67
75
155
33
525
35
123
140
333
180
233
600
4228
267
350
367
275
2200
475
71
83
170
360
114
92
85
100
100
485
35
38
39
180
170
180
100
1400
141
281
350
44
1100
191
40
43
155
300
75
114
107
117
21
295
10
32
38
50
56
25
64
450
71
275
300
30
1000
40
44
22
63
266
40
74
130
86
9
148
84
238
767
2500
240
300
900
544
650
400
833
550
138
38
250
300
550
130
133
44
160
100
12
192
105
217
600
2600
600
700
500
810
700
2067
1500
600
600
200
440
400
767
210
300
86
245
130
20
35
5
114
14
25
8
33
210
27
50
120
243
83
667
36
140
69
13
92
7
18
56
30
288
Table 4
Some binary separations of metal ions achieved on the polyaniline Sn(IV) tungstoarsenate column
Separations
achieved
Amount loaded
(mg)
Amount found
(mg)
% Error
Eluent
used
Volume of
eluent (ml)
Cd(II)
Zn(II)
1686.0
980.85
1663.5
993.9
21.4
11.3
A
B
40
50
Cd(II)
Pb(II)
1967.0
2591.3
1967.0
2621.1
0.0
21.2
A
C
50
50
Cd(II)
Hg(II)
1742.2
1905.7
1719.7
1935.8
21.3
11.6
A
B
40
50
Cd(II)
Mg(II)
1124.0
364.7
1107.1
370.7
21.5
11.7
A
B
40
60
Cd(II)
Cr(III)
1686.0
780.0
1674.7
790.2
20.7
11.3
A
D
40
60
Cd(II)
Cu(II)
1124.0
635.5
1135.2
627.9
11.0
21.2
A
C
40
50
Mg(II)
Ba(II)
243.1
1373.0
243.1
1359.3
0.0
21.0
B
C
40
50
A50.1 M HNO 3 ; B5DMW; C50.1 M HNO 3 10.1 M NH 4 NO 3 (1:1); D50.1 M CH 3 COOH10.1 M CH 3 COONa (1:2).
Electrode
Polyaniline Sn(IV)
tungstoarsenate
289
n1
Selectivity coefficients (K POT
)
Cd.M ) for interfering cations (M
Na 1
K1
Mg 21
Ca 21
Sr 21
Cu 21
Mn 21
Zn 21
Pb 21
Hg 21
Al 31
Fe 31
0.02
0.03
0.02
0.06
0.08
0.09
0.03
0.04
0.18
0.07
0.04
0.05
Acknowledgements
The authors are thankful to the Department of
Applied Chemistry, Z.H. College of Engineering and Technology, Aligarh for providing
research facilities, and Central Drug Research
Institute (Lucknow) and Regional Sophisticated
Instrumentation Center (Nagpur) for technical
assistance.
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