Reactive & Functional Polymers 55 (2003) 277290

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Synthesis, characterization and analytical applications of a new

and novel organicinorganic composite material as a cation
exchanger and Cd(II) ion-selective membrane electrode:
polyaniline Sn(IV) tungstoarsenate
Asif Ali Khan*, M. Mezbaul Alam
Analytical and Polymer Research Laboratory, Department of Applied Chemistry, Faculty of Engineering and Technology,
Aligarh Muslim University, Aligarh 202 002, India
Received 29 July 2002; received in revised form 18 October 2002; accepted 19 February 2003

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).

in diverse fields such as purification of nuclear

reactor cooling water at high temperature and
pressure, development of ion-selective electrodes, construction of ion-exchange membranes
and their applications to electrodialysis, extraction of uranium from sea water and separation
of metal ions, etc. Advancement in inorganic

1381-5148 / 03 / $ see front matter 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016 / S1381-5148(03)00018-X

278

A. A. Khan, M.M. Alam / Reactive & Functional Polymers 55 (2003) 277290

ion exchangers is not only due to their high

thermal stability and resistivity towards radiation fields but also for their unusual selectivity
for ionic species and versatility in separation.
Inorganic ion exchangers of double salts, based
on tetravalent metal acid (TMA) salts often
exhibit much better ion-exchange behavior as
compared with single salts [1]. Derivatization of
inorganic ion exchangers by organic molecules
depends on the nature of the inorganic matrix.
TMA salts can be derivatized by organic moieties bearing inorganic groups such as OH,
COOH, SO 3 H, NH 2 , etc., which also act as
ion exchangers, and are known as organoinorganic ion exchangers or as derivatized tetravalent metal acid (DTMA) salts. Many organic
inorganic composite ion exchangers have been
developed earlier by incorporation of organic
monomers in the inorganic matrix, by way of
pillaring or non-pillaring methods [213].
Efforts have been made to improve the
chemical, thermal and mechanical stability of
ion exchanger and to make them highly selective for certain metal ions. An inorganic ion
exchanger based on organic polymeric matrix
must be an interesting material, as it should
possess the mechanical stability due to the
presence of organic polymeric species and the
basic characteristics of an inorganic ion exchanger regarding its some selectivity for some
specific metal ions. It was therefore considered
to synthesize such hybrid ion exchangers with a
good ion-exchange capacity, high stability, reproducibility and selectivity for heavy metal
ions, indicating its useful environmental application. A number of organicinorganic composite samples of polyaniline Sn(IV) tungstoarsenate have been synthesized in our laboratory.
Cadmium is considered as highly toxic element and responsible for several cases of
poisoning through water, food and smoking.
When excessive amounts of Cd 21 are ingested,
it replaces Zn 21 at key enzymatic sites, causing
metabolic disorders, kidney damage, renal
dysfunction, anemia, hypertension, bone marrow disorders, cancer and toxicity to aquatic
biota. Cadmium is released into the atmosphere

from smelters and factories processing Cd and

also from the incineration or disposal of cadmium-bearing products. Cadmium enters natural
water through industrial discharges mainly from
electroplating industry and nickelcadmium
battery industry or the deterioration of galvanized water pipes. Cd is therefore a potential
pollutant in the environment. The utility of this
composite ion exchanger has been explored for
the quantitative separation of Cd 21 from some
binary mixtures on its column.
Precipitate based ion-selective membrane
electrodes are well known as they are successfully employed for determination of several
anions and cations [14]. The ion-exchange
membranes obtained by embedding ion exchangers as electroactive materials in a polymer
binder, i.e., epoxy resin (Araldite) or polystyrene or poly(vinyl chloride) (PVC), have
been extensively studied as potentiometric sensors, i.e., ion sensors, chemical sensors or more
commonly ion selective electrodes. Besides the
electrodes that respond directly to the change in
concentration of particular ion for which it is
made, a number of electrodes are used for
indirect determination of certain ions. An attempt has also been made to obtain a new
heterogeneous precipitate based membrane electrode by using the polyaniline Sn(IV) tungstoarsenate composite cation exchanger as electroactive material for the determination of
Cd(II) ions present in the solutions. This paper
presents the preparative conditions, ion-exchange properties, physicochemical properties
and analytical applications of this organicinorganic composite material used as a cation
exchanger and Cd(II) ion-selective membrane
electrode.

2. Experimental

2.1. Reagents and instruments

The main reagents used for the synthesis of
the material were obtained from CDH, Loba
Chemie, E-Merck and Qualigens (India). All

A. A. Khan, M.M. Alam / Reactive & Functional Polymers 55 (2003) 277290

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.

2.2. Preparation of the reagent solutions

0.1 M Sodium arsenate (Na 2 HAsO 4 ? 7H 2 O)
and sodium tungstate (Na 2 WO 4 ? 2H 2 O) were
prepared in demineralized water (DMW) while
0.1 M stannic chloride (SnCl 4 ? 5H 2 O) was
prepared in 4 M HCl. Solutions of 10% (v / v)
doubly distilled aniline (C 6 H 5 NH 2 ) and 0.1 M
potassium persulphate (K 2 S 2 O 8 ) were prepared
in 1 M HCl.

2.3. Preparation of polyaniline Sn( IV)

tungstoarsenate
At first, green colored polyaniline gels were
obtained by mixing the acidic solutions of 10%
aniline (C 6 H 5 NH 2 ) and 0.1 M potassium persulfate (K 2 S 2 O 8 ) in different volume ratios with
continuous stirring by a magnetic stirrer below
10 8C for an hour. Inorganic precipitate ion
exchanger gels of Sn(IV) tungstoarsenate were
prepared at room temperature (2562 8C) by

Sample

S-1

279

adding the solution of 0.1 M stannic chloride to

an aqueous mixture of 0.1 M sodium arsenate
and 0.1 M sodium tungstate in different volume
ratios and at different pH values. The white
precipitates were obtained when the pH of the
mixture was adjusted by adding ammonia water
with constant stirring.
After this, the gel of polyaniline was added to
the inorganic precipitate of Sn(IV) tungstoarsenate and mixed thoroughly with constant stirring. The resultant green colored gel was allowed to settle overnight at room temperature
(2562 8C). The supernatant liquid was decanted
and the gel was filtered under suction and
washed with 1 M HNO 3 to remove excess
reagent. The excess acid was removed by
washing with DMW and again washed with
acetone by soxhlation. The materials were dried
in an air oven at 50 8C for 48 h. The dry
products were crushed into small granules of
uniform size suitable for column separations
when immersed in DMW. They were then
treated with large excess of 1 M HNO 3 for 24 h
at room temperature with occasional shaking,
intermittently replacing the supernatant liquid
with a fresh acid to ensure the complete conversion to the H 1 -form. The excess acid was
removed after several washing with DMW. The
materials were finally dried at 50 8C in the oven,
sieving to obtain particles of a particular size
range ( | 125 mm) and kept in a desiccator.
Hence, a number of samples of polyaniline
Sn(IV) tungstoarsenate were prepared by changing the mixing volume ratios of the reagents. On
the basis of appearance, percentage of yield,
Na 1 ion-exchange capacity and reproducibility,
following sample was chosen for further
studies:

Mixing volume ratio

Sn
(0.1 M)

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

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A. A. Khan, M.M. Alam / Reactive & Functional Polymers 55 (2003) 277290

2.4. Ion-exchange capacity

A 1-g amount of the dry cation exchanger,
sample S-1 in the H 1 -form was placed in a
glass column having an internal diameter (I.D.)
| 1 cm and fitted with glass wool support at the
bottom. The bed length was approximately 1.5
cm long. 1 M alkali and alkaline earth metal
nitrates as eluents were used to elute the H 1
ions completely from the cation-exchange column, maintaining a very slow flow rate ( | 0.5
ml min 21 ). The effluent was titrated against a
standard (0.1 M) NaOH solution and the ionexchange capacities in mequiv. g 21 were as
follows: Li 1 , 1.46; Na 1 , 1.67; K 1 , 1.54; Mg 21 ,
1.73; Ca 21 , 1.78; Sr 21 , 1.86 and Ba 21 , 2.03.

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,

followed by equimolar solutions of alkali metal

chlorides and their hydroxides in different volume ratio, the final volume being 50 ml to
maintain the ionic strength constant. The pH of
the solution was recorded every 24 h until
equilibrium was attained which needed | 5
days, and pH at equilibrium was plotted against
the milliequivalents of OH 2 ions added. The
results are shown in Fig. 1.

2.6. Chemical dissolution

Portions (250 mg) of the cation exchanger in
the H 1 -form were equilibrated with 25 ml each
of different acids (such as HCl, HNO 3 , H 2 SO 4 ,
acetic acid, formic acid, oxalic acid and citric
acid); bases (such as NaOH, KOH); organic
solvents (such as n-butanol, acetone, dimethyl
sulfide) and also NH 3 and DMW for 24 h with
occasional shaking. The supernatant liquid was
analyzed for tin and arsenic by atomic
absorption spectrophotometry (AAS), while
tungsten was analyzed by the Vis spectrophotometric method [16]. The results are summarized in Table 1.

2.7. Thermal stability

To study the effect of drying temperature on
the ion-exchange capacity, 1-g samples of the
1
material in the H -form were heated at various
temperatures in a muffle furnace for 1 h each
and the Na 1 ion-exchange capacity was determined by column process after cooling them
at room temperature. The results in mequiv. g 21
are given below: 1.67 (50 8C); 1.43 (100 8C);
1.27 (200 8C); 0.92 (400 8C); 0.78 (500 8C);
0.59 (600 8C).

2.8. Chemical composition

Fig. 1. pH-titration curves for polyaniline Sn(IV) tungstoarsenate

composite cation exchanger with various alkali metal hydroxides.

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,

A. A. Khan, M.M. Alam / Reactive & Functional Polymers 55 (2003) 277290

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

hydrogen and nitrogen contents of the material

were determined by elemental analysis. The
percent composition of the material was: Sn,
7.60; W, 11.85; As, 37.14; C, 9.00; H, 1.79; N,
1.41.

2.9. Selectivity studies

The distribution coefficients (Kd -values) of
metal ions on the sample material (S-1) were
determined by the batch method in various
solvent systems. Various 200-mg portions of the
exchanger in the H 1 -form were taken in Erlenmeyer flasks with 20 ml different metal nitrate
solutions in the required medium and kept for
24 h with intermittent shaking or continuous
shaking for 6 h in a shaker at 2562 8C to attain
equilibrium. The initial metal ion concentration
was so adjusted that it did not exceed 3% of its
total ion-exchange capacity. The metal ions in
the solutions before and after equilibrium were
determined by EDTA titration [17]. The alkali
and alkaline earth metal ions (K 1 , Na 1 , Ca 21 )
were determined by flame photometry and some
heavy metal ions, such as Pb 21 , Cd 21 , Cu 21 ,
Cr 31 , Hg 21 , Ni 21 , Mn 21 and Zn 21 were determined by AAS. Distribution coefficients were
calculated using the formula given as:

mmol of metal ions / g of ion exchanger

Kd 5 ]]]]]]]]]]]]
mmol of metal ions / ml of solution
(ml g 21 )
21

i.e., Kd 5(I2F ) /F 3V /M (ml g ), where I is

the initial amount of metal ion in the aqueous
phase, F is the final amount of metal ion in the
aqueous phase, V is the volume of the solution
(ml) and M is the amount of cation exchanger
(g).

2.10. Quantitative separation of metal ions

Quantitative separations of some important
metal ions of analytical utility were achieved on
polyaniline Sn(IV) tungstoarsenate (sample S1) column. A 2-g amount of the cation exchanger in the H 1 -form was packed in an open
glass column (35 cm height and |0.6 cm I.D.).
After washing the column thoroughly with
DMW, the mixture of two metal ions of 0.01 M
each, was loaded on it, and was allowed to pass
gently (maintaining a flow rate of 23 drops /
min) until the level was above the surface of the
material. The process was repeated two or three
times to ensure complete adsorption of the
mixture on bead. The separation was achieved
by passing a suitable solvent at a flow rate of 1

A. A. Khan, M.M. Alam / Reactive & Functional Polymers 55 (2003) 277290

282

ml min 21 through the column as eluent. The

metal ions in the effluent were determined
quantitatively by AAS and EDTA titration.

2.11. Fabrication of ion selective electrode

The cation exchanger (100 mg) was ground
to a fine powder, and was mixed thoroughly
with Araldite (Ciba-Geigy) (100 mg) on Whatmans filter paper No. 42, and a master membrane of 0.35 mm thickness was prepared. A
piece of membrane was cut out and fixed at one
end of a pyrex glass tube (0.8 cm O.D.30.6 cm
I.D.) with Araldite. The tube was filled with 0.1
M cadmium nitrate. A saturated calomel electrode was inserted in the tube for electrical
contact and another saturated calomel electrode
was used as external reference electrode. The
whole arrangement can be shown as:

Internal reference Internal electrolyte

electrode (SCE) (0.1 M Cd 21 )

External reference
Uelectrode
(SCE)

Membrane Sample solution

In advance of measurements of the electrode

potential (at 2562 8C) for a series of standard
27
21
solutions of Cd(NO 3 ) 2 (10 M10 M), the
membrane of the electrode was conditioned by
soaking in 0.1 M Cd(NO 3 ) 2 solution for 7 days
and for 1 h at least before use. In order to study
the characteristics of the electrode, the following parameters were evaluated: lower detection
limit, slope response curve, response time and
working pH range.

reproducible behavior and chemical and thermal

stability.
Polyaniline gel was prepared by oxidative
coupling using K 2 S 2 O 8 in acidic aqueous
medium as given in the following reaction:

The effect of temperature on the reaction

seems to be very pronounced. Aniline under
went oxidative coupling only at below 10 8C
very efficiently, leading to a good quantity of
polyaniline with fairly good yield. The formation of inorganic precipitate Sn(IV) tungstoarsenate was significantly affected by the pH of the
mixture, and the most favorable pH of the
mixture was |1.0. The preparation of the
inorganic precipitate at pH lower or higher than
1.0 lead to decrease in yield and ion-exchange
capacity of the material. The mixing volume
ratio of the mixture is also critical. The binding
of polyaniline into the matrix of Sn(IV) tungstoarsenate can be shown as:

3. Results and discussion

In this work, various samples of new and
novel polyaniline based organicinorganic
composite ion-exchange materials were developed by incorporating polyaniline into inorganic matrices of Sn(IV) tungstoarsenate.
Among them, sample S-1 possessed high percentage of yield, better ion-exchange capacity,

However, sample S-1 of polyaniline Sn(IV)

tungstoarsenate exhibited high granulometric
and mechanical properties, showing a good
reproducible behavior as is evident from the fact
that these materials obtained from various batches did not show any appreciable deviation in
their ion-exchange capacities. It was also found

A. A. Khan, M.M. Alam / Reactive & Functional Polymers 55 (2003) 277290

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

for 1 h, the ion-exchange capacity of the dried

material decreased as the temperature increased.
However, the material was found to possess
higher thermal stability as it maintained about
55% of the initial ion-exchange capacity by
heating up to 400 8C. From a comparative study
of heating effect on Na 1 ion-exchange capacity
of polyaniline Sn(IV) tungstoarsenate with
those of other ion exchangers, as shown in Fig.
2, it is apparent that this composite cation
exchanger is more thermally stable than others.
Scanning electron microscopy (SEM) photographs of Sn(IV) tungstoarsenate and polyaniline Sn(IV) tungstoarsenate obtained at different
magnifications (Fig. 3), indicating the binding
of inorganic ion-exchange material by organic
polymer, i.e., polyaniline. It has been revealed
that Sn(IV) tungstoarsenate shows a plate like
morphology. After the binding of polyaniline
with Sn(IV) tungstoarsenate, the morphology
has been changed. The detail analysis of these
SEM photographs informs that its particle size
may be about 3.0 mm. The X-ray powder
diffraction pattern of this cation exchanger in
original form (sample S-1) clearly exhibited the
presence of two sharp peaks with d-values 3.31
and 1.66 A
at angles (2u ) 26.915 and
A
55.2108, respectively, that suggesting a
semicrystalline nature of the material.
The thermogravimetry (TGA) analysis curve
(Fig. 4) of the material showed a continuous
weight loss of mass (about 6.0%) up to 198 8C,
which may be due to the removal of the external
water molecules [20]. An inflection point observed at 99.01 8C may be due to the formation
of As 2 O 5 by removal of water molecules from
initial composition As 2 O 5 ?nH 2 O. Slow weight
loss observed between 200 8C and 271 8C may
be due to a slow decomposition of the material.
Further weight loss between 275 8C and 672 8C
may be due to complete decomposition of the
organic part of the material. At 675 8C onwards
a smooth horizontal section which represents
the complete formation of the oxide form of the
material. These transformations have also been
supported by differential thermal analysis

284

Ion-exchange materials

Reagents

Mixing ratio

pH of the
inorganic
precipitates

Na 1 -exchange
capacity
(mequiv. g 21 )

Polyaniline Sn(IV) tungstoarsenate

(sample S-1)

0.1 M Tin(IV)chloride10.1 M sodium tungstate10.1 M sodium

arsenate110% aniline10.1 M K 2 S 2 O 8

1:1:1:1:1

1.0

1.67

Sn(IV) tungstoarsenate
[18]

0.25 M Tin(IV)chloride10.25 M sodium tungstate10.25 M sodium arsenate

2:1:1

1.0

1.06

Sn(IV) tungstoarsenate
(as prepared)

0.1 M Tin(IV)chloride10.1 M sodium tungstate10.1 M sodium arsenate

1:1:1

1.0

1.55

Polyaniline Sn(IV) arsenophosphate

[13]

0.1 M Tin(IV)chloride10.1 M sodium arsenate10.1 M H 3 PO 4 1

10% aniline10.1 M (NH 4 ) 2 S 2 O 8

1:1:1:1:1

1.0

1.58

Polyaniline Zr(IV) tungstophosphate

[19]

0.1 M Zirconium oxychloride10.1 M sodium tungstate10.1 M ammonium

sodium hydrogen phosphate1aniline10.4 M (NH 4 ) 2 S 2 O 8

2:1:2:1:2

1.02.0

1.46

Polyaniline Sn(IV) tungstate (as prepared)

0.1 M Tin(IV)chloride10.1 M sodium tungstate110% aniline10.1 M K 2 S 2 O 8

1:1:1:1

1.0

0.75

Polyaniline Sn(IV) arsenate

(as prepared)

0.1 M Tin(IV)chloride10.1 M sodium arsenate110%aniline10.1 M K 2 S 2 O 8

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

A. A. Khan, M.M. Alam / Reactive & Functional Polymers 55 (2003) 277290

Table 2
Comparison of the preparation and properties of polyaniline Sn(IV) tungstoarsenate with those of other cation exchangers

A. A. Khan, M.M. Alam / Reactive & Functional Polymers 55 (2003) 277290

285

Fig. 2. Comparison of heating effect upon ion-exchange capacity.

(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

1:1:1.75:11.71:27.74:1.57, which can suggest

the following tentative formula of the material:
[(SnO 2 )(WO 3 )(As 2 O 5 ) 4 (

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).

A. A. Khan, M.M. Alam / Reactive & Functional Polymers 55 (2003) 277290

Fig. 4. Simultaneous TGADTA curve of polyaniline Sn(IV)

tungstoarsenate (as prepared).

where, X is the percent weight loss (|6.0%) in

the exchanger by heating up to 198 8C, and
(M 118n) is the molecular weight of the materi-

287

al. The calculation gives |5 for the external

water molecules (n) per molecule of the cation
exchanger (sample S-1).
In order to explore the potentiality of the
material in the separation of metal ions, distribution studies for 24 metal ions were performed in seven solvent systems. It is apparent
from the data given in Table 3 that the Kd values can vary with the composition and nature
of the contacting solvents. On the basis of
distribution studies, the most promising property
of the material was found to be the high
selectivity towards Cd(II), which is a major
polluting metal in the environment. The separation capability of the material has been demonstrated by achieving some important binary
separations such as Cd 21 Zn 21 , Cd 21 Pb 21 ,
Cd 21 Hg 21 , Cd 21 Mg 21 , Cd 21 Cr 31 , Cd 21
Cu 21 and Mg 21 Ba 21 . Table 4 summarizes the

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

A. A. Khan, M.M. Alam / Reactive & Functional Polymers 55 (2003) 277290

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).

salient features of these separations. It was also

observed that Cd(II) retained strongly on the
cation exchanger column. The weakly retained
metal ions appear out of the column faster than
Cd(II) and Cd(II) was eluted after by HNO 3
solution.

Fig. 5. Calibration curve for polyaniline Sn(IV) tungstoarsenate

membrane electrode in aqueous solutions of Cd(NO 3 ) 2 .

The heterogeneous precipitate Cd(II) ionselective membrane electrode obtained from

polyaniline Sn(IV) tungstoarsenate exchanger
material gives linear response (Fig. 5) in the
given range of 1310 21 1310 24 M with a
slope of 27 mV per decade change in Cd(II) ion
concentration and the slope value is nearly close
to Nernstian value, 29.6 mV/ concentration decade for divalent cations. Below 1310 24 M, a
non linear response was observed but the calibration curve could be utilized for the determination of Cd(II) down to 1310 24 M. A constant potential was obtained after 25 s and it
was also observed that the electrode potential
remained unchanged within the pH range 3.0
8.0.
The selectivity coefficients, K POT
Cd.M of various
interfering cations for the Cd(II) ion-selective
polyaniline Sn(IV) tungstoarsenate electrode
were determined by the mixed solution method
[24] and the following numerical values were
obtained:

A. A. Khan, M.M. Alam / Reactive & Functional Polymers 55 (2003) 277290

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

Thus the selectivity coefficient indicates the

extent to which a foreign ion (M n 1 ) interferes
with the response of the electrode towards its
primary ion (Cd 21 ). The results reveal that the
electrode is selective for Cd(II) in presence of
interfering cations.
The analytical utility of this membrane electrode has been established by employing it as an
indicator electrode in the titration of 0.01 M
Cd(NO 3 ) 2 solution against 0.01 M EDTA solution. It was observed that a sharp rise in the
titration curve occurs at the equivalence point
(Fig. 6). It has been used in the determination of
Cd 21 ions in some synthetic samples containing
a number of different metal ions as well as
samples obtained from electroplating units and
the error has been found as 649%.

Acknowledgements
The authors are thankful to the Department of

Fig. 6. Precipitation titration of Cd(II) against EDTA solution.

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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