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CAMAN IOP Publishing
IOP Conf. Series: Materials Science and Engineering 17 (2011) 012010 doi:10.1088/1757-899X/17/1/012010

A Novel Ion – selective Polymeric Membrane Sensor for

Determining Thallium(I) With High Selectivity

Anuar Kassim1, Majid Rezayi1, Saeid Ahmadzadeh1, Gholamhossein Rounaghi2,

Masoomeh Mohajeri2, Noor Azah Yusof1, Tan Wee Tee1, Lee Yook Heng3, Abd.
Halim Abdullah1
1
Department of Chemistry Faculty of Science, Universiti Putra Malaysia 43400
Serdang, Selangor, Malaysia
2
Department of Chemistry, Factuality of Sciences, Islamic Azad University of
Mashhad, Mashhad, Iran
3
School of Chemical Sciences and Food Technology, Faculty of Science and
Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor D.E., Malaysia

Email: anuar@science.upm.edu.my

Abstract Thallium is a toxic metal that introduced into the environment mainly as a waste
from the production of zinc, cadmium, and lead and by combustion of coal. Thallium causes
gastrointestinal irritation and nerve damage when people are exposed to it for relatively short
period of time. For long term, thallium has the potential to cause the following effects: change
in blood chemistry, damage to liver, kidney, intestinal and testicular tissue, and hair loss. In
this work a membrane was prepared by use of 4'–nitrobenzo –18–crown–6 (4'NB18C6) as an
ion carrier, polyvinylchloride (PVC) as a matrix, and diocthylphetalate (DOP) as a plasticizer
for making an ion selective electrode for measurement of Tl+ cation in solutions. The amount
of 4'–nitrobenzo–18C6 and polyvinylchloride were optimized in the preparation of the
membrane. The response of the electrode was Nernstian within the concentration range 1.0 ×
10-8 to 1.0 × 10-1M. This sensor displays a drift in Nernstian response for this cation with
increasing the amount of ionophore and decreasing the amount of polyvinylchloride.The
results of potentiometric measurements showed that, this electrode also responses to Cu2+,
Ni2+ and Pb2+ cations, but the electrode has a wider dynamic range and a lower detection limit
to Tl+ cation. The effects of various parameters such as pH, different cations interferences,
effect of the amount of ionophore and polyvinylchloride and time on response of the coated
ion selective electrode were investigated. Finally the constructed electrode was used in
complexometric and precipitation titrations of Tl+ cation with EDTA and KBr, respectively.
The response of the fabricated electrode at concentration range from 1.0× 10-8 to 1.0× 10-1M
is linear with a Nernstian slope of 57.27 mV.

1. Introduction
Thallium is a toxic metal that is introduced into the environment mainly as a waste from the
production of zinc, cadmium, and lead by combustion of coal [1].
Thallium causes gastrointestinal irritation and nerve damage when people are exposed to it for
relatively short period of time [2]. For long term, thallium has the potential to cause the following
effects: change in blood chemistry, damage to liver, kidney, intestinal and testicular tissue, and hair
loss [3]. Due to the high toxicity of thallium and its compounds, their accurate determination is
demanded. Spectrophotometry after extraction[4], flame atomic absorption spectrometry (FAAS),
Published under licence by IOP Publishing Ltd 1
CAMAN IOP Publishing
IOP Conf. Series: Materials Science and Engineering 17 (2011) 012010 doi:10.1088/1757-899X/17/1/012010
graphite-furnace atomic absorption spectrometry after extraction [5], inductive-coupled plasma mass
spectrometry (ICP-MS), voltammetry and potentiometry have been reported for the determination of
thallium(I) cation. Potentiometric methods using ion-selective electrodes have found wide
applications, being simple and economical. Ion-selective electrodes (ISE) are one of the most
convenient and reliable analytical tools for estimating metal ions concentration [6]. There have been
only a few reports concerning Tl+ liquid-membrane electrodes. They need to be improved with regard
to their low selectivities against alkali metal ions, linearity and pH dependence.
Thallium (I) cation is an interesting inorganic cation for developing ionophores. Although various
crown ethers have been tested as Tl+ ionophores in construction of ion selective electrode, but most of
these crown ethers have a dynamic range from 1.0 × 10-1 to 1.0 × 10-5 for Tl+ cation, also if we want to
determine thallium (I) ion in trace concentrations in solutions, we will in front of with a big challenge
for the construction of ion selective electrodes based on these crown ethers [7].
In this research, we report the use of 4'-nitrobenzo-18C6 (Schem Ι) as an ionophore in
construction of highly sensitive and selective polyvinyl chloride (PVC) membrane sensor for the
determination of ultra trace amounts of thallium (I) cation in solution.
The electrode exhibited Nernstian responses to thallium (I) ion over a wide concentration rang with
low detection limit (10-8M). the electrode possess fast response time, appropriate lifetime and most
importantly good selectivity toward Tl+ relative to variety of other common inorganic cations.

Scheme I: 4'-nitrobenzo-18C6

2. Experimental

2.1 Apparatus
All potentiometric measurements were made at 25°C using an Schott pH/mV meter (Model CG 825)
and an Orion double junction Ag-/AgCl reference electrode (Model 90-02) containing 10% (w/v)
potassium nitrate in the outer compartment. A combined Ross glass pH electrode (WTW) was used
for all pH measurements.

2.2 Reagents and materials

All chemicals were of analytical reagent grade unless otherwise stated and doubly distilled water was
used throughout. Polyvinyl chloride (PVC) powder of high molecular weight, dioctylphthalate (DOP),
tetrahydrofuran (THF) of purity >/99%,and thallium nitrate were all obtained from Prolabo Chemical
Company, and other salts such as sodium nitrate (Fluka), potassium nitrate (Fluka), silver nitrate
(Merck), ammonium nitrate (Merck), copper nitrate (Merck), nickel nitrate (Merck), barium nitrate
(Merck), cadmium nitrate (Merck), strontium nitrate (Merck), magnesium nitrate (Merck), Lead(II)
nitrate (Merck), calcium nitrate (Merck), chromium nitrate (Merck), tetraethylamonium perchlorate
(Merck) were used as received. Ammonia buffer of pH 9.0 was prepared by mixing of 0.25%
ammonia solution with 0.1 M ammonium nitrate.

2.3 Membrane preparation and electrode construction

The electrode was prepared by dip – coating method from a graphite rod (2 mm diameter and 40 mm
long). The working surface of the electrode was polished with a polishing cloth [8]. The electrode was
rinsed with water and THF and allowed to dry. A mixture of PVC and diocthylphtalate (DOP) as
plasticizer to give a total mass of 100 mg was dissolved in approximately 4 ml of THF, then the
macrocyclic ligand, 4'-NB-18C6, as an ion carrier was added, and the solution was mixed well. After
removing air bubbles, the polished graphite electrode was repeatedly dipped (several times, a few
minutes between dips) into the membrane solution. A membrane was formed on the graphite surface,
which was allowed to set overnight. The electrode was rinsed with water, conditioned for 24 h in a

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CAMAN IOP Publishing
IOP Conf. Series: Materials Science and Engineering 17 (2011) 012010 doi:10.1088/1757-899X/17/1/012010
0.1M thallium nitrate solution and stored in the same solution when not in use. The coating solutions
were stable for several weeks and could be used for the construction of new membranes.
This electrode was constructed by two different matrixes from different amounts of PVC and ion
carrier that are shown in Table 1.

Table 1. Comparison of the main characterization data for different amount of PVC and ion
pair sensors.

Electrode Electrode
1 2
ro Polymer amo amo
% %
w matrix unt unt
4' –
Nitroben
13.4 6.0 9.6 4.2
1 zo – 18 –
7 mg 0 mg 74
Crown –
6
Poly
121. 53. 55.
(vinyl 125.0
2 16 94 67
chloride) 4 mg
mg 6 2
/ PVC
Dioctyl 20. 20.
45
3 phthalate 03 45 ml 03
ml
/ DOP 5 5
Tetrahyd __ __
3-4 3-4
4 rofuran __ __
ml ml
/THF __ __
Activated 20. 20.
44.9 44.96
5 charcoal 03 03
6 mg mg
/C 5 5

2.4 Potential measurements

All measurements were made at 25±1 ◦C with a cell of the type: Ag|AgCl(s), 4 moll−1 KCl saturated
with AgCl(s) | sample solution | membrane , graphite. The performance of each electrode was
investigated by measuring its potential in thallium nitrate solutions prepared in the concentration
range 0.1M to 1.0×10-8M by serial dilution of the 0.1M stock solution at a constant pH. The solutions
were stirred and potential readings were recorded when they reached steady-state values. The data
were plotted as observed potential versus the logarithm of the Tl+ ion concentration.

3. Results and discussion

In these experiments, 4'-NB-18C6 was used as an ion carrier to prepare thallium (I) selective
membrane electrode in a PVC matrix. The potential response of the membrane electrodes to Tl+ cation
is shown in Figure 1. It is seen that the membrane electrode responds to thallium (I) ion with
Nernstian slope at a wide concentration range. Thus the membrane (I) gives the best response to Tl+
cation. The presence of nitrogen atom in the macrocycle is expected to show strong complexation
behaviour of the carrier for Tl(I) ion. The ratio of ionophore (electrode 1) to PVC was varied in order
to obtain a composition, which gives a membrane of best performance with regard to working
concentration range, slope and response time. It was found that the membrane having 9.6 mg of
ionophore and 45 mg PVC gave the best results. Therefore, the ionophore 4'NB18C6 was selected as
suitable sensor material for Tl+ ion in PVC matrix.

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CAMAN IOP Publishing
IOP Conf. Series: Materials Science and Engineering 17 (2011) 012010 doi:10.1088/1757-899X/17/1/012010

Figure 1. Potential response of thallium(I) sensor based

on 4'NB18C6 at the best conditions.

Addition of appropriate amount of plasticizers leads to optimum physical properties and ensures
high mobility of ions in the membrane. These solvent mediators strongly influence the working
concentration range of the sensors. It is well known that plasticizers improve the electrochemical
properties of the ion selective electrodes [9].
The potentiometric selectivity coefficients of the electrode, ( ), toward different cationic
-3 -4
species were evaluated by Fixed interference method using 10 and 10 M solutions of metal nitrate
as an interference and are given in Table 2 [10,11]. It can be seen from Table 2, that the electrode is
characterized by a high selectivity towards Tl+ ion with respect to alkali and alkaline earth metal ions
(Na+, K+ , Ca2+ and Mg2+) and also other cations.

In the FIM, an entire calibration curve is measured for the primary ion in a constant interfering ion
background (aj (BG)). The linear (i.e., Nernstian) response curve of the electrode as a function of the
primary ion activity is extrapolated until, at the lower detection limit ai (DL), it intersects with the
observed potential for the background alone.

Table 2. Selectivity coefficients of the coated-graphite electrode, determined by use of Fixed

interference method.
/ 10- Interfering
-3
/10 4 ion
-0.11 -0.15 K+
-0.00027 -0.00034 Na+
-0.017 -0.026 Ca2+
-0.00014 -0.00041 Mg2+

The dependence of sensor’s potential response on the pH has been tested over the range of 2.0–14.0
for 1.0×10−2 and 1.0×10−5M Tl(I) ion solutions (Fig. 2). The operational range was studied by varying
the pH of the test solutions with nitric acid or sodium hydroxide solutions. The graphical results in
Figure 2, show that the suitable range of pH for our experiments is pH= 5-14.

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CAMAN IOP Publishing
IOP Conf. Series: Materials Science and Engineering 17 (2011) 012010 doi:10.1088/1757-899X/17/1/012010

Figure 2. Effect of the pH on potentials [Tl+]=10−2 and 10−5 M.

The response time of the electrode was measured for thallium(I) solutions in various
concentrations. It was found to be 2 min for two concentrations (1.0×10-5 and 1.0×10−3M) of
thallium(I) ion. However, the response time of the electrode was 60 s when thallium(I) concentration
changed from 1.0×10−5 to 1.0×10−3M. The change of potential with time by addition of thallium(I) ion
at different concentrations is given in Fig.3. The minimum response time of this electrode being 30 s,
which is a short period, and it is a good advantage for response of these electrodes and, therefore, they
can easily be used for routine analyses.

Figure 3. Effect of the time on potentials: [Tl+] =10−3 and 10−5 M.

The membrane sensor was successfully used in the potentiometric titration of Tl+ with EDTA and
KBr. A 70 ml (1.0×10-2 M) solution of Tl+ was titrated with 1.0×10-1 M EDTA at pH 9.0 (Figure 4).
The pH of the solution was adjusted by addition of nitric acid and ammonium hydroxide. Upon
addition of EDTA, the concentration of Tl+ ions decreases, which results a decrease in potential of the
solution. As is evident in Figure 4, the titration curve is not in standard shape which may be due to the
interference caused by potassium ion present in EDTA solution. The break point of the titration curve
is sharp and corresponds to the stoichiometry of Tl(I)–EDTA complex. After the end-point, potentials
are almost constant because now the sensor is not responding to small changes in Tl+ concentration.
The potential generated after this stage may be attributed to the response of electrode towards
potassium ions only. Thus, the electrode assembly can be used for thallium ion determination by
potentiometric titration using EDTA.

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CAMAN IOP Publishing
IOP Conf. Series: Materials Science and Engineering 17 (2011) 012010 doi:10.1088/1757-899X/17/1/012010

Figure 4. Potentiometric titration plot of 1.0×10−2M Tl+ solution (70 ml) with
EDTA(1.0×10−1 M).

In another experiment, we used the thallium(I) selective memberane electrode for potentiometric
titration of Tl+ cation by Br- anion.The graphical results are shown in Figure 5. As is evident, in this
Figure, the titration curve is in standard shape and, therefore, this electrode could be used for
measurement of concentration of Tl+ cation in solutions.

Figure 5. Potentiometric titration plot of 1.0×10−2 M Tl+ solution (70 ml) with Br-(1.0×10−1 M)

4. Conclusion
A new PVC-memberan electrode for Tl+ ions based on 4'-NB-18C6 as Ionophore, was investigated.
The optimized formulation of the membrane (9.6 mg 4'-NB-18C6, 125.04 mg PVC, 45 ml DOP,
44.86 mg Carbon active) resulted in a linear concentration range of 1.0 × 10-8 to 1.0 × 10-1M with a
slope of 57.27 mV/decade.
The fast response time, wide linear range, fair selectivity coefficients and long lifetime of the
response sensor are advantageous over most of the reported Tl+ ion-selective electrodes. The proposed
electrode can be used successfully as an sensor in potentiometric titration.

Acknowledgements
We gratefully acknowledge the support of this work by department of chemistry - University Putra
Malaysia - Selangor - Serdang - Malaysia

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