Talanta 59 (2003) 101
/105

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A mercury(II) ion-selective electrode based on neutral

salicylaldehyde thiosemicarbazone
R.K. Mahajan , Inderpreet Kaur, T.S. Lobana
Department of Chemistry, Guru Nanak Dev University, Amritsar 143005, India
Received 4 March 2002; received in revised form 12 August 2002; accepted 23 August 2002

Abstract
A new ion-selective PVC membrane electrode based on salicylaldehyde thiosemicarbazone as an ionophore is
developed successfully as sensor for mercury(II) ions. The electrode shows excellent potentiometric response
characteristics and displays a linear log[Hg2 ] versus EMF response over a wide concentration range of 1.778 /
10 6
/1.0 /10 1 M with Nernstian slope of 29 mV per decade with the detection limit of 1.0 /10 6 M. The response
time of the electrode is less than 30 s and the membrane electrode operates well in the pH range of 1.0
/3.0. The lifetime
of the sensor is about 2 months. The electrode shows better selectivity towards Hg2 ions in comparison with the alkali,
alkaline and some heavy metal ions; most of these metal ions do not show significant interference (KPot
Hg, M values of the
order of 10 3
/10 4). The present sensor showed comparable or even better performance vis-a`-vis similar PVC based
ion-selective electrodes reported in literature. The sensor was also applied as an indicator electrode for potentiometric
titration of Hg2 ions with I  and Cr2O2
7 .
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Sensor; Mercury(II); Potentiometry; Thiosemicarbazone

1. Introduction
During the past two decades, a large number of
neutral ionophores with high selectivities for
specific metal ions have been developed which

 Corresponding author. Fax: /91-183-258820

E-mail
addresses:
rakesh_chem@yahoo.com
Mahajan), tarlok@angelfire.com (T.S. Lobana).

(R.K.

find extensive applications in potentiometric and

optical sensors for determination of metal ions in
various environmental and biological samples [1
/
11]. The potentiometric sensors based on ionselective electrodes provide a simple, selective,
precise and economic method for on line monitoring of concentrations of selected species without
any pretreatment of sample.
Mercury(II) ion known for its toxicity shows
strong affinity for the ligands containing S atoms

0039-9140/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 3 9 - 9 1 4 0 ( 0 2 ) 0 0 4 7 3 - 3

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R.K. Mahajan et al. / Talanta 59 (2003) 101
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and thus causing the blocking of sulphydryl

groups (
/SH) of proteins, enzymes and membranes. Hg2 ions are also responsible for the
injury of kidney and gastrointestinal tract. Because
of its serious hazardous effects to human
health,there is strong need to develop new methods to determine mercury(II) ions in the chemical
and biochemical samples. There is no commercially available mercury(II) ion-selective electrode.
In literature also not many mercury(II) ion-selective electrodes have been reported [9]. The coordination chemistry of organomercury(II) has
established binding of mercury(II) ions with S
and N donor atoms of thiosemicarbazones [12
/
14]. As a part of our interest to develop metal ion
sensors [6
/8], in this paper we report mercury(II)
ion-selective electrode based on salicylaldehyde
thiosemicarbazone (I) as an ionophore. Thiosemicarbazones are an important class of ligands with
enormous biochemical applications [12]. The electrode exhibits high selectivity for mercury(II) ions
over alkali, alkaline and some transition metals
(Na , K , Ca2, Mg2, Ba2, Cu2, Zn2,
Pb2, Ni2, Co2, Cd2, Fe3, Ag ). This is the
first report on use of a thiosemicarbazone as
ionophore for metal ions [9,12
/14].

2.2. Electrode preparation

A mixture of about 100 mg of PVC, 200 mg of
bis(2-ethylhexyl)sebacate as plasticizer and 5 mg of
salicylaldehyde thiosemicarbazone was dissolved
in 5 ml of tetrahydrofuran. The mixture was
shaken and poured into a 50 mm petridish. The
solvent was allowed to evaporate at room temperature for 24 h. A semi-transparent membrane
of 0.4 mm thickness was obtained. The membrane
was cut to the size, attached to the PVC tube with
the help of PVC glue and conditioned with 1.0 /
103 M Hg(NO3)2 solution for 3 days.
All the potentiometric measurements were made
with an Elico-LI-Model-120 pH meter. The electrochemical system was as follows:
Ag
AgCl=1:0103 M Hg(NO3 )2 =
PVC membrane=test solution=Ag
AgCl
Standard solutions of Hg(NO3)2 were obtained
by dilution of 0.1 M Hg(NO3)2 solution. As the
pH of pure solutions lies in the functional range of
the sensor, one does not require any pH adjustment.

3. Results and discussion

The potentiometric responses of the plasticized
PVC based membrane electrode, incorporating
salicylaldehyde thiosemicarbazone as an ionophore towards some alkali, alkaline earth and
heavy metal ions were tested in the preliminary
experiments. The potentiometric responses of

2. Experimental
2.1. Reagents
All reagents used were of Analytical-Reagent
grade. Doubly distilled deionised water was used
throughout. Salicylaldehyde thiosemicarbazone
was synthesised as reported in literature [12]. The
plasticizer, bis(2-ethylhexyl)sebacate and high molecular weight poly(vinylchloride) (PVC) were used
as received from Fluka.

Fig. 1. Potentiometric response of ionophore electrode for

various metal ions.

R.K. Mahajan et al. / Talanta 59 (2003) 101
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these electrodes are shown in Fig. 1. Among these

metal ions, Hg2 provides the most suitable ionselective electrode. The PVC based membrane of
salicylaldehyde
thiosemicarbazone
generates
stable potential when placed in contact with
Hg2 solutions. The detection limit of the electrode, as determined from the intersection of two
segments of calibration curve was 1.0 /106 M.
The response time of the electrode, tested by
measuring the time required to achieve a steady
state potential (within 9/1 mV) was less than 30 s
for the solution of Hg2 in the concentration
range of 1.78 /106
/1.0 /101 M. The electrode potentials were reproducible and remained
stable for 5 min, after which a very slow divergence
was observed [12]. The slow divergence in potentiometric response of the sensor may be explained
as follows:
It has been observed that the salicyldehyde
thiosemicarbazone coordinated to phenyl mercury(II), which remains stable in dmso for a few days
and then turns black. It shows that the complex
undergoes desulfurization forming HgS and salicylaldehyde semicarbazone (II).

The standard deviation of ten identical measurements was 9/2mV. The sensor is stable and can be
used over a period of 2 months without observing

103

any significant change in potentiometric response

characteristics.
The potentiometric response of the electrode
was found to be sensitive to pH changes. The effect
of pH on membrane electrode was examined over
the pH range of 1
/8 at Hg2 ion concentration of
1.0 /10 2 M and the results are shown in Fig. 2.
As seen, the potential was constant from pH 1
/3
beyond which the potential decreases sharply.
The selectivity is an important characteristic of
the sensor as it measures the response of the sensor
towards primary ion in the presence of the other
cations. This is measured in terms of the selectivity
coefficient (KPot
Hg , M) which has been evaluated
using fixed interference method at 1.0 /10 2 M
concentration of interfering ions. The fixed interference method is based on semi emperical
Nikolsky
/Eisenman equation. Under ideal conditions, the electrode response function follows
Nernst equation
Z Hg =ZM
Pot
]
EISE E 0 9RT=ZHg F ln[aHg SKHg;
M (aM )

where, EISE is measured potential, E0 is standard

cell potential aHg and aM are the activities of
primary (Hg2) and interfering ions. This treatment is usually adequate if interfering ions of same
charge as the analyte ions are compared. This
equation is not well suited, however, when ions of
different charges are involved and can provide
incorrect description of the observed potentiometric response. The values of the selectivity
coefficients are either very large or small depending on whether the ion of higher charge is
considered as primary ion or interfering species.
The reason behind the distorted values of selectivity coefficients, is the superscript on the activity/
concentration terms, which are essential in
Nikolsky
/Eisenman equation to account the different potentiometric response for the ions of
different charges. In order to eliminate this problem, KPot
Hg , M were evaluated with the help of
normal expression [15
/17] bearing superscripts,
i.e.
ZHg =Z M
Pot
ln KHg;
M ln aHg =(aM )

Fig. 2. Plot showing the variation of membrane potential with

pH at 1.0 /10 2 M Hg2 ions.

and also by an expression without superscript, i.e.

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R.K. Mahajan et al. / Talanta 59 (2003) 101
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Fig. 3. Selectivity coefficients (log KPot

Hg, M) of various interfering ions when calculated (a) by normal expression and (b) by expression
without superscript.

Pot
In KHg;
M In aHg =(aM ):

The resulting values are shown in Fig. 3. KPot

Hg,M
values are low for divalent and polyvalent ions,
indicating no interference when present with the
primary Hg2 ion. As regards the monovalent
Na , K and NH4 ions, they do not cause much
disturbance to the functioning of the electrode
assembly if present in small amounts. However,

Fig. 4. Plots showing E vs. Log [Hg2 ] in the presence of Ag 

ions at varying level of interference (") 1.0/10 2, (j) 1.0/
10 4, (') 5.0 /10 6 and (+) 0.0 M Ag  .

Ag is the usual interferent [8] as revealed by the

selectivity coefficient value for Ag. In order to
establish the concentration of Ag , that can be
tolerated by the sensor, a series of experiments
were carried out by varying Ag ion concentration, i.e 1.0 /102, 1.0 /104, 1.0 /105 and
5.0 /10 6 M. It is clearly shown in the Fig. 4 that
the electrode assembly can tolerate Ag  ion
concentration somewhat less than 5 /106 M.
Finally, a comparison with PVC based Hg2ion
sensors reported in the literature is made [9,10,18].
The present ion selective electrode based on
salicylaldehyde thiosemicarbazone is comparable
and superior in many respects than those reported
in literature (Table 1). Thus a great scope exists in
developing metal ion sensors based on noncyclic
thiosemicarbazones which are relatively cheap and
easily accessible reagents.
The electrode was also used to determine the
end-point in potentiometric titration of Hg2 with
I (Fig. 5). Similar curve is obtained in potentiometric titration of Hg2 with Cr2O2
7 .

R.K. Mahajan et al. / Talanta 59 (2003) 101
/105

105

Table 1
Comparison studies of Hg2 -ion selective electrode based on salicylaldehydethiosemicarbazone and previously reported in literature
Ionophore

Salicylaldehyde thiosemicarbazone
1,4-Dithia-12-crown-4 [18]
AntimonyIII arsenate [10]
Hexathiacyclooctadecane [9]

Response time (s)

B/30
60
/60

/

Fig. 5. Application of Hg2 ion selective electrode based on

salicylaldehydethiosemicarbazone in the titration of Hg2 with
I  ion.

Acknowledgements
One of the authors (I.K.) is thankful to the
Guru Nanak Dev University, Amritsar, India for
providing Research Fellowship.

References
[1] S.R. Shean, L.S. Shih, Analyst 117 (1992) 1691.
[2] S.K. Srivastva, V.K. Gupta, S. Jain, Anal. Chem. 68 (1996)
1272.
[3] F.N. Assubaie, G.J. Moody, J.D.R. Thomas, Analyst 114
(1989) 1545.

Linearity (M)

1.8/10 6
/1.0/10 1
1.0/10 6
/1.0/10 3
5.0/10 5
/1.0/10 2

/

log KPot
Hg,M
Fe3

Mg2

Pb2

/2.48
/1.5
//0.5
/0.7

/2.70
/2.9
//0.5

/

/3.23
/3.6
//0.5
/0.8

[4] K. Suzuki, H. Yamada, K. Sato, K. Watanabe, H.

Hisamoto, Y. Tobe, K. Kobiso, Anal. Chem. 65 (1993)
3404.
[5] S.K. Srivastva, V.K. Gupta, S. Jain, Analyst 120 (1995)
495.
[6] R.K. Mahajan, M. Kumar, V. Sharma, I. Kaur, Analyst
126 (2001) 505.
[7] R.K. Mahajan, M. Kumar, V. Sharma, I. Kaur, H. Singh,
R. Kumar, Tetrahedron Lett. 42 (2001) 5315.
[8] R.K. Mahajan, O. Parkash, Talanta 52 (2000) 691.
[9] P. Buhlmann, E. Pretsch, E. Bakker, Chem. Rev. 98 (1998)
1593.
[10] A.K. Jain, V.K. Gupta, L.P. Singh, Bull. Electrochem. 12
(1996) 418.
[11] V.K. Gupta, S. Jain, U. Khurana, Electroanalysis 9 (1997)
478.
[12] T.S. Lobana, A. Sanchez, J.S. Casas, A. Castineiras, J.
Sordo, M.S. Garcia-Tasende, E.M. Vazquez-Lopez, J.
Chem. Soc. Dalton Trans. (1997) 4289 and references
cited inside.
[13] T.S. Lobana, A. Sanchez, J.S. Casas, A. Castineiras, J. Sordo, M.S. Garcia-Tasende, Polyhedron 17
(1998) 3701.
[14] T.S. Lobana, A. Sanchez, J.S. Casas, A. Castineiras, J.
Sordo, M.S. Garcia-Tasende, Main Group Metal Chem.
24 (2001) 61.
[15] E. Bakker, R.K. Meruva, E. Pretsch, M.E. Meyerhoff,
Anal. Chem. 66 (1994) 3021.
[16] M. Nagele, E. Bakker, E. Pretsch, Anal. Chem. 71 (1999)
1048.
[17] S.K. Srivastava, V.K. Gupta, S. Jain, Analyst 120 (1993)
495.
[18] M.T. Lai, J.S. Shih, Analyst 111 (1986) 891.