Materials Science and Engineering C 29 (2009) 2154–2159

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Materials Science and Engineering C

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m s e c

Mercury(II) selective membrane electrode based on

1,3-bis(2-methoxybenzene)triazene
Mohammad Kazem Rofouei a,⁎, Moslem Mohammadi a, Mohammad Bagher Gholivand b
a
Faculty of Chemistry, Tarbiat Moallem University, Tehran, Iran
b
Department of Chemistry, Razi University, Kermanshah, Iran

a r t i c l e i n f o a b s t r a c t

Article history: A plasticized poly (vinyl chloride) membrane electrode based on 1,3-bis(2-methoxybenzene)triazene (MBT)
Received 10 February 2009 for highly selective determination of mercury(II) has been developed. The electrode showed a good Nernstian
Received in revised form 18 April 2009 response (30.2 ± 0.3 mV decade− 1) over a wide concentration range (1.0× 10− 7−1.0× 10− 2 mol L− 1). The limit
Accepted 27 April 2009
of detection was 5.0 × 10− 8 mol L− 1. The electrode has a response time about 15 s and can be used for at least
Available online 5 May 2009
1 month without observing any deviation from Nernstain response. The proposed electrode revealed an
excellent selectivity toward mercury(II) ion over a wide variety of alkali, alkaline earth, transition, and heavy
Keywords:
Mercury(II)
metal ions and could be used in the pH range 2.6–4.2. The electrode was used in the determination of Hg2+
Sensor in aqueous samples and as an indicator electrode in potentiometric titration of Hg(II) ions.
PVC membrane © 2009 Elsevier B.V. All rights reserved.
Potentiometry
1,3-bis(2-methoxybenzene)triazene (MBT)

1. Introduction However, despite extensive combinatorial chemistry scientific re-

Mercury is a toxic element that can be absorbed readily by humans
and other organisms. It is well known that mercury ion inactivates
sulfhydril enzymes and also combines with amine. The need for highly
sensitive and selective mercury determination arises from its wide
application in industry and its long term toxicity toward human
beings [1–3]. The most widely used techniques for quantification of
Hg2+ are based on cold vapor atomic absorption spectrometry [4] and
cold vapor atomic fluorescence spectrometry [5]. Other published
methods include neutron activation analysis [6], anodic stripping
voltammetry [7], X-ray fluorescence spectrometry [8] and inductivity
coupled plasma mass spectrometry [9]. However, these methods are
either time-consuming, involve multiple sample manipulations, or are
too expensive for most analytical laboratories. Among the available
analytical techniques, the application of carrier based ion-selective
electrodes (ISEs), has become a well-established routine analytical
technique. The most important properties of these electrodes are the
high speed sample analysis, portability of the device, sample non-
destruction, online monitoring, cost effectiveness and large measuring
range [10–14].
Triazene compounds, characterized by having a diazoamino group
(–N = N–N–), have been studied for over 130 years concerning their
interesting structural, anticancer and reactivity properties. They
have been used in medicinal, and as organometalic ligands [15].
⁎ Corresponding author. Tel.: +98 21 88848949; fax: +98 21 88820993.
E-mail address: rofouei@tmu.ac.ir (M.K. Rofouei).
ports on the synthesis, characterization and crystalline structure of
the transition metal triazenide complexes, reports on analytical
application of these ligands are quite spare. In the present study, we
describe the fabrication and characterization of a new ISE based on
1,3-bis(2-methoxybenzene)triazene as a selective and lipophilic
ionophore.
2. Experimental
2.1. Reagents
All of the chemicals used were of analytical reagent grade
(Merck). Doubly distilled water was used throughout. The 1,3-bis
(2-methoxybenzene)triazene (MBT) was recently synthesized and
its structures has been approved [16]. Dibutylphethalate (DBP),
dioctylphethalate (DOP), tris(2-ethylhexyl)phosphate (TEHP), dioc-
tylsebasate (DOS), tetrahydrofuran (THF), sodium tetraphenylborate
(NaTPB) and high relative molecular weight poly (vinyl chloride)
(PVC) were obtained from Merck or Sigma and used without any
further purification. 2-Nitrophenyloctylether (O-NPOE) was pur-
chased from Acros. Also, the nitrate salts of all cations used (all from
Merck) were of the highest purity available and were used without
any further purification except for vacuum drying over P2O5. A mixed
buffer (pH 3.5), containing appropriate amount of 0.1 mol L− 1 acetic
acid and 0.1 mol L− 1 sodium acetate was used for adjusting the pH of
test solutions.

0928-4931/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.msec.2009.04.017
 M.K. Rofouei et al. / Materials Science and Engineering C 29 (2009) 2154–2159 2155

Fig. 1. Structure of 1,3-bis(2-methoxybenzene)triazene (MBT).

2.2. Preparation of the electrode

Poly(vinyl chloride)-based Hg2+ membrane sensors were prepared

as described in [17,18] by thoroughly mixing 1 mg of ionophore (MBT),
1 mg of additive (NaTPB), 33 mg of powdered PVC and 65 mg of
plasticizer TEHP in a glass dish of 2 cm diameter. The mixture was then
completely dissolved in 5 mL of fresh THF. The solvent was evaporated
slowly until an oily concentrated mixture was resulted. A Pyrex or Teflon
tube (3–5 mm i.d on top.) was dipped into the mixture for 10 s so that a
membrane was formed. The tube was then pulled out from the mixture
and kept at room temperature for 24 h. The tube was then filled with
internal filling solution of 1.0 × 10− 3 mol L− 1 of Hg(II). The electrode
was finally conditioned for 24 h by soaking in a 1.0 × 10− 3 mol L− 1
solution of Hg(II).
2.3. EMF measurements
A cell assembly of the following type was used:
Ag/AgCl, KCl (3 mol L− 1)| internal solution: Hg(NO3)2 (1.0×10− 3 mol
−1
L ) PVC membrane|test solution|Hg/Hg2Cl2, KCl (satd.).
A Metrohm-692 pH/mV meter was used for measurements at
25.0 ± 0.1 °C. All measurements were carried out at 25.0 ± 0.1 °C.
Fig. 3. Electronic absorption spectra of ligand (MBT) in acetonitrile (5.0 × 10− 5 M) in
the presence of increasing concentration of mercury(II) ion. Corresponding mole ratio
plot at 368 nm is shown in the inset.
the same experimental conditions (except for 24 h conditioning in a
0.001 mol L− 1 of the corresponding cations) are shown in Fig. 2. As
it can be seen, among different tested cations, mercury(II) with the
most sensitive response seems to be suitably determined with the PVC
membrane based on MBT and the emf responses obtained for all other
cation-selective electrodes are much lower than that predicted by
the Nernst equation. The unique potentiometric selectivity towards
Hg2+ must be related to the coordinate interaction between MBT and
a Hg2+ ion. In a MBT molecule, the N, O atoms can play the role of an
electron donor which can coordinate metal ions as electron acceptors.
Therefore, the response mechanism of the electrode suggests that an
interaction between the N and O atoms in a complex and Hg2+ may
take place [19–21].

3. Results and discussion 3.1. Complex study

Due to its sufficient insolubility in water and the presence of donor
atoms (N, O) in its structure, ligand MBT (Fig. 1) was expected to act as
a suitable ion carrier in the PVC membranes with respect to special
transition and heavy metal ions of proper size and charge. Thus, in
preliminary experiments, it was used as a neutral carrier to prepare
PVC-based membrane electrodes for a variety of metal ions. The
potential responses of the most sensitive electrodes, prepared under
In order to determined the stoichiometry and stability of the
resulting MBT complex with mercury ion in a acetonitrile solution, the
spectra of a series of solutions containing a constant concentration of
ligand (5.0 × 10− 5 M) at 25 °C and varying amounts of the metal ion
were obtained and the results is shown in Fig. 3. As can be seen, the
complexation was accompanied by decreasing in the absorption band
of the MBT at 368 nm, and produce a new absorption band at about
264 nm. The obtained mole ratio plot (absorbance vs. [Hg2+]/[MBT) at
wavelength of 368 nm for MBT are shown in the inset of Fig. 3. As seen
the absorbance–mole ratio plot revealed a level off at [Hg2+]/[MBT)
molar ratio of 1, emphasizing the formation of 1:1 (metal to ligand)
complex in solution. Also, the complexation of MBT with a number of
metal ions was investigated. The formation constants of the resulting
1:1 complexes are listed in Table 1. As it can be seen, the MBT with the
most stable complex with Hg(II) ion is expected to act as a selective

Table 1
Formation constants of different metal—MBT complexes in acetonitrile.

Metal Log Kf
Hg(II) 7.29 ± 0.02
Ag(I) 4.73 ± 0.03
Cu(II) 3.17 ± 0.02
Pb(II) 3.42 ± 0.02
Zn(II) 2.85 ± 0.02
Cd(II) 3.66 ± 0.04
Al(III) 2.13 ± 0.03
Ni(II) 2.68 ± 0.03
Co(II) 2.04 ± 0.02
Mn(II) 2.29 ± 0.04
Sr(II) 2.01 ± 0.03
Fig. 2. Potential response of ion-selective electrode based on MBT (composition No. 6) Fe(III) 2.18 ± 0.04
for various metal ions.
2156 M.K. Rofouei et al. / Materials Science and Engineering C 29 (2009) 2154–2159

Table 2
Optimization of the membrane ingredients (n = 5).

Membrane Composition of membrane (wt.%) Slope Linear range

−1 −1
No. PVC Plasticize Additive Ionophore (mV decade ) (mol L )
1 33 66(NPOE) 0 1 36.5 ± 0.5 5.3 × 10− 5−
1.0 × 10− 2
2 33 66(DOS) 0 1 15.4 ± 0.5 4.1 × 10− 5 −
1.0 × 10− 2
3 33 66(DBP) 0 1 20.2 ± 0.3 7.5 × 10− 6 −
1.0 × 10− 2
4 33 66(DOP) 0 1 24.6 ± 0.4 3.2 × 10− 6 −
1.0 × 10− 2
5 33 66(TEHP) 0 1 28.1 ± 0.4 1.0 × 10− 6−
1.0 × 10− 2
6 33 65(TEHP) 1 1 30.2 ± 0.3 1.0 × 10− 7−
1.0 × 10− 2
7 33.5 65(TEHP) 0.5 1 28.8 ± 0.3 5.4 × 10− 7−
1.0 × 10− 2 Fig. 4. Effect of pH on the response of the mercury ion-selective electrode (composition
8 32.5 65(TEHP) 1.5 1 29.4 ± 0.4 3.0 × 10− 7− No. 6).
1.0 × 10− 2
9 33.5 65(TEHP) 1 0.5 27.3 ± 0.5 8.2 × 10− 7−
1.0 × 10− 2 lipophilicity and polarity, where the best results for response was
10 32.5 65(TEHP) 1 1.5 29.1 ± 0.3 4.3 × 10− 7− obtained when these properties reach an intermediate value. Solvent
1.0 × 10− 2 polymeric membrane ion-selective electrodes are usually based on a
11 34 65(TEHP) 1 0 7.5 ± 0.5 5.0 × 10− 4−
matrix of the solvent mediator/PVC ratio about 2. Polymeric films
1.0 × 10− 2
with such a plasticizer/PVC ratio will result in optimum physical
properties and high enough mobility of their constituents. In this
study, a plasticizer/PVC ratio of nearly 2 was found to be the most
ionophore for preparation of Hg(II) ion-selective membrane elec- suitable ratio. Moreover, 1 mg of MBT was chosen as the optimum
trodes. The formation constants of the resulting complex be- amount of the ionophore in the PVC-membrane (No. 6). Although
tween cations and MBT were evaluated by computer fitting of the neutral-carrier-based ISE membranes may work properly even when
corresponding mole ratio data to a previously derived equation [22] they contain only a very small amount of ionic sites (e.g., as impu-
using a non-linear curve-fitting program, KINFIT [23]. Absorbance rities), the addition of a salt of lipophilic ion is advisable and beneficial
spectra were recorded using a HP spectrophotometer (Agilent 8453) for various other reasons as well. In fact, the use of additives may
equipped with a thermostated bath (Huber polystat cc1). For com- catalize the exchange kinetic at the sample-membrane surface and
plexation studies, the temperature of the cell holder was maintained gives rise to significant changes in selectivity [30]. Thus, addition of a
at 25 ± 0.1 °C. little amount of additive improves the response characteristics of the
proposed electrode. From the data presented in Table 2, it is seen that
3.2. Effect of electrode composition the addition of NaTPB increased the sensitivity of the electrode
response considerably. Use of 1 mg NaTPB resulted in a Nernstian
It is well known that some important features of the PVC based behavior of the electrode (No. 6). Thus the obtained results indicate
membranes, such as the nature and amount of ionophore, the prop- that the best sensitivity and linear range is obtained for the membrane
erties of the plasticizer, the plasticizer/PVC ratio and the nature of No. 6 with a PVC: TEHP: MBT: NaTPB percent ratio of 33:65:1:1 which
additives used, significantly influence the sensitivity and selectivity of resulted in a Nernstian behavior of the membrane electrode over a
the ion-selective electrodes [24–26]. Thus, different aspects of wide concentration range.
membrane preparation based on MBT were optimized and the results
are given in Table 2. Plasticizers play an important role in the behavior 3.3. Effect of pH on potential response of electrode
of polymeric liquid membrane ion-selective. For a plasticizer to be
adequate for its use in polymeric liquid membrane ion selective The influence of the pH of the test solution (1.0 × 10− 3 mol L− 1
electrode, it should gather certain properties and characteristics such mercury(II)) on the sensor potential was investigated over the pH
as having high lipophilicity, high molecular weight, low tendency for
exudation from the polymeric matrix, low vapor pressure and high
capacity to dissolve the substrate and other additives present in the
polymeric membrane. Additionally, its viscosity and dielectric con-
stant should be adequate [27]. Table 3, lists the values of the dielectric
constant, lipophilicity, viscosity and molecular weight of the plasti-
cizers used in the present work [28,29]. Among of these plasticizers,
the best result was obtained when TEHP was used as solvent mediator
(Table 2). These results seem to indicate a synergism between

Table 3
Physical parameters of different plasticizers.

Plasticizer Dielectric constant Lipophilicity Viscosity Molecular weight

(ε) (log PTLC) (η)
DOS 4.0 10.1 25.0 426
DBP 6.4 4.5 15.7 278
DOP 5.1 7.1 39.0 390
TEHP 4.8 10.2 11.0 435
NPOE 23.9 5.9 13.8 251 Fig. 5. Dynamic response of the MBT membrane electrode for step changes in
concentration: (A) 10− 2, (B) 10− 3, (C) 10− 4, (D) 10− 5, (E) 10− 6 and (F) 10− 7 mol L− 1.
 M.K. Rofouei et al. / Materials Science and Engineering C 29 (2009) 2154–2159 2157

Table 5
Selectivity coefficient of various interfering ions (n = 5).

Interfering ion −Log K Interfering ion −Log K

Ag+ 2.01 ± 0.30 Al3+ 3.23 ± 0.25
Zn2+ 2.74 ± 0.28 Mn2+ 3.44 ± 0.26
Pb2+ 2.42 ± 0.29 Co2+ 3.01 ± 0.23
Ni2+ 2.63 ± 0.28 Cr3+ 3.12 ± 0.28
Cd2+ 2.24 ± 0.30 Ba2+ 3.02 ± 0.26
Mg2+ 4.71 ± 0.26 Ca2+ 4.09 ± 0.24
Cu2+ 2.21 ± 0.31 K+ 4.63 ± 0.22
Fe3+ 3.05 ± 0.26 Na+ 4.85 ± 0.21
Sr2+ 3.93 ± 0.23 Li+ 4.76 ± 0.23

ionophore and plasticizer which ensures stable potentials and long

lifetime [34–36].

Fig. 6. Calibration graph for mercury(II) ion selective electrode based on MBT (compo- 3.5. Potentiometric selectivity
sition No. 6).
The most important characteristic of a membrane sensor is its
range 1–6, where pH was adjusted with dilute HNO3 or NaOH response to the primary ion in the presence of other ions. This is
solutions. The potential-pH plot (Fig. 4) reveals that, within the pH measured in terms of the potentiometric selectivity coefficient (KPot
A,B)
range 2.6–4.2, the potential did not vary by more than/±1.0 mV. At which has been evaluated by the fixed interference method [37] that is
lower pH values, protonation of the nitrogen atoms carrier is possible based on the semi empirical Nikolsky-Eisenman equation.
which can result in the loss of its complexing ability with mercury
ions, then the membrane sensor responds to hydrogen ions [31,32], B RT h X Pot Z =Z
i
EISE = E F ln aA + KA;B ðaB Þ A B
while the observed drift at higher pH values could be due to the ZA F
formation of some hydroxyl complexes of Hg2+ ion in solution [33].
Thus, the above range may be taken as the working pH range of the Where EISE is the measured potential, E° the standard cell potential,
proposed sensor. aA and aB are the activities of primary and interfering ions, and all
other symbols have their usual meanings. In the fixed interference
method, the concentration of the mercury ion is varied while that of
3.4. Response time, calibration curve and life time the interfering ions is fixed at 1.0 × 10− 2 mol L− 1. From the plots of
EISE vs. log aHg and using the expression.
The average time required for mercury ion selective electrode No.6
aA
to reach a potential within ±0.5 mV of the final equilibrium value after Pot
ln KA;B = ln ZA = ZB
successive immersion in a series of mercury(II) solutions, each having aB
a 10-fold difference in concentration from 1.0 × 10− 7 to 1.0 × 10− 2 mol
L− 1 was considered. The results are given in Fig. 5. As can be seen, in The selectivity coefficients were determined. The value of aA that is
the whole concentration range the static response times of the estimated by determining the Hg(II) activity for which the linear and
membrane electrode were obtained in a short times (about 15 s). rising portion of the graph deviates by 2.303RT log 2/F mV from the
The PVC membrane electrode prepared, filled by conventional inner curved part [38] and the value of aB2/ZB (aB and ZB are the activity and
filling solution and operated under optimal experimental conditions charge of interfere ion, respectively) were used to calculate the
shows a linear response to the activity (concentration) of mercury ion
in the range 1.0 × 10− 7 to 1.0 × 10− 2 mol L− 1 (r2 = 0.998), with a
Nernstian slope of 30.2 mV per decade of mercury ion concentra-
tion (Fig. 6). The limit of detection, as determined from the intersection
of the two extrapolated segments of the calibration graph, was
5.01 × 10− 8 mol L− 1.
For the investigation of the stability and the lifetime of the Hg(II)
membrane sensor, five sensors were tested over a period of 1 month.
During this period, the sensors were used daily over an extended time
period (1 h per day). Their slopes and linear ranges were measured.
The results are summarized in Table 4, where it is concluded that, after
1 month, slight changes were observed in the slopes and linear ranges.
This prominent feature rises from the optimum lipophilicity of the

Table 4
The lifetime behavior of the Hg(II) membrane sensor (n = 5).

Day Slope (mV decade− 1) Linear range (mol L− 1)

1 30.2 ± 0.3 1.0 × 10− 7–1.0 × 10− 2
5 30.0 ± 0.3 1.0 × 10− 7–1.0 × 10− 2
10 29.7 ± 0.4 2.2 × 10− 7–1.0 × 10− 2
15 29.3 ± 0.5 2.9 × 10− 7–1.2 × 10− 2
20 28.7 ± 0.5 3.5 × 10− 7–1.6 × 10− 2
25 28.2 ± 0.4 4.2 × 10−7–1.8 × 10− 2
30 27.7 ± 0.5 5.0 × 10− 7–2.1 × 10− 2 Fig. 7. Potentiometric titration curve of 25 mL of a 1.0 × 10− 4 mol L− 1 solution of Hg2+
with 1.0 × 10− 2 mol L− 1 of EDTA.
2158 M.K. Rofouei et al. / Materials Science and Engineering C 29 (2009) 2154–2159

Table 6 Typical results of titration of Hg(II) is shown in Fig. 7. The added

Determination of the mercury ions in different water samples a (n = 5). titrant caused a decrease in the potential as a result of a decrease in
Sample Added (mol L− 1) Found (mol L− 1) Recovery (%) free Hg(II) ion due to formation of a complex with EDTA. The amount
Tap water 5 × 10−4
(4.90 ± 0.16) × 10− 4 98.0 of Hg(II) ions in solutions can be accurately determined from the
3 × 10− 5 (3.08 ± 0.12) × 10− 5 102.7 resulting titration curves.
7 × 10− 6 (6.84 ± 0.36) × 10− 6 97.7
Mineral water 5 × 10− 4 (4.87 ± 0.19) × 10− 4 97.4
3 × 10− 5 (3.13 ± 0.15) × 10− 5 104.3 3.6.2. Determination of mercury in water samples
7 × 10− 6 (7.40 ± 0.41) × 10− 6 105.7 The proposed electrode has been used for the determination of Hg2+
River water 5 × 10− 4 (5.16 ± 0.24) × 10− 4 103.2 in different water samples. For the analysis, water samples were
3 × 10− 5 (2.84 ± 0.18) × 10− 5 94.7
collected and filtered. The filtered samples were then acidified to the
7 × 10− 6 (7.51 ± 0.59) × 10− 6 107.3
optimal pH (3.5), and the resultant samples were stored at 4 °C [39]. The
a
Standard addition method was used. characteristic data on the performance of the electrode No. 6 for the
determination of Hg2+ are given in Table 6.

Table 7
Recent mercury(II) sensors based on various organic ionophores. 4. Conclusions

Slope Linear range Detection limit Response time Reference

The results obtained from the above-mentioned study reveal
(mVdecade− 1) (mol L− 1) (mol L− 1) (s)
−6 −2 −7
that a potentiometric PVC-based membrane sensor based on 1,3-bis
29.6 6.2 × 10 –8.0 × 10 5.0 × 10 30 [21]
26.1 5.0 × 10− 6–1.0 × 10− 2 2.6 × 10− 6 20 [33]
(2-methoxybenzene)triazene functions as an excellent mercury(II)
30.0 7.0 × 10− 8–1.0 × 10− 1 4.4 × 10− 8 10 [39] ion selective sensor and can be used for the determination of this
30.0 1.0 × 10− 7–1.0 × 10− 1 5.0 × 10− 8 25 [40] ion in the presence of considerable concentrations of common in-
30.0 1.4 × 10− 6–1.0 × 10− 1 6.3 × 10− 6 18 [41] terfering ions. Applicable pH range, lower detection limit, and
34.0 1.0 × 10− 8–1.0 × 10− 3 1.0 × 10− 8 30 [42]
potentiometric selectivity coefficients of the proposed sensor make
25.0 1.25 × 10− 5–1.0 × 10− 1 8.9 × 10− 6 10 [43]
29.2 2.0 × 10− 6–1.0 × 10− 1 8.0 × 10− 7 10 [44] it a superior device both compared to other methods used for the
30.0 1.0 × 10− 7–1.0 × 10− 1 6.5 × 10− 7 60 [45] determinations of this ion. It also can be employed for the estima-
30.2 1.0 × 10− 7–1.0 × 10− 2 5.0 × 10− 8 15 This work tion of mercury content in real samples. Table 7, lists slope, linear
range, detection limit and response time of some of the mercury(II)
selective electrode against proposed solvent polymeric mercury
selective electrode for comparative purposes [21,33,39–45].
potentiometric selectivity coefficient. The resulting selectivity coeffi-
cients are summarized in Table 5.
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