ISSN 10619348, Journal of Analytical Chemistry, 2015, Vol. 70, No. 6, pp. 731–737. © Pleiades Publishing, Ltd., 2015.

ARTICLES

Potentiometric Determination of Cadmium Using Coated Platinum

and PVC Membrane Sensors Based
on N,N'bis(salicylaldehyde)phenylenediamine (salophen)1
Mohammad Mirzaei* and Hadi Behrooj Pili
Department of Chemistry, Shahid Bahonar University of Kerman, Kerman P.O. 76169, Iran
*email: m37mirzaei@gmail.com
Received August 28, 2013; in final form, October 14, 2014

Abstract—The construction and performance characteristics of novel PVC membrane (PME) and coated
platinum (CPtE) cadmium ion selective electrodes based on N,N'bis(salicylaldehyde)phenylenediamine
(salophen) are described. The electrodes exhibit linear responses along with near Nernstian slopes of 28.9 ±
0.4 (PME) and 29.2 ± 0.6 (CPtE) mV/decade of concentration within the Cd2+ ion concentration range of
5.7 × 10–8 to 3.7 × 10–3 M for PME and 3.0 × 10–8–3.0 × 10–3 M for CPtE. These sensors are applicable in
a pH range of 2.5–7.5. The lower detection limits by PME and CPtE are 3.2 × 10–8 and 1.6 × 10–8 M, respec
tively. They have a response time less than 14 s and can be used practically for a period of at least 2 months
without any measurable divergence in results. The electrode can also tolerate partially nonaqueous media
(ethanol, methanol and acetone) up to 30%. The electrodes showed excellent selectivity towards Cd2+ ion
over a wide range of alkali, alkaline earth, and transition metals ions. They were successfully applied to the
direct determination of Cd2+ ions in tap water, aqueduct water, and river water and soil sample. In addition
the electrodes were used as an indicator electrode in potentiometric titration of Cd2+ ion with EDTA.

Keywords: potentiometric, PVC membrane, sensor, salophen, cadmium

DOI: 10.1134/S1061934815060076

1
Cadmium is one of the highly toxic transition met
als and should be handled with care due to its harm to
the environment and human health. Cadmium occurs
naturally in the environment in its inorganic form, and
anthropogenic sources have further contributed to
background levels of cadmium in soil, water and living
organisms. The general population is exposed to cad
mium from multiple sources, including smoking, but
in the nonsmoking general population food is the
dominant source. Experimental and epidemiological
studies have provided substantial evidence that low
levels of longterm exposure to cadmium can contrib
ute to an increased risk of cancer. In the body of ani
mals, cadmium is primarily bound to metallothionein
and these complexes are filtered in the kidney so that
cadmium accumulates in the renal cortex [1–3].
There are several sources of human exposure to cad
mium, including employment in primary metal indus
tries, production of certain batteries, some electro
plating processes and consumption of tobacco prod
ucts [4]. The permissible limits of cadmium discharge
in wastewater and drinking water are 0.1 and
0.05 mg/L, respectively. Several analytical methods,
including atomic absorption spectrometry (AAS), cold
vapor AAS or AAS–ETA (electrothermal atomiza
1 The article is published in the original.
tion) [5–7], inductively coupled plasma–optical
emission spectroscopy [8], anodic stripping voltam
metry [9, 10], chromatography (usually HPLC) [11],
photometry [12] have been utilized for determination
of Cd2+ at low concentration level. These methods give
accurate results but are not very convenient for large
scale monitoring. Potentiometric ion selective sensors
are known as excellent low cost tools for selective, sen
sitive and rapid determination of a vast variety of ana
lytes in different fields of application. They are ex
tremely versatile tools to chemical sensing science in
which selectivity can be chemically adjusted by incor
porating different ionophores into the membrane
phase. Thus, during last three decades, intensive ef
forts have been made to develop good ionsensors for
Cd2+ determination. A number of sensors based main
ly on Ag2S–CdS mixture [13–15], cadmium chelates
[16], petrol compound [17], crown ethers [18–20] and
variety of other ionophores [21] have been reported.
However, most of these methods show some limita
tions in one or more of their working activity range, se
lectivity, response time, pH range and lifetime. Thus,
the development of reliable ion selective sensors for
determination of Cd2+ ion has a considerable impor
tance for environment and human health. To improve
the analytical selectivity, it is essential to search novel

731
732 MOHAMMAD MIRZAEI, HADI BEHROOJ PILI
carrier compounds that would interact with Cd2+ ion
with high selectivity.
In this work, N,N'bis(salicylaldehyde)phenylene
diamine is used as an ionophore, and it is introduced
as a selective carrier for cadmium ion in polymeric
membrane electrode and coated platinum electrode.
EXPERIMENTAL
Reagents. All reagents were of analytical grade.
Chloronaphthalene (CN), dioctyl phthalate (DOP),
dibutyl phthalate (DBP) and dimethyl sebacate
(DMS) were obtained from Aldrich (Milwaukee, WI,
USA). High molecular weight polyvinylchloride
(PVC) powder, tetrahydrofuran (THF), sodium tet
raphenylborate (NaTPB) and potassium tetrakis(p
chlorophenyl)borate (KTpClPB) were purchased from
Merck (Darmstadt, Germany) or Fluka (Buchs, Swit
zerland). The chloride and nitrate salts of metals were
obtained from Merck (Darmstadt, Germany) and
were used without further purification except for vac
uum drying over P2O5. Doubly distilled deionized wa
ter was thoroughly used to prepare all the metal ion so
lutions. N,N'bis(salicylaldehyde)phenylenediamine
(Scheme) was used as a ligand and was synthesized ac
cording to the method described in reference [22].
OH HO
N N
Chemical structure of N,N'bis(salicylaldehyde)
phenylenediamine (salophen).
Apparatus and potential measurements. Atomic ab
sorption spectrophotometric measurements were made
on AA220 spectrometer (Varian, Australia) under the
recommended conditions based on the manufacturer’s
instructions. All potentiometric measurements were
made with a 713 pH–mV meter (Metrohm, Swiss) at
laboratory ambient temperature. All electromotive force
(emf) measurements with the PME and CPtE were car
ried out with the following cell assemblies:
Platinum surface|PVC membrane|Test solution|Salt
bridge (1 M KNO3)|3 M KCl|Ag/AgCl (CPtE);
Ag/AgCl, 3 M KCl|Internal solution, 1.0 × 10–3 M
Cd(NO3)2|PVC membrane|Test solution|Salt bridge
(1 M KNO3)|3 M KCl|Ag/AgCl (PME).
All the emf observations were made relative to an
Ag/AgCl double junction electrode (Azar electrode,
Iran) as an external reference electrode and an
Ag/AgCl electrode was used as the internal reference
electrode under magnetic stirring. Activities were cal
culated according to the Debye–Huckel procedure,
using following equation [23]:
JOURNAL OF ANALYTICAL CHEMISTRY
logf = –0.511z2[µ1/2/(1 + 1.5µ1/2)] + 0.2µ,
where μ is the ionic strength and z is the valence of ion.
Preparation of the electrodes. The PVCbased
membranes were prepared by dissolving appropriate
amounts of ionophore along with anionic additives
(NaTPB or KTpClPB), plasticizer (DBP, DMS, CN
or DOP) and PVC in THF (Table 1). The components
were added in terms of weight percentages. After com
plete dissolution of all the components and thorough
mixing, homogeneous mixture was poured into glass
rings (20 mm i.d.) and placed on a smooth glass plate.
The solution was then allowed to evaporate for 24 h at
ambient temperature. The master PVC membrane of
about 0.4 mm thickness was sectioned with a cork bor
er (5 mm diameter) and attached to a polyethylene pi
pette as a body of the electrode (5 cm length and 4 mm
i.d. on top), with PVC–THF slurry. The membrane was
placed carefully at the bottom of the tube and filled with
an internal filling solution, 1.0 × 10–3 M Cd(NO3)2. The
electrode was finally conditioned by soaking in cadmi
um nitrate solution (1.0 × 10–2 M) for 24 h till reproduc
ible and stable potential were achieved.
In order to prepare the coated platinum disk elec
trode, Pt wire with area 0.0314 cm2 was washed with
30% HNO3 and dried overnight. This was placed in a
10 cm long, 3 mm i.d. Pyrex tube sealed at one end.
One end of the wire was then sealed in the glass by
heating coil temperature. The sealed end was polished
with sandpaper until the wire cross section was ex
posed. Electrical connection to the unsealed end of
the Pt wire was made with a Cu wire. The working sur
face of the platinum disk electrode was polished with a
nanoAl2O3 powder (Fluka) on a polishing pad, soni
cated in doubly distilled water and dried in air. Mem
brane solution was prepared by thoroughly dissolving
ionophore, PVC and plasticizer in about 5 mL THF.
The resulting mixture was evaporated slowly at ambi
ent temperature until an oily concentrated mixture
was obtained. The coating process of polished plati
num electrode was performed by dipping electrode
three times into the membrane solution. After coating,
the membrane was airdried until a thin film was
formed, and the electrode was allowed to stabilize over
night. The electrode was finally conditioned for 12 h in
a 1.0 × 10–2 M Cd(NO3)2 solution.
RESULTS AND DISCUSSION
Potential response. Nitrogen and oxygen donor at
oms in the structure of ligand with high lipophilic
character, salophen were expected to act as suitable
ion carriers in the PVC membrane with respect to spe
cial transition and heavy metal ions. Thus, in the pre
liminary experiments, the ligand was used as a neutral
carrier for the preparation of polymeric membrane
and coated platinum electrodes, for a variety of metal
ions. The potential responses obtained with the ion se
Vol. 70 No. 6 2015