Potentiometric Chromate

Journal of The Electrochemical Society, 161 (6) B129-B136 (2014)
0013-4651/2014/161(6)/B129/8/$31.00 The Electrochemical Society
B129
Potentiometric Chromate Anion Detection Based on Co(SALEN)2

Ionophore in a PVC-Membrane Sensor
Majid Rezayi,a,b,z Mostafa Ghasemi,c Reza Karazhian,b Mehran Sookhakian,a
and Yatimah Aliasa,
a Chemistry Department, Faculty of Science, University Malaya, 50603 Kuala Lumpur, Malaysia
b Food Quality and Safety Research Department, Food Science and Technology Research Institute,
ACECR Mashhad Branch, 91775-1376 Mashhad, Iran

Cell Institute, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor D.E., Malaysia
c Fuel
Fabrication of a polymeric membrane sensor based on N,N Bis(salicylidene) ethylenediamino cobalt(II) hydrate (Co(SALEN)2 ) as
an ionophore was focused upon for the purpose of optimizing a PVC matrix. The membrane contained Co(SALEN)2 , PVC matrix,
2-Nitrophenyl octyl ether (oNPOE) as a plasticizer, and tetradodecylammonium chloride (TDDACl) as a lipophilic ionic additive
with the composition of 5:30:62:3 (w/w), and underwent optimization. The Nernstian slope, detection limit, and response time were
28.33 0.10 mV/decade, 7.9 107 M, and <10 s respectively. The direct determination of 2 to 48.5 g/ml of chromate standard
solution showed an average recovery of 96.03% and a mean relative standard deviation of 1.6% at 100.0 g/ml for Co(SALEN)2
sensors. The ionophore functionality in the polymeric membrane and the strengths of anion-carrier interaction were studied by
UVVis, Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM) analysis.
2014 The Electrochemical Society. [DOI: 10.1149/2.051406jes] All rights reserved.
Manuscript submitted December 9, 2013; revised manuscript received April 14, 2014. Published April 30, 2014.
Many researchers have undertaken substantial studies and advanced understanding for the verification of electrochemical sensors
to determine chemical and biological quantities. A large variety of
electrochemical methods have been used in the fabrication and optimization of electrochemical sensors.19 Anion selective electrodes are
regarded as important groups of ion selective electrodes (ISEs). Frant
and Ross (1966) were among the first to research the mechanism of
anion sensors,10 and closely followed by Park and Simmons work
(1968) on synthetic inorganic anion receptors.11,12 However, there are
fewer anion selective electrodes compared to cation selective electrodes due to their large size, diverse shapes, and large hydration
energies.13
The desirable chemical and physical properties of organometallic
compounds ensure their usage as ionophores in the field of ISEs
studies.1416 There are many publications on the subject of anion
receptors, whereupon metal-based complex compounds are regarded
with interest as receptors due to the specific reaction between the
central metal ion and primary anions.1719
The complex reaction between metal ions and different ligands such as Schiff bases,20,21 calixarenes,22,23 phthalocyanines,24
porphyrins25 and metal-salens26,27 have been reported for high specific metal-ligand interactions. These reactions induce the selectivity
of membranes toward the anions that are somewhat different from
classical anion exchangers. The coordination of anionic species to
the metal center of ionophore molecules leading to the potentiometric
response of the membrane includes these types of complexes.
As expressed in the previous article,28 the stoichiometry complexation between Co(SALEN)2 and CrO4 2 achieved a 1:1 ratio with a
stability constant (log Kf ) of 3.02. The 1:1 binding reaction between
chromate anion and the Co(SALEN)2 ligand (Figure 1) is determined
via the following equilibrium:
chromate ions.29
2
HCrO

CrO4 2
4 Cr2 O7
pH > 6.5
46
<4
In this work, the pH of all solutions was between 7 and 10 and

correspondingly the Cr(VI) form is mostly CrO4 2 ions.
Cr(VI) finds widespread use in many industrial applications, and
its harmful and toxic effect on health30 have prompted development of
various techniques such as spectrophotometry,31,32 chromatography,33
polarography,34 and capillary zone electrophoresis35 in order to detect
trace amounts of chromium. While most approaches employ sophisticated and high-cost equipment, potentiometric methods utilize ISEs
as simple and economical tools with benefits of fast response time,
low detection limit, and good selectivity.8,14,3639 ISE usage has recently been reported for the quantification of chromium ions in sample
solutions.40,41
Despite efforts to expand studies for chromium (VI) selective electrodes, real world application remains limited: Most such electrodes
suffer major defects such as insensitivity at low concentrations of
chromate (<1 ppm), poor selectivity, and high response time.4244
These considerations for the contxt of this work have led to the
chromate anion being determined as fabricated polymeric sensors
based on metal-salens, since these anion receptors have highly selective complexation properties for anions. The N,N Bis(salicylidene)
ethylenediamino cobalt(II) hydrate (Co(SALEN)2 ) is introduced as
a suitable ionophore, and is utilized as a major component to fab-
2
(Co(SALEN)2 )orq + (CrO4 2 )aq
((Co(SALEN)2 , CrO4 )org
The use of Co(SALEN)2 , as a suitable carrier in the fabrication of

membrane polymeric chromate selective electrode was duly investigated.
In a highly acidic aqueous solution where pH<1, the dominant
form of Cr(VI) is H2 CrO4 ; in the range of pH 24 the dominant
form is dichromate, and between pH 4 and 6, it is in equilibrium
between Cr2 O7 2 and HCrO4 ions. Under alkaline or slightly acidic
conditions of pH > 6.5, Cr(VI) exists predominantly in the form of
Electrochemical Society Active Member.

E-mail: chem_rezayi@yahoo.com
Figure 1. The structure of the ligand-anion (Co(SALEN)2 -CrO4 2 ).
Downloaded on 2014-05-11 to IP 130.194.164.106 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
B130
ricate the membrane anion-selective electrode in order to determine

the amount of chromate anion in the solutions. The UV-Vis, Fourier
transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM) were utilized in order to investigate the strength of
the complex reaction between Co(SALEN)2 carrier and CrO4 2 anion, and the functional role of Co(SALEN)2 as a basic reagent for the
fabrication of membranes.
Chemicals
For membrane fabrication, N,N Bis(salicylidene) ethylenediamino
cobalt(II) hydrate (Co(SALEN)2 ), high molecular weight polyvinyl
chloride (PVC) powder, dioctylphthalate (DOP), dibutylphthalate
(DBP), 2-Nitrophenyl octyl ether (oNPOE), benzyl acetate (BA),
tetrahydrofuran (THF) with a purity of >/ 99%, tridodecylmethylammonium chloride (TDDMACl), tetradodecylammonium chloride
(TDDACl) and Dried acetonitrile (AN) (max. 0.005%H2 O) were obtained from Fluka (Germany) and Merck (Germany) chemical companies. All the sodium or potassium salts of the anions being used (exclusively from Merck (Germany), Aldrich (Germany), BDH (England)
or HmbG (Germany) are of high purity, and were used as received.
Di-ionized water was used throughout the experiments.
Apparatus
The experiments were all conducted at room temperature (25.0
0.1 C). All potentiometric measurements were undertaken using a
digital potentiometer (Seven Multi by Mettler Toledo, Switzerland) by
employing the Mettler Toledo double junction silver/silver chloride
reference electrode as the external reference electrode and silver/silver
chloride electrode containing a 3 molL1 solution of KCl as the internal reference electrode.
A pH-meter (DKK-TOA, HM-7J, Japan), laboratory balance
(A&D, HR-200, England), temperature controlled shaker (Fisher
Scientific Stirring Hot Plate, IP 21 KLO, England), digital conductivity meter (Hanna, HI 255, USA), FT-IR spectrophotometer
(Perkin Elmer, spectrum 100 series, USA), UV-Vis spectrophotometer (SHIMADZU, 1650 pc, Japan), JEOL scanning electron microscope (SEM) (Model 1455 LEO, Japan), Perkin-Elmer optical emission spectrometer (model Optima 2000 DV, USA) as an inductively
coupled plasma (ICP), and Thermo SCIENTIFIC atomic absorption
spectrometer (AAs) (model S SEIES, England) were employed in the
experiment.
Sample characterization. An investigation on immobilization of

ionophore on the solid or liquid membranes is a priority field of interest, especially in the context of ISEs. In this study, the Co(SALEN)2
immobilized PVC membrane was evaluated using UV-Vis (Perkin
Elmer model SHIMADZU, 1650 pc) in the range of 190590 nm and
FT-IR (spectrum 100 series) in the wave number range of 4004000
cm1 spectrophotometers. The complex formation reactions between
Co (SALEN)2 and CrO4 2 anions were investigated using UV-Vis
spectroscopy via application of three separated sample solutions 1
104 M of Co(SALEN)2 , K2 CrO4 and their binary mixture in
acetonitrile-water (1:1 v/v) media. The morphology of ionophoreimmobilized PVC membrane surface was studied by SEM (1455
LEO). For this work, the fabricated membranes are fixed on polished
and washed sample holders then coated with gold using the vacuum
chamber in order to render high resolution images facilitated by the
increased conductance of the samples.
Preliminary study of complexation. The UV-Vis spectroscopy
method was used to investigate the complexation ability of
Co(SALEN)2 ligand with CrO4 2 anions in this study. As shown
in Figure 2, 1 104 M of Co(SALEN)2 ionophore with two absorption maxima at 366 and 267 nm (via the transition * and n*
respectively) is added to an equal concentration of K2 CrO4 with three
absorption maxima at 380, 247 and 220 nm, and a consequent decrease
in absorbance shows an absorption maxima shift to 375, 252, and 225
nm. This result is evidence the Co(SALEN)2 ionophore has a high
affinity toward the chromate anions via complex formation reaction
between Co(II) metal center and CrO4 2 anions. According to previous studies, the central metal Co(II) in the Co(SALEN)2 ligand with
four oxygen and nitrogen hard donor atoms became relatively hard,
and are able to accept chromate anions. Another factor is the -back
bonding that renders Co(II) harder and more reactive in regards to
chromate anions.45,46 Other anions did not show any detectable spectral changes within the spectrum of Co(SALEN)2 ionophore complex.
In a further investigation, the conductometric method was used
to evaluate the complexation between the Co(SALEN)2 carrier and
anions (Nn ) via the calculation of complex constant formation in
acetonitrile-water (1:1, V/V) mixture at 25 C. The results for 1:1
complexes were obtained by fitting non-linear least squares using the
GENPLOT software.47 As shown in Table I, the obtained formation
constants for Co(SALEN)2 -CrO4 2 are higher than for other tested
anions, which indicate the strong reaction between Co(SALEN)2 and
chromate anions.
Membrane preparation and electrode construction. The mixture

includes 5.0 mg of ionophore Co(SALEN)2 , 62.0 mg of the plasticizer
oNPOE, 30.0 mg of polymeric matrix PVC, and 3.0 mg of TDDACl as
the lipophilic ion exchanger, and this mixture was dissolved in 3.0 mL
of dry THF. An oily product was the result of the slow evaporation
of the solution. The 0.3 mm thick non-transparent membrane was
formed by dip-coating a Pyrex tube (3 mm o.d) into the oily mixture.
The fabricated membrane was kept at room temperature for 24 hours
to air dry. An internal solution (1.0 102 M K2 CrO4 ) was used
inside the Pyrex tube, and was then soaked for 24 hours in the same
solution by placing an Ag | AgCl electrode as an internal reference
electrode.
Potential measurements. All potential measurements were carried out at 25.0 0.1 C, using the following cell(s):
Ag | AgCl KCl (3M) | internal solution (1.0 102 M K2 CrO4 )
| PVC membrane | test solution | Ag | AgCl KCl (3M).
The performance of the electrodes was investigated in the concentration range of 1.0 106 1.0 101 M potassium chromate from
the serial dilution of 0.1M stock solutions at a constant pH. In all of the
experiments, the solutions were stirred and all the potentials recorded
upon achieving static values. The resulting observed potentials were
plotted against the logarithm of CrO4 2 anion concentration.
Figure 2. UV-Vis absorption spectra of ANH2 O binary mixture solutions of

1.0 104 M Co(SALEN)2 (A); 1.0 104 M K2 CrO4 (B); and Co(SALEN)2
1.0 104 M treated with1.0 104 M K2 CrO4 solution (C).

Table I. The formation constants of Co(SALEN)2 -Nn complexes.
Anion
Log Kf SDa
CrO4 2
C2 O4 2
SO4 2
CO3 2
Br
NO3
3.14 0.06
2.11 0.08
1.85 0.17
1.98 0.10
1.25 0.05
1.87 0.14
a SD:
standard deviation.
This study provides a clear justification for the utilization of

Co(SALEN)2 as an excellent neutral ion-carrier for the construction of a highly selective chromate PVC-based membrane sensor,
whereby results showed this membrane possesses high selectivities
toward chromate anions and allow satisfactory performance in the
chromate selective sensor field.
Results and Discussion

Immobilization of ionophore. FT-IR spectroscopy was employed to study the immobilization procedure-PVC grafted with the
Co(SALEN)2 ionophore, and also the physical stability of the optimized membrane. Four types of membranes were used in these
B131
studies,: blank membrane i.e. without ionophore (spectra A), initial

membrane before (spectra B) and after stocking in 1.0 102 M
K2 CrO4 solution (spectra C), and when two months have elapsed
(spectra D). As illustrated in Figure 3 for the blank membrane, the
absorption band assigned to stretching NO2 groups is seen at 1350.32
and 1523.60 cm1 . Furthermore, the absorption band associated with
the C-O and C = C stretching are observed at 1012.39 to 1258.03
cm1 and 1465.95 to 1606.78 cm1 respectively. Following interaction between the CrO4 2 anion and the central metal of ionophore, the
absorption bands related to M-O bridges were apparent in the range
of 960 to 1000 cm1 , and led to the extension and increase in the
absorption bands in this area.48,49 The results of spectra D showed no
significant changes occurred in the absorption bands for the fabricated
membrane after two months.
Further results were obtained from the surface membrane morphologies of the fabricated sensor membrane surface via investigation by SEM. As shown in Figure 4, the membrane without the
Co(SALEN)2 ionophore and oNPOE plasticizer exhibited a physically tight structure (Figure 4A) that agrees with previously reported morphologies of membrane PVC sensors.41,50 The optimized
PVC membrane included the Co(SALEN)2 ionophore and oNPOE
plasticizer, whereby the existence of channels that allow the diffusion of chromate anions (Figure 4B) demonstrate a physically loose
structure. As shown in Figure 4C, the morphology of the surface
membrane showed a physically swollen structure, due to the effect
of the K2 CrO4 solution, without any leakage during a two month
period.
Figure 3. Fourier transforms infrared (FT-IR) spectra of the PVC membrane based on the Co(SALEN)2 ionophore in different states: (A) blank membrane, (B)
before, and after being destocked in 1.0 102 M K2 CrO4 solution for (C) 24 hours and (D) two months.
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Figure 4. SEM pictures of the surface membrane based on Co(SALEN)2 (A) bare membrane (without ionophore and oNPOE); (B) fresh optimized membrane;
and (C) two months employed membrane.
fect the partition coefficient of anions in the form of anion-ionophore

complex formation constants. It would appear that oNPOE, as a relatively high dielectric constant ( = 23.9) plasticizer, provides the
appropriate condition for Co(SALEN)2 carrier mobility and complexation reaction with chromate anions in the organic membrane
layer.
Also shown in Table II, the existence of two different lipophilic
cationic additives in the membrane composition (membrane nos. 3
& 7) enhanced the selectivity of the polymeric sensor without using
additives (membrane nos. 5 & 9), and via the reduction of the ohmic
resistance of membrane. An investigation into the effectiveness of the
cationic additive with different additive/inophore mol ratio determined
the optimized amount of 0.6 for both additives over the range of
chromate concentration.
The internal solution effects on the response of the optimized
sensor were investigated, with resultant findings on four measurements
from 105 M to 101 M and corresponding EMF versus log [CrO4 2 ]
plot as shown in Figure 5C. The optimal concentration of internal
solution was 1.0 102 M potassium chromate, in which the highest
response of Nernstian behavior was obtained.
Finally, a study into the effect of pH on the electrode potential (Figure 5D) showed that the potential remained constant when the working
pH range was 710. Diluting NaOH or HNO3 solutions altered the
pH of the aqueous 1.0 103 and 1.0 102 M CrO4 2 solution,
and the potential of the solutions was duly monitored. The deterioration in the potential at lower pH values was due to the formation
of dichromate and polychromate that appear to affect the electrode,
while the drift in higher pH values develops as a result of interfering
hydroxide anions-coordinated central metal caused by the addition of
sodium hydroxide.
Optimization of membrane composition

All membranes were soaked for 24 hours in 0.01M of K2 CrO4 solution prior to any potential measurements. The ratio of the ionophore
and membrane elements was optimized in order to obtain the best
performance of membrane composition.
It is observed in Table II that membrane no. 3, with a composition
of 5:30:62:3 mg (Co(SALEN)2 , PVC, oNPOE, TDDACl) exhibited
a linear working range from 1.0 106 to 1.0 101 M, with a
Nernstian slope of 28.33 0.10 mV per decade. Co(SALEN)2 , as
an ionophore, plays a fundamental role as a membrane in relation to
CrO4 2 anions. As shown in Table II, membranes 10 and 12 (without
ionophore) demonstrated narrow working concentration ranges and
slight non-Nernstian slopes (see Figure 5A).
As previously mentioned, the plasticizer possesses an important
element in the ionophore immobilized membrane, as it provides mobility to the ionophore bearing the ion within the membranes and
forms channels for target ionic species.41 This work measured the
potentiometric response of the fabricated CrO4 2 membrane sensor
based on Co(SALEN)2 as an electroactive material, and also various
plasticizers with different polarities (DBP, DOP, oNPOE and BA)
in the PVC matrix and the concentration ranges of 1.0 106 to
1.0 101 M. As shown in Table II and Figure 5B, the oNPOE
palsticizer was determined in this study to be the most suitable material, as it enhances the selectivity and Nernstian slope in the context of membrane construction. The optimum PVC/oNPOE ratio that
showed the best performance was determined to be about 1:2. Despite
the fact that plasticizers lack any role in the context of selectivity
changes of ionophore-based membrane sensors, it is reasonable to
assume that various plasticizers with different dielectric constants af-
Table II. Composition of membranes of Co(SALEN)2 ionophore and performance characteristics of CrO4 2 sensor at 298.15 K.
Composition of membrane (%)
Membrane
no.
Co(SALEN)2
PVC
DBP
DOP
1
2
3
4
5
6
7
8
9
10
11
12
5
5
5
5
5
5
5
2
5
30
30
30
30
30
30
30
33
33
33
33
33
63
62
62
oNPOE
BA
TDDMACl
TDDACl
Working concentration
range (M)
Slope
(mV/decade)
Detection
limit (ppm)
R2
62
62
62
62
62
64
61
66
62
2
3
3
3
3
1
1
1.0 106 0.1

1.0 106 0.1
1.0 106 0.1
1.0 106 0.1
1.0 106 0.1
1.0 106 0.1
1.0 106 0.1
1.0 106 0.01
1.0 106 0.01
1.0 105 0.1
1.0 106 0.1
1.0 104 0.1
23.6 0.2
24.8 0.2
28.3 0.1
25.6 0.1
22.4 0.3
19.5 0.2
26.5 0.2
15.8 0.3
21.1 0.2
9.8 0.4
26.9 0.1
10.5 0.5
0.7
0.6
0.5
0.7
0.9
0.5
0.6
6.9
0.5
10.0
0.6
40.0
0.98
0.98
0.99
0.99
0.99
0.99
0.99
0.99
0.99
0.96
0.99
0.98
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Figure 5. Effect of membrane composition: (A) with ionophore, without ionophore (blank membrane) and without additive (B) various mediators,
oNPOE, DBP, DOP, and BA (C) internal solution, and (D) pH at two different CrO4 2 concentrations, (a) 1.0 102 M and (b) 1.0 103 M on the
potential response of the chromate-selective sensor at 298.15 K.
Working concentration range and slope

The potential response of the proposed membrane based on Co
(SALEN)2 to CrO4 2 anions are shown in Figure 6. The optimized
electrode shows a linear response to chromate ions in a wide working
Figure 6. The potential response of the membrane based on Co(SALEN)2

electrode to CrO4 2 anion at 298.15 K.
concentration range (1.0 106 1.0 101 M), with a detection

limit of 7.9 107 M and a Nernstian slope of 28.33 0.10 mV
per decade of concentration, and a correlation coefficient of 0.99.
In preliminary experiments, the Co(SALEN)2 ionophore was employed as a potential anion carrier in the construction of polymeric
PVC membrane sensors for a wide variety of common inorganic anions such as fluoride, chloride, bromide, perchlorate, hydroxide, thiocyanate, acetate, nitrate, permanganate, sulfate, carbonate and oxalate
anions. The potential responses of the fabricated electrode for halides,
single charged and double charged anions are shown in Figure 7A,
7B and 7C respectively. The optimized membrane sensor provides a
good selectivity toward the chromate anions over other anions. Results are derived from the presence of a specific reaction of central
metal ion with chromate anions, and this reaction is believed to be the
anti-Hofmeister selectivity.51
Dynamic and static response times. The dynamic responses
of the proposed chromate electrode for step changes in the concentration of the CrO4 2 ion from 1.0 106 to 1.0 101 are
shown in Figure 8A. The time for the electrode to reach 90% of
the steady response was less than 10 s. Measurements were performed from high-to-low aqueous sample concentrations in order to
evaluate the reversibility of the sensor, and the results are shown
in Figure 8B. These latter results show that the potentiometric response of the electrode was reversible, and the equilibrium time of
about 114 seconds for the electrode to reach the constant value in
the low-to-high sequence was much longer than for the high-to-low
sequence.
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Figure 8. Dynamic response time of the potentiometric sensor for (A) different concentrations of chromate, and (B) several high-to-low sample cycles at
298.15 K.
As shown in Table III, the membrane demonstrated excellent Nernstian behavior without any significant changes in the slope and detection limit within the time interval studied. The electrode was stored in
a 0.01 M K2 CrO4 solution during usage.
Selectivity of the sensor. The selectivity of the proposed sensor
was investigated by separate solution method (SSM) (ai = aj = 102
Pot
M) and the potentiometric selectivity coefficient K Cr
, which
O4 2 ,B
was calculated in the presence of certain inorganic anions using an
equation similar to the one described in Table IV.
The selectivity coefficient patterns clearly indicate that the proposed electrode is highly selective toward the chromate anion. The
interfering effect of the anions is in the following order:
C2 O4 2 > CO3 2 > Cl > SO4 2 > NO3 > F > OH > ClO4
Figure 7. The response of the CrO4 2 ISE based on ionophore Co(SALEN)2
toward (A) halide, (B) single charged, and (C) double charged anions at
298.15 K.
Lifetime of the electrode. The stability of the potential response

of the proposed electrode was investigated to examine whether the
immobilized ionophores could function in an ion-selective membrane
without leaching. Table III shows the results of an extended duration
test on the response stability.
> Br > SCN > Mno4 > CH3 COO

Based on the Hofmeister series, the sequence is:
ClO4 > SCN > NO3 > Cl > SO4 2
A reason why the selectivity coefficient of the proposed chromate
electrode failed to comply with the Hofmeister series could be due
to the specific interaction of the anions with the metal center in the
carrier Co(SALEN)2 used in this study.52 Further investigation of this
anti-Hofmeister effects confirmed that the Hofmeister sequence is not
unique and depends on several factors such as nature and physical
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Table III. The life time behavior of the chromate-selective electrode based on Co(SALEN)2 at 298.15 K.
No.
Period
Working concentration range (M)
Detection limit (M)
Slope (mV/decade)
R2
1
2
3
4
5
6
Initial
1 week
2 weeks
4 weeks
8 weeks
12 weeks
1.0 106
1.0 106
1.0 106
1.0 106
1.0 106
1.0 106
7.9 107
4.0 107
9.0 107
1.0 106
1.6 106
2.5 106
28.3 0.1
28.2 0.1
28.1 0.2
27.2 0.2
27.6 0.3
26.7 0.2
0.99
0.99
0.99
0.99
0.99
0.99
1.0 101
1.0 101
1.0 101
1.0 101
1.0 101
1.0 101
Table IV. Selectivity coefficients of chromate ISE as determined

by separate solution method (SSM) at 298.15 K.
Interference
anion
F
Cl
Br
SCN
CH3 COO
OH
log K Pot
Cr O42 ,B
2.8
2.2
3.2
4.1
5.3
2.9
Interference
anion
ClO4
NO3
Mno4
SO4 2
C2 O4 2
Co3 2
log K Pot
Cr O42 ,B
3.1
2.5
4.7
2.3
1.4
1.7
properties of the solvents, the origin of ionic-effects, electrostatic and

hydrogen binding effects, and also coordination action of species ions
to form the complex. Moreover, the weakly acidic systems added to
the discrepancy in behavior for the sequence of anions. Such discrepancy is caused by the protonated anions and results in the loss of
charges. In this case, the utilization of the polar oNPOE plasticizer
increased the reaction of the Co(SALEN)2 carrier with divalent anions in comparison to the monovalent ones. This conclusion agrees
with the Born model, where the nature of the plasticizers are based on
the dielectric constant, which in turn influences the reaction of ionic
charged species.53 As shown in Table IV, the anions that are most
actively interacting with the electrodes are C2 O4 2 and CO3 2 .
Potentiometric titration
The proposed sensor was used as an indicator electrode in the
titrimetric determination of chromate ions. Potentiometric titration
was conducted using a 25 mL solution of 1.0 103 M K2 CrO4
with a 1.0 102 M Pb(NO3 )2 solution in a constant pH range of
710. The addition of Pb2+ to the solution will increase the potential
via a corresponding decrease in the concentration of CrO2 4 in the
solution, and this in turn causes the formation of 1:1 stoichiometry of
the CrO4 -Pb complex. The end point obtained from the potentiometric
curve corresponds to this result (Figure 9).
Validation with AAs and ICP. The proposed chromate sensor
was also used for the determination of chromium by detection of
chromate in certain series sample solutions (standard solution).Three
CrO4 2 solutions with different concentrations, 3.88, 19.41 and 38.83
Figure 9. Potentiometric titration plot of 1.0 103 M K2 CrO4 solution (25

mL) with Pb(NO3 )2 (1.0 102 M) at 298.15 K.
ppm, were analyzed with the proposed sensor using AAs and ICP
spectrometric methods. As illustrated in Table V, the results obtained
from the chromate sensor are in satisfactory agreement, corresponding
to approximately 2% variation, with those determined by AAs and ICP
spectrometry.
Comparison of chromate-selective electrode in this work with

other reported chromate-selective electrodes
Table VI presents a comparison of the proposed sensor with previously reported chromate electrodes. The results show that the proposed
chromium (VI) electrode is superior in terms of working concentration range, detection limit, and response time compared to previous
works. The ISE proposed in this paper is one of the few electrodes
prepared as a chromate selective PVC membrane electrode, and provides a highly respectable performance when tested alongside other
electrodes.
Table V. Potentiometric determination of chromium(VI) ion in sample solutions at 298.15 K.

Cr(VI) in ppm determineda
No.
Sample solution
Concentration (M) / ppm
sensor
AAs
ICP
Recovery%
1
2
3
2.0 105 / 3.8

1.0 104 / 19.4
2.0 104 / 38.8
3.5 0.2
19.2 0.2
38.7 0.1
3.59 0.10
19.35 0.05
38.79 0.10
3.62 0.08
19.36 0.03
38.80 0.07
89.4
98.9
99.7
a Average
of three measurements.
B136
Table VI. Compression of proposed CrO4 2 sensor between this study and previous studies at 298.15 K.
No.
1
2
3
4
5
6
Reference
no.
Nernstian slope
(mV per decade)
Working concentration
range (M)
Detection
limit (ppm)
Response
time (s)
Life time
(month)
This study
28.3 0.1
28.0 0.2
29.0 0.2
26.3 0.2
26.8 0.2
27.7 0.2
1.0 106
3.0 105
1.7 105
2.1 106
2.0 105
8.0 106
0.15
1.50
0.30
0.22
1.05
0.40
<10
12
13
NM*
NM*
30
3
3
5
6
23
6 weeks
40
54
41
44
55
to 1.0 101
to 1.0 101
to 1.0 101
to 1.0 101
to 1.0 101
to 2.0 102
*NM: not mentioned.
Conclusions
A novel ionophore-immobilized membrane based on Co(SALEN)2
for the determination of the chromate anion, with composition of
5:30:62:3 (mg) Co(SALEN)2 :PVC:oNPOE:TDDACl, was prepared
by the dip-coating method. The developed sensor is shown to perform
well in comparison to other sensors over a wide concentration range
from 1.0 106 to 1.0 101 M with Nernstian slope (28.33
mV/decade) and a deviation of 0.10 mV between pH 710. Thus,
this paper can conclude the novel Co(SALEN)2 sensor is stable, reproducible, provides selective response over a prolonged period as well
as fast response time (< 10 s), and excellent detection limits (0.15
ppm). It is expected that these findings are useful for applications and
further work in this area.
Acknowledgments
This work was supported by University of Malaya, Kuala Lumpur,
Malaysia by using the High Impact Research grant UM-MOE
UM.C/625/1/HIR/MOE/F00004-21001 from the Ministry of Higher
Education Malaysia and PV 124-2012A and the department of chemistry, Unversiti Putra Malaysia, Serdang, Selangor, Malaysia.
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