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JIEC 2496 18
Journal of Industrial and Engineering Chemistry xxx (2015) xxxxxx

Contents lists available at ScienceDirect

Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec
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Polyurethane-based cation exchange composite membranes:

Preparation, characterization and its application in development of
ion-selective electrode for detection of copper(II)
Q1 Umair

Baig a,b, Asif Ali Khan a,*

Analytical and Polymer Research Laboratory, Department of Applied Chemistry, Faculty of Engineering and Technology, Aligarh Muslim University, Aligarh
202002, UP, India
b
Center of Excellence for Scientic Research Collaboration with MIT, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 23 February 2014
Received in revised form 18 November 2014
Accepted 31 December 2014
Available online xxx

Polyurethane-cerium(IV) phosphate composite cation exchange membranes were prepared by solution

casting method in different stoicheometric ratios of polyurethane and cerium(IV) phosphate. The
structure and morphology of the prepared membranes were ascertained by FTIR, SEM, TGA and DTA. The
membrane having composition 1:2 (PU: cerium(IV) phosphate) shows best results for ion-exchange
capacity, water content, porosity, thickness and swelling. The Cu(II) selective electrode was developed by
using this membrane for the determination of Cu(II) in solutions. The accuracy of the procedure has been
tested on drinking water samples spiked with known amounts of Cu(II) and results were comparable to
those generated by Atomic Absorption Spectrophotometer.
2015 Published by Elsevier B.V. on behalf of The Korean Society of Industrial and Engineering
Chemistry.

Keywords:
Polymer
Composite membranes
Cation exchanger
Cu(II) selective electrode

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Introduction

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24
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27

In the recent years, research focusing on polymer-based

composite ion-exchange membranes either by blending of
different polymers or by incorporating inorganic materials/ionexchanger into polymers, has attracted considerable attention in
the academic and industries [14]. Composite ion-exchange
membranes with new or improved properties such as improved
mechanical, thermal, and ion-exchange properties may offer better
characteristics than their single-polymer material counterparts
[5,6]. Polymer based composite ion-exchanger/membranes are
now widely used for application in such elds as membrane
electrolysis, electrochemical separations, solid polymer electrolysis, fuel cells, separation of heavy toxic metal ions and in making
ion selective membrane electrodes [117].
Copper is broadly utilized as a part of mechanical, antimicrobial,
natural and ecological applications because of its properties of high
electrical conductivity, substance and warm soundness, pliancy and
ability to make composites with numerous metals. Copper is a vital

* Corresponding author. Tel.: +91 571 2720323; fax: +91 9045462192.

E-mail addresses: asifalikhan2008@gmail.com, umair.alig@gmail.com (A.A. Khan).

component on account of their utilization as key supplements to

amphibian organic entities and is additionally dangerous at high
xation (>15 mg day1), the maximum permissible concentration
limits of copper is 2 mg day1 [18]. Copper insufciency brings
about weakness while its collection brings about human body
dyslexia, hypoglycemia, liver and kidney harm, gastrointestinal
issues and Wilson sickness (WD) [19]. In the point of view of such
noxious effects of copper, its determination in ecological specimens
is of utmost importance. A lot many analytical methods such as ionexchange chromatography, neutron activation analysis, atomic
absorption spectrometry (AAS), cold vapour AAS or ame atomic
absorption spectrometry-electrothermal atomization (AASETA),
gravimetry have generally been utilized for the determination of
trace amount of copper in aqueous solutions and water bodies. Most
of these methods suffer from many disadvantages such as time
consuming, multiple sample manipulations, excessively costly and
non-applicability in eld work. Recently, the potentiometric method
by using an ion sensor or ion-selective membrane electrode is an
alternative, simple and low cost method for determination of
copper. Thus, in this work, a new Cu(II) ion-selective electrode based
on polyurethane-cerium(IV) phosphate cation exchange composite
membrane is prepared and characterized for the potentiometric
determination of Cu(II).

http://dx.doi.org/10.1016/j.jiec.2014.12.045
1226-086X/ 2015 Published by Elsevier B.V. on behalf of The Korean Society of Industrial and Engineering Chemistry.

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JIEC 2496 18
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Table 2
Conditions of preparation and ion-exchange capacity of various Polyurethanecerium(IV) phosphate cation-exchange composite membranes.

51

Experimental

52

Reagents and chemicals

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56
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58

For the preparation of cation exchange composite membranes

the main chemicals were used: Polyurethane (PU) from Research
design and standard organization, India, tetrahydofuran, ceric
sulfate (Ce(SO4)2.4H2O), orthophosphoric acid (H3PO4) were used
as received from Qualigens (India Ltd.). All other reagents and
chemicals were of analytical grade (AR).

59

Synthesis

60
61
62
63
64
65

Cerium(IV) phosphate
Preparation of cerium(IV) phosphate was carried out by taking
different ratios of 0.1 mol L1 Ce(SO4)24H2O (prepared in
1 mol L1 H2SO4 solution) and an aqueous solution of ortho
phosphoric acid (prepared with demineralized water) under
varying conditions given in Table 1 [20,21].

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Preparation of polyurethane-cerium(IV) phosphate cation exchange

composite membrane

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73
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75
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79
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85
86
87
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89
90

Polyurethane-cerium(IV) phosphate cation exchange composite membranes were prepared in various weight ratios of
cerium(IV) phosphate with polyurethane by solution casting
method. 500 mg polyurethane was dissolved in tetrahydrofuran
(THF) at room temperature. A controlled amount of cerium(IV)
phosphate (200, 300, 400, 500, 800 and 1000 mg) were dispersed in
to polyurethane solution in THF. Mechanical stirring was applied
for at least 24 h at room temperature in order to obtain
homogeneous cerium(IV) phosphate dispersed polyurethane
solution. The polymer dispersed was cast on to clean glass plates
and kept for 48 h at room temperature to allow complete
evaporation of THF. The resultant composite membranes were
cautiously peeled out of the glass plates and rinsed with doubly
distilled water on both sides and dried at room temperature.
Polyurethane membrane was prepared with a similar method. The
dried polyurethane-cerium(IV) phosphate composite membranes
were converted into H+-form through immersion in 1 mol L1
HNO3 for 2 days with occasional shaking intermittently replacing
the supernatant liquid with fresh 1 mol L1 HNO3 two to three
times. The excess was removed after several washings with DMW
and nally dried at room temperature. The condition of preparation and the ion-exchange capacity (IEC), of the cation exchange
composite membranes are given in Table 2.

91

Ion-exchange capacity measurement (IEC)

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93
94
95

For determination of ion exchange capacities (IECs) of the

cation exchange composite membranes, accurately weighed dry
composite membranes were converted in to H+-form through
immersion in 1 mol L1 HNO3 for 2 days. Excess HNO3 was washed
Table 1
Conditions of preparation and the ion-exchange capacity of cerium(IV)phosphate
cation exchanger.
Sample Mixing volume ratios (%)
code

Appearance
of the
sample

Na+ ion-exchange
capacity in
(mequiv./g)

Ortho-phosphoric
Cerium
acid
sulphate
(stock solution)
CP-1
CP-2
CP-3

1
2
3

1 (2 mol L1)
1 (2 mol L1)
1 (2 mol L1)

Light yellow 1.14

Light yellow 1.02
Light yellow 0.94

Amount of Amount of
Stirring Ion-exchange
Membrane Amount of
polyurethane cerium(IV) tetrahydofuran time (h) capacity
no.
(PU) in mg
phosphate (T.H.F) in ml
(mequiv./g)
(mg)
PUCPM-1
PUCPM-2
PUCPM-3
PUCPM-4
PUCPM-5
PUCPM-6

500
500
500
500
500
500

200
300
400
500
800
1000

50
50
50
50
75
75

24
24
24
24
24
24

0.95
1.16
1.19
1.24
1.34
1.79

off and then the composite membranes were immersed in 200 mL

0.5 mol L1 NaNO3. The amount of H+ ion was determined using a
titration with NaOH; cation exchange values were obtained and
expressed as mequiv./g of dry exchanger (In H+ form). The cation
exchange composite membrane having maximum ion-exchange
capacity (1.79 mequiv./g) was selected for further studies.

96
97
98
99
100
101

Characterization

102

Fourier transform infra red (FTIR) studies

The FTIR spectrum of polyurethane membrane, cerium(IV)
phosphate and polyurethane-cerium(IV) phosphate cation exchange composite membrane were obtained using a FTIR
spectrophotometer (Perkin-Elmer, USA, model Spectrum-BX) in
the original form.

103
104
105
106
107
108

Field emission scanning electron microscopy (FE-SEM) studies

The surface morphology of the original form of polyurethane,
cerium(IV) phosphate and polyurethane-cerium(IV) phosphate
cation exchange composite membrane were studied by eld
emission scanning electron microscopy (FE-SEM) using a LEO
microscope at various magnications.

109
110
111
112
113
114

Thermal studies
The degradation process and the thermal stability of polyurethane membrane and polyurethane-cerium(IV) phosphate cation
exchange composite membranes were investigated by thermogravimetic analysis (TGA) and differential thermal gravimetry
(DTG) using thermal analyzer-V2.2A DuPont 9900.

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116
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118
119
120

Physicochemical characterization of polyurethane-cerium (IV)

phosphate cation exchange composite membranes

121
122

The Water content (% total wet weight), porosity, thickness and

swelling etc. were determined by the same method as discussed in
our previous studies [1214]. Those membrane which exhibited
good surface qualities like porosity, thickness and swelling etc.
were selected for further investigation.

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124
125
126
127

Fabrication of ion-selective membrane electrode

128

Fabrication and conditioning of the ion-selective membrane

electrode was done by the same method as we have described
previously [1214]. The membrane sheet of 0.20 mm thickness as
obtained by the above procedure was cut in the shape of disk and
mounted at the lower end of a Pyrex glass tube (outer diameter
0.8 cm, internal diameter 0.6 cm) with araldite. Finally, the
assembly was allowed to dry in air for 24 h. The glass tube was
lled with 0.1 mol L1 Cu(II) solution. Electrode was then
equilibrated with Cu(II) solution (0.1 mol L1) for 57 days. The
tube was lled 3/4th with cupric sulphate solution (0.1 mol L1)
and then immersed in a beaker containing the test solution of

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133
134
135
136
137
138
139

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varying concentration of Cu(II) ion, keeping the level of inner lling

solution higher than the level of the test solution to avoid any
reverse diffusion of the electrolyte.

143

Potential measurements

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145
146
147

A saturated calomel electrode (SCE) was inserted in the tube for

electrical contact and another saturated calomel electrode (SCE)
was used as external reference electrode. All the potential
measurements were carried out using the following cell assembly:

148

1

SCEj0:1 mol L

CuIIjjMembranejjtest solutionjSCE

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157
158
159

Potentiometric measurements were observed for a series of

standard solutions of cupric sulphate (1010 to 101 mol L1),
prepared by gradual dilution of the stock solution, as described by
IUPAC Commission for Analytical Nomenclature [22]. Potential
measurements were made in unbuffered solutions to avoid
interference from any foreign ion. In order to study the
characteristics of the electrode, the following parameters were
evaluated: lower detection limit, slope response curve, response
time and working pH range. The calibration graphs were plotted.

160

Characteristics of the electrode

Effect of pH
pH solution ranging from 1 to 13 were prepared at
1  103 mol L1 constant ion concentration. The value of electrode potential at each pH was recorded and plot of electrode
potential versus pH was plotted.

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166
167
168
169

The response time

The method of determining response time in the present work
is being outlined as follows: The electrode is rst dipped in a
1  103 mol L1 solution of cupric sulphate and then 10 fold
higher concentrations. The potential of the solution was read at
zero second; just after dipping of the electrode in the second
solution and subsequently recorded at the intervals of 10 s. The
potentials were then plotted vs. the time.

170
171
172
173
174
175
176
177

Potentiometric selectivity coefcient of interfering anions

One of the most important characteristics of a membrane
sensor is its response for the primary ion in the presence of other
foreign ions, which is measured in terms of the potentiometric
selectivity coefcient (KABpot). In the present work we used the
mixed solution method [23]. The selectivity coefcient was
calculated using the equation given below:

178
179
180
181
182
183
184

v
KAB

161
162
163
164

The characteristics of the fabricated membrane electrode, for

example, effect of pH, response time, potentiometric selectivity
coefcient and storage of electrodes were measured by the
methods as described earlier [1214].

aA
aB zA=zB

(1)

where aA and aB activities of primary and interfering ion and zA and

186
185

zB are charges on the ions.

187

Fig. 1. FTIR spectra of polyurethane (a), cerium(IV)phosphate (b) and polyurethane-cerium(IV) phosphate cation exchange composite membrane (c).

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U. Baig, A.A. Khan / Journal of Industrial and Engineering Chemistry xxx (2015) xxxxxx

Fig. 2. SEM image of pure polyurethane (a), cerium(IV) phosphate (b) and polyurethane-cerium(IV) phosphate composite membrane at different magnications (c).

196
197
198
199
200
201
202
203
204
205
206

Polyurethane
Polyurethane-ce(IV)phosphate

4000
3500
3000

Intensity (a.u.)

188
189
190
191
192
193
194
195

2500
2000

Storage of electrodes
The polyurethane-cerium(IV) phosphate composite membrane
electrode was stored in distilled water when not in use for more
than one day. It was activated with (0.1 mol L1) Cu(II) solution by
keeping immersed in it for 2 h, before use, to compensate for any
loss of metal ions in the membrane phase that might have taken
place due to a long storage in distilled water. Electrode was then
washed thoroughly with DMW before use.
Results and discussion

1500
1000
500
0
0

10

20

30

40

50

60

70

80

90

2Theta (Degree)
Fig. 3. X-ray diffraction pattern of polyurethane and polyurethane-cerium(IV)
phosphate cation exchange composite membrane.

Various samples of organicinorganic polyurethane-cerium(IV)

phosphate cation exchange composite membranes were prepared
by solution casting method under different stoichiometric ratios. A
variety of cation exchange composite membranes by varying the
stoichiometry between polyurethane and cerium (IV) phosphate
were prepared, but highest ion-exchange capacity was observed in
1:2 stoichiometry (Table 2). The cation exchange membrane
(sample PUCPM-6) possessed better Na+ ion exchange capacity
(1.79 mequiv./g) as compared to the inorganic particles (sample
CP-1) of cerium(IV)phosphate (1.14 mequiv./g) [20,21]. Due to

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U. Baig, A.A. Khan / Journal of Industrial and Engineering Chemistry xxx (2015) xxxxxx

10 0 .0
1.0 0 0

9 0 .0

0 .5 0 0

10 0 .0

(a)

9 0 .0

8 0 .0

8 0 .0

7 0 .0

7 0 .0

6 0 .0

6 0 .0

5 0 .0

5 0 .0

4 0 .0

4 0 .0

3 0 .0

3 0 .0

2 0 .0

2 0 .0

10 .0

10 .0

TG %

-0 .5 0 0

TG %

DTG mg/min

0 .0 0 0

-1.0 0 0

-1.5 0 0

-2 .0 0 0

0 .0

0 .0

1 0 0 .0

2 0 0 .0

3 0 0 .0

4 0 0 .0
5 0 0 .0
T em p C el

6 0 0 .0

7 0 0 .0

1 0 0 .0

10 0 .0

2 0 0 .0

9 0 .0

1 0 0 .0

-1 0 0 .0

TG %

DTG ug/min

0 .0

9 5 .0

(b)

9 0 .0

8 5 .0

8 5 .0

8 0 .0

8 0 .0

7 5 .0

7 5 .0

7 0 .0

7 0 .0

6 5 .0

6 5 .0

6 0 .0

6 0 .0

5 5 .0

5 5 .0

5 0 .0

5 0 .0

4 5 .0

4 5 .0

TG %

9 5 .0

-2 0 0 .0

-3 0 0 .0

-4 0 0 .0

1 0 0 .0

2 0 0 .0

3 0 0 .0

4 0 0 .0
5 0 0 .0
T em p C el

6 0 0 .0

7 0 0 .0

Fig. 4. TGA and DTA curves of polyurethane (a) and polyurethane-cerium(IV) phosphate cation exchange composite membrane (b).

higher ion exchange capacity, and thermal stabilities, sample

PUCPM-6 (Table 2) was selected for further studies.
The FTIR spectra of polyurethane, cerium(IV)phosphate, and
polyurethane-cerium(IV) phosphate cation exchange composite
membrane are shown in Fig. 1. In the polyurethane spectrum, the
absorption band at 3333 cm1 corresponds to NH stretching. The
sharp peaks at 2874 cm1 and 2959 cm1 are associated with CH2
stretching, while other modes of CH2 vibrations are identied by
the bands at 1457, 1415, 1311, and 1228 cm1. In addition, the
absorption band at 1735 cm1 is associated with a C5
5O group in
polyurethane. The group of NH vibrations is identied by the bands
at 1532 cm1. The band at 1703 cm1 is assigned to hydrogen
bonding between NH and C5
5O groups in the hard segment and
the ester or ester-oxygen groups of the soft segments of urethane
linkage. The presence of cerium(IV) phosphate in the polyurethane-cerium(IV) phosphate composite membrane is further
Table 3
Physicochemical characterization of Polyurethane-cerium(IV)phosphate cation
exchange composite membranes.
Membrane No.

Thickness (mm)

Total wet
weight (%)

Porosity

Swelling (%)

PUCPM-1
PUCPM-2
PUCPM-3
PUCPM-4
PUCPM-5
PUCPM-6

0.165
0.174
0.182
0.194
0.199
0.201

1.906
1.813
1.983
1.997
1.772
1.476

0.0019
0.0021
0.0022
0.0021
0.0023
0.0017

0.3412
0.3682
0.4352
0.4561
0.5672
0.1201

strengthen from the presence of broad band at 3137 cm1 which

may be due to the vibration of hydroxyl groups, the broadness of
this hump may also be due to the presence of occluded water
molecule. The band between 1200 and 800 cm1 with a peak of
intensity at 1066 cm1 may be assigned to symmetric and
antisymentric stretching of the PO bond in PO3 groups [24].
550

500

Electrode Potential (mV)

207
208
209
210
211
212
213
214
215
216
217
218
219
220
221
222

450

400

350

300
12

10

2+

-log [Cu ]
Fig. 5. Calibration curve for polyurethane-cerium(IV) phosphate cation exchange
composite membrane (PUCPM-6) electrode in aqueous solution of Cu(NO3)2.

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Table 4
Potentiometric response of ve independent polyurethane-cerium(IV)phosphate
membrane electrodes for Cu2+.

1
2
3
4
5

Linear range

30.00
29.96
29.95
29.95
29.96

1  101
1  101
1  101
1  101
1  101

to
to
to
to
to

RSD (%)
(n = 6)

1  108 mol L1

1  108 mol L1
1  108 mol L1
1  108 mol L1
1  108 mol L1

1.5
1.6
1.5
1.5
1.8

Compared with Fig. 2(a), some peaks are shifted in the polyurethane-cerium(IV) phosphate composite membrane from 1228,
1415, 609, 508 cm1, to 1224, 1401, 616, 539 cm1 respectively,
indicating the formation of polyurethane-cerium(IV) phosphate
composite membrane.
Fig. 2(ac) shows the FE-SEM image of pure polyurethane,
cerium(IV) phosphate and polyurethane-cerium(IV) phosphate
composite membrane at different magnications, indicating the
binding of inorganic material, i.e. silica gel with organic polymer,
i.e. polyurethane. The pictures showed that the difference in
surface morphology of organic polymer, inorganic material and
composite membrane. It has been revealed that after binding of
polyurethane with cerium(IV) phosphate, the morphology has
been changed. It is also observed in Fig. 2(c) that the prepared
organic-inorganic polyurethane-cerium(IV) phosphate composite
membrane is homogeneous and dense.
Fig. 3 illustrates the diffractograms of pure polyurethane and
polyurethane-cerium(IV) phosphate composite membrane in the
2u range between 58 and 808. In the diffractogram of pure
polyurethane there are no sharp diffraction peaks, conrming their
amorphous nature. The polyurethane is known to be an amorphous
polymer and shows a broad diffraction peak at 2u values 10308.
On the addition of cerium(IV)phosphate in the polyurethane
matrix, the intensity of the peak 10308 become shifted. These
intensity changes in the composite membrane due to the
interaction between polyurethane and cerium(IV)phosphate and
some small peaks are situated in the diffractogram of polyurethane-cerium(IV) phosphate composite membrane at 2u values
28.28, 32.18, 428 and 488.
Fig. 4 shows the thermogravimetric stability data of polyurethane and polyurethane-cerium(IV) phosphate composite membrane. It can be concluded from this gure that the thermal
500

480

Electrode Potential (mV)

229
230
231
232
233
234
235
236
237
238
239
240
241
242
243
244
245
246
247
248
249
250
251
252
253
254
255
256
257
258
259
260

Nerstian slope
(mV/decade)
(n = 6)

460

435

Electrode Potential (mV)

Electrode

440

430
425
420
415
410
405
400
0

10

20

30

40

50

60

Time (Sec)
Fig. 7. Dynamic response time of polyurethane-cerium(IV) phosphate cation
exchange composite membrane electrode for Cu2+ ions.

stability of polyurethane-cerium(IV) phosphate composite membrane is higher than that of pure polyurethane. At 800 8C the
percentage of residual weight of polyurethane and polyurethanecerium(IV) phosphate composite membrane is 0.00% and 44.00%
respectively. Therefore the addition of cerium(IV) phosphate
cation exchanger improves the thermal stability of composite
membrane.
The thickness, swelling, porosity, water content capacity, etc. of
the polyurethane-cerium (IV) phosphate cation exchange composite membrane was investigated and the results are summarized
in Table 3. Thus, the low orders of water content, swelling and
porosity with less thickness of this membrane suggest that the
interstices are negligible and diffusion across the membrane would
occur mainly through the exchange sites. Hence, membrane

Table 5
The selectivity coefcient of various interfering cations for Cu2+ selective
polyurethane-cerium(IV) phosphate membrane electrode.
Interfering ion (Mn+)

Selectivity
coefcients (KMSM)

K+
Na+
Mg2+
Ca2+
Mn2+
Fe2+
Zn2+
Cd2+
Pb2+
Hg2+

2.8  103
1.89  103
5.5  103
2.9  103
2.15  103
1.56  104
0.98  104
0.87  104
1.30  105
0.56  105

440
Table 6
Determination of Cu2+ added to a drinking water sample containing different
concentrations of copper.

420

Detected
RSD (%) Recovery
Added Detected RSD (%) Recovery
Cu2+ by
(n = 5) by membrane Cu2+ By AAS (n = 5) by AAS (%)
Cu2+
electrode (%) (mg L1)
(mg L1) membrane
electrode
(mg L1)

400

380
0

10

pH
Fig. 6. Effect of pH on electrode potential of polyurethane-cerium(IV) phosphate
cation exchange composite membrane (PUCPM-6)) electrode at 1  103 M Cu2+ ion.

2.0
4.0
6.0
8.0
10.0

1.88
3.76
5.69
7.62
9.69

1.05
1.11
1.07
1.08
1.04

94.00
94.00
94.83
95.25
96.90

1.93
3.82
5.75
7.80
9.81

1.01
1.03
1.01
1.02
1.03

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96.00
95.50
95.88
97.50
98.10

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264
265
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267
268
269
270
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Table 7
Comparison of the proposed Cu(II) ion membrane electrode with the reported electrodes.
Refs.

Electroactive material

Response
time (s)

Linear range

pH range

[26]

Diaminopyridine and o-vanilin

Schiff base
Dithiane,2-(4-methoxyphenyl)
Quinolinoxymethyl)-trimethylbenzene
Tetrathiabicyclo[9.2.1] tetradeca-diene
Polyurethane-cerium(IV) phosphate

30 s

105 to 101 mol L1

1.05.3

29.6

4.7  106 mol L1

5s
30 s
10 s
14 s

105 to 102 mol L1

106 to 101 mol L1
106 to 101 mol L1
1.0  108 to 1.0  101 mol L1

1.35.5
1.06.0
0.66.0
2.56.5

29.5  1
30
28  1
30.00

1  106 mol L1

4.0  107 mol L1
3.2  107 mol L1
1.0  108 mol L1

[27]
[28]
[29]
Present work

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sample PUCPM-6 (thickness 0.201 mm) was selected for the

preparation of an ion-selective electrode for further studies.

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Performance of Cu(II) selective membrane electrode

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Working concentration range and slope

Using the optimized membrane composition described above,
the potentiometric response of the membrane electrode was
studied for Cu2+ in the concentration range of 1012 mol L1 to
101 mol L1 at 25 8C as shown in Fig. 5. The results showed a
Nernstian response of 30.00 mV/decade of Cu2+ concentration, and
the wide linear range within the concentration range from
108 mol L1 to 101 mol L1 of Cu2+ ions. All the potentiomertic
measurements were conducted a number of times (n = 10) to check
the reproducibility of the results. EMFs were plotted against log of
activities of copper ions and calibration curves were drawn for ve
sets of experiments. The relative standard deviation (RSD) of a
single electrode (within electrode variation) was also determined.
The relative standard deviation (RSD) of a single electrode was
found to be 1.5%, shows good reproducibility behavior and the
homogenous nature of the proposed membrane electrode. The
detection limit of membrane electrode was determined according
to IUPAC recommendations from the intersection of two extrapolated linear portions of the curve [25] and was found to be
1  108.
The reproducibility of the optimized membrane electrode was
also studied by measuring the potentiometric response of ve
independent Cu2+ ion selective membrane electrodes with the
same composition. These measurements were additionally done in
six replicates. The relative standard deviation (between electrode
variations), slope and linear range were investigated and the
results are summarized in Table 4.

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Effect of pH on electrode potential and response time

The pH effect on the potential response of the electrode was
measured for 1  103 mol L1 Cu2+ ion concentration at different
pH values. The pH was adjusted with hydrochloric acid and sodium
hydroxide. Fig. 6 depicts that the pH dependence of the potential is
insignicant in the pH range 2.56.5 which can be taken as a
working pH range for the electrode. Another important factor is the
promptness of the response of the ion-selective membrane
electrode. The average response time is dened as the time
required for the electrode to reach a stable potential.
The response time in contact with 1  103 mol L1 Cu2+
solution was determined, and the results are shown in Fig. 7. It
is clear from the gure, that the response time of the membrane is
14 s.
Lifetime and durability of the ion-selective electrode is one of
the important factors in choosing the appropriateness of ionselective electrode. Durability of the proposed ion-selective
membrane electrode was evaluated by monitoring the change in
the slope and linear range with time. These measurements were
also done in six replicates. The lifetime of the electrode was
determined by reading its potentials and plotting the calibration

Nerstian slope
(mV/decade)

Detection limit

curves for a period of 6 months, while this period the electrode

were used extensively (one hour per weeks). During this time no
signicant changes in the slope were observed. Thus, The
membrane electrode could be successfully used up to 6 months
without any notable drift in potential during which the potential
slope is reproducible within 1 mV per concentration decade.
Whenever a drift in the potential is observed, the membrane is reequilibrated with 0.1 mol L1 cupric sulfate solutions for 34 days.

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Potentiometric selectivity

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The selectivity behavior is obviously one of the important

characteristics of the ion-selective electrodes, determining whether reliable measurement in the target sample is possible or not. The
selectivity preference of the membrane for an interfering ion
relative to Cu2+ was determined by the mixed solution method
(MSM). It is evident from Table 5 that most of the interfering ions
showed low values of selectivity coefcient, indicating no
interference in the performance of the membrane electrode
assembly. Such remarkable selectivity of the proposed ionselective electrode over other ions reects the high afnity of
the membrane toward the Cu2+ ions.

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Accuracy

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The proposed membrane electrode was found to work well

under laboratory conditions. To evaluate the accuracy, an Cu2+ ion
selective electrode was satisfactorily applied for the determination
of Cu2+ ions in various samples of drinking water containing
different amount of Cu2+ spiked with increasing known concentration of Cu2+ ranging from 2 to 10 mg L1, Each sample was
analyzed in ve replicate measurements by membrane electrode
and the results was tested by the standard addition method. The
results are given in Table 6, shows that the amount of Cu2+
recovered with the help of the membrane electrode is in good
agreement with that determined by atomic absorption spectroscopy (AAS), thereby reecting the utility of the proposed method
for the analysis of real water samples.
Table 7 compares the working concentration range, response
time, life time, pH range and detection limit of the proposed
electrode with other reported Cu2+ ion-selective electrode [2629].
The results clearly indicated the superiority of the proposed
electrode in terms of linear range, pH, response behavior and
detection limit.

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Conclusion

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The proposed potentiometric sensor of polyurethane-cerium(IV) phosphate composite membrane showed good operating
characteristics including Nernstian response, reasonable detection
limit, relatively high selectivity, wide dynamic range and fast
response. These characteristics and the typical applications
presented in this paper makes this sensor suitable for measuring
Cu(II) content in real samples without a signicant interaction

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Please cite this article in press as: U. Baig, A.A. Khan, J. Ind. Eng. Chem. (2015), http://dx.doi.org/10.1016/j.jiec.2014.12.045

G Model

JIEC 2496 18
8

U. Baig, A.A. Khan / Journal of Industrial and Engineering Chemistry xxx (2015) xxxxxx

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from cationic species. A comparison between the response

characteristics of the proposed potentiometric sensor and those
of previously reported Cu (II) ion-selective electrode indicated that
the present sensor is invariably superior.

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Acknowledgements

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The author Dr. Umair Baig gratefully acknowledges to

University Grant Commission, Government of India, [42-336/
2013 (SR)] for nancial support and Department of Applied
Chemistry, Z.H. College of Engineering and Technology, A.M.U.,
(Aligarh) for providing research facilities. The support of this work
by KFUPM through the project # R15-CW-11 (MIT-13104, 13105)
under the Center of Excellence for Scientic Collaboration with MIT
is also gratefully acknowledged.

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