A CONDUCTIVE POLYPYRROLE BASED AMMONIUM ION

SELECTIVE ELECTRODE

DO PHUC QUAN, CHU XUAN QUANG, LE THE DUAN and PHAM HUNG VIET∗
Centre of Environmental Chemistry, Vietnam National University, Hanoi, Vietnam
(∗ author for correspondence, e-mail: cec@fpt.vn)

Abstract. In view of the development of miniaturized sensor arrays, a solid-contact ammonium

ion selective electrode has been investigated. A conductive polypyrrole film was electrochemically
deposited on a glassy carbon surface and used as an internal solid contact layer between the sensing
membrane and solid electrode surface. A systematic evaluation of the important parameters affecting
the electromotive force (emf) response is presented. The performances of this solid-contact sensor
were verified using a batch-mode measurement setup and a wall-jet flow cell system. The designed
sensor exhibited excellent selectivity for the primary ion and a linear response over the pNH+
4 range
1–5 with a slope of 56.3 mV decade−1 . The sensor has a fast response and is relatively robustness,
and was also used to determine ammonium concentrations in natural waters, with promising results.

Keywords: ammonium, conductive polypyrrole, ion selective electrode, solid-contact sensor

1. Introduction

The presence of ammonium ions in environmental samples can indicate the extent
of pollution and the eutrophication of natural water (Nigel, 1994; Gerald et al.,
1999), and over recent years, the growing importance of controlling the levels of
environmental pollutants has increased interest in the development of novel sensors
for the detection of these ions (Erkang et al., 1997; Magalhaes et al., 1997; Deviteri
and Diamond, 1994; Peter et al., 1997). Ion selective electrodes (ISES) offer a
simple and useful method for the direct detection of inorganic ammonium ions.
They offer great advantages, which include, speed and ease of preparation, simpli-
fied procedures, relatively fast response, reasonable selectivity, and a wide linear
dynamic range, at a relatively low cost. Furthermore, ISE developments offer the
possibility of sensor miniaturization, based on solid-state ion sensors, which use
solvent polymeric membranes that allow the sensing liquid membrane to be cast
on the solid electrode surfaces and eliminates the need for an internal solution
(Henry, 1987; Lemke and Cammann, 1989).
However, instability is a problem frequently encountered with solid-state ion
selective electrodes. It is generally agreed that this is caused by the lack of a stable
internal reference potential at the boundary between the sensing membrane and the
inner reference element. Attempts have been made to overcome this problem, not-
ably by the development of solid contact membrane sensors, in which, the transfer

Environmental Monitoring and Assessment 70: 153–165, 2001.

© 2001 Kluwer Academic Publishers. Printed in the Netherlands.
154 DO PHUC QUAN ET AL.

from ionic to electronic conductivity is provided by a solid contact layer having a

mixed ionic and electronic conductivity between the inner reference element and
the sensing membrane. Using this approach, a photo-cured ammonium electrode
(Peter et al., 1997), and an ammonium-ISFET sensor (Cecilia and Jordi, 1997)
based on a graphite-epoxy composite used as the conductive layer between the
ISFET surface and the PVC membrane, have been fabricated.
Recently, the use of conducting electroactive polymers, such as those incorpor-
ating polypyrrole, polythiophene or polyaniline as the active components of am-
perometric sensors have attracted much intention. These are based on the system’s
ability to incorporate and expel ionic species during the switching of the polymer
from the oxidized to the reduced state (Erkang and Anhua, 1991; Omowunmi and
Wallace, 1994; Barisci et al., 1997). Further application of conducting polymers
in potentiometric sensors involve the incorporation of an organic solvent soluble
ionophore in the polymer, which then allows the fabrication of wholly solid-state
potentiometric sensors (Pia et al., 1999).
In this study, it was found that adding the polypyrrole film by electropolymer-
ization, as solid contact layer, significantly improves the potentiometric stability
of solid-state potentiometric sensors, which is believed to be the result of a better
defined interfacial potential between the sensing membrane and the solid electrode
contact. We report upon the determination of ammonium levels in a range of natural
waters using such a solid-contact ammonium ion selective electrode.

2. Materials and Methods

2.1. M ATERIALS

All reagents used were of analytical reagent grade. Standards and buffer solutions
were prepared with Milli-Q water. Pyrrole purchased from Fluka was redistilled
under vacuum prior to use and covered with aluminium foil in the refrigerator to
prevent UV degradation.
Nonactin and monactin were kindly donated by Dr. Beat Muller of EAWAG,
Switzerland. 2-nitrophenyl-octyl ether (2-NPOE), bis(1-butylpentyl)adipate
(BBPA), high molecular weight polyvinyl chloride (PVC), potassium tetrakis(4-
chlorophenyl)borate (KT4ClPB) and tetrahydrofuran (THF) were obtained from
Fluka (Buchs, Switzerland).

2.2. E LECTRODE PREPARATION

2.2.1. Preparation of a Conventional Internal Electrolyte Electrode

The membrane components in Table I (200 mg in total) were dissolved in 6 mL of
fresh the distilled THF. This solution was placed in a glass ring of 24 mm i.d. rest-
ing on a glass plate. After solvent evaporation overnight, the resulting membrane
was peeled off the glass mould and discs of 7 mm i.d. were cut out, and mounted
 A CONDUCTIVE POLYPYRROLE BASED AMMONIUM ION SELECTIVE ELECTRODE 155
TABLE I
Composition of the ammonium solvent polymeric membrane mixtures
prepared in this study

Membrane composition Membranes

AM1 AM2 AM3 AM4

(w./w. %)

Nonactin/monactin 3 3 3 3
2-Nitrophenyl-octyl ether 67 – – –
Dioctyl sebacate – 67 – –
Bis(1-butylpentyl) adipate – – 67 67
Potassium tetrakis(4-chlorophenyl) – – – 1
borate in a 70% molar to the inophore
High molecular weight PVC 30 30 30 30

in Philips IS 561 electrode bodies (Eindhoven, The Netherlands) for electromotive

force (EMF) measurements in batch-mode setup. A 10 mM solution of NH4Cl was
used as the internal filling solution.

2.2.2. Fabrication of the Solid-Contact Ion Selective Electrode

Polypyrrole (PPy) synthesis and characterization were performed in a conventional
three electrode system comprising, the 2 mm i.d. glassy carbon disc (GC) working
electrode (6.1204.110 GC, Metrohm, Switzerland), a platinum wire gauze auxili-
ary electrode and an Ag/AgCl (3 M NaCl) reference electrode, against which all
potentials were measured. A laboratory-made microgalvanostat was used for the
electropolymerization. Chronopotentiograms were recorded using this instrument
with data acquisition system support. Cyclic voltammetric measurements of con-
ductive polymer were performed using a PC-controlled system for Voltammetry
(Model 757 VA Computrace, Metrohm, Switzerland).
Before polymerization, the surface of the glassy carbon working electrode was
polished on a polishing cloth with alumina slurry (0.05 µm) and then cleaned with
double distilled water and finally in a water-filled ultrasonic bath for 30 sec. The
polypyrrole film was prepared by anodic galvanostatic electropolymerization of the
pyrrole monomer from aqueous solution (0.5 M) onto the electrode surface. The
counterion solution used for polymerization contained 1 M of chloride. Solution
was deoxygenated with nitrogen for 5 min to remove any trace of oxygen from
the solution, prior to the polymer synthesis. A current density of 2 mA cm−2 for
150 sec was used to achieve electropolymerisation.
156 DO PHUC QUAN ET AL.

Scheme 1.

The polymeric membrane-coated modified electrode was a solution of a mixture

of ammonium membrane AM4 solution (30 µL) was applied directly on the top of
the polypyrrole film, then dried for 2 hr under a gently nitrogen atmosphere, and
conditioned overnight in 10 mM of the selected primary ion solution prior to any
measurement.

2.3. P OTENTIOMETRIC MEASUREMENTS

Batch-mode potentiometric measurements were made while stirring at a constant

rate and with the electrodes immersed to the same depth in the solution. The calib-
ration curve was obtained by a standard addition method, involving the additions
of 10−6 to 10−1 M of the primary ion.
The potentials were measured against a double junction Ag/AgCl reference
electrode (Orion 90-02-00) using a 692 pH/Ions meter (Metrohm, Switzerland),
the accuracy of the potential measurements were +0.1 mV.
Flow injection potentiometric measurement was performed with a simple flow
manifold including a four channel peristaltic pump (Ismatec - Switzerland), a low
pressure six way injection valve (5020 Rheodyne) with 100 µL sample loop and a
wall-jet flow cell (Metrohm, Switzerland). The carrier eluent in the flow injection
experiments contained 3 mM of sodium acetate and 2 mM of sodium chloride
including 1 µM of ammonium, to provide base line stability.
All measurements were carried out at room temperature.

3. Results and Discussion

3.1. C YCLIC VOLTAMMETRY MEASUREMENTS

A polypyrrole film was deposited on electrode surface by oxidation of monomer

 A CONDUCTIVE POLYPYRROLE BASED AMMONIUM ION SELECTIVE ELECTRODE 157

Figure 1. Cyclic voltammetry of a PPy/Cl electrode in 0.1 M of different cation solutions (a) NH+
4;
(b) K+ ; (c) Na+ ; (d) Li+ at scan rate 100 mV sec−1 .

from an aqueous solution containing the appropriate counterion as supporting elec-

trolyte. Chronopotentiograms were recorded during film growth. Relatively con-
stant potential was observed throughout the polymerization, indicating the forma-
tion of a conductive polymer layer. Since the polypyrrole film plays the role of the
solid contact layer in the ion selective electrode, the investigation of the incorpor-
ation process of ions of interest into the polymer film is of great importance to the
development process.
Counterion injection and release to accompany the redox cycling of electro-
polymerized polypyrrole films in electrolytes is well known. Recent studies (Lien
et al., 1991; John and Wallace, 1993) of the doping-dedoping process occurring at
polypyrrole have reported that, at least in some instances, two distinct processes
occur, as shown in Scheme 1, one involving anion transport and the other cation
transport. The degree to which each of these processes occur depends upon the
nature of the polymer materials used and the mobilities of the corresponding anion
and cation in solution and through the polymer.
In the present study, cyclic voltammograms recorded after the electropolymer-
ization of the polypyrrole indicated that polymer PPy/Cl was conductive in the
158 DO PHUC QUAN ET AL.

Figure 2. Cyclic voltammetry of a PPy/Cl electrode in 0.1 M of different cation solutions (a) NH+
4;
(b) Ba2+ ; (c) Ca2+ ; (d) Mg2+ at scan rate 100 mV sec−1 .

counterion solution. In order to investigate the incorporation of cation into the

polypyrrole film, cyclic voltammogram measurements of the PPy/Cl electrode in
solutions of different cations were taken. The most striking feature of these voltam-
mograms was the fact that the second reduction wave which occurs at a more
negative potential was present in the univalent cation solutions (Figure 1). Figure 1
also indicates that the second reduction response moved in the positive direction
with a decrease in the solvated cation size according to Li+ > Na+ > K+ > NH+ 4.
The absence of a second reduction response in the divalent cation solutions (Fig-
ure 2) suggests that polymer was not reduced to the extent that occurred in the
univalent cation solutions. This was confirmed by the fact that the subsequent
oxidation peaks were smaller in solutions containing the divalent cations.

3.2. P OTENTIOMETRIC RESPONSE CHARACTERISTICS OF ELECTRODES

Principle electrode characteristics, such as a Nerntian slope, dynamic linear range,

detection limit and selectivity, depend on the composition of the ion selective
membrane. One of the first tasks in a development of this type involves the determ-
 A CONDUCTIVE POLYPYRROLE BASED AMMONIUM ION SELECTIVE ELECTRODE 159
TABLE II
Determination of ammonium in natural water samples using the designed
solid-contact ammonium selective electrode as compared with the ammo-
nia gas electrode. Real samples were prefiltered through filter membrane of
0.45 µm pore size

Sample place Solid-contact NH+4 NH3 gas electrode

selective liquid (Orion Inc., U.S.A.)
membrane electrode

Ammonium (NH+
4 ) in groundwater samples, mg L
−1 (SRD)

Phap Van 13.9 (0.88%) 13.4 (0.95%)

Ha Dinh 10.2 (0.87%) 9.5 (0.92%)
Yen Phu 4.7 (0.79%) 4.4 (0.86%)
Tuong Mai 6.9 (0.82%) 6.4 (0.89%)

Ammonium (NH+
4 ) in river and ponds water samples, mg L
−1 (SRD)

Thanh Tri fish pond 1 3.8 (1.45%) 3.2 (1.49%)

Thanh Tri fish pond 2 5.1 (1.46%) 4.6 (1.52%)
Kim Nguu River 5.5 (1.53%) 5.0 (1.62%)
To Lich River 5.2 (1.51%) 4.8 (1.58%)
Lu River 5.0 (1.48%) 4.3 (1.53%)

ination of the best composition for the preparation of a solid-contact ammonium

ion selective electrode. The optimal composition of the ion selective membrane for
the ammonium was determined in several experiments by varying the nature and
the percentage of various liquid membrane plasticizers, results are summarized in
Table II.
Three ammonium membrane electrodes employing three different plasticizers
were prepared. The electrode responses observed for the AM1, AM2 and AM3
ISEs were both Nernstian in character over range between 0.01 and 100 mM in
pure ammonium chloride solutions. However, the AM2 and AM3 ISE gave super-
ior response characteristics with a Nernstian slope of 57.6 and 58.3 mV dec−1 ,
respectively. Furthermore, this study also indicated that anion interference at con-
centrations >100 mM, for the liquid membrane – based ISE, are more evident for a
polar plasticizer, such as NPOE. The severity of the anion interference is also de-
pendent on the lipophilicity of the anion, that is, the greater the lipophilicity of the
anion, the greater the penetration of the anion into the liquid membrane, and con-
sequently, the greater the interference exerted upon the cation selective membrane
at higher concentrations. Therefore, in order to reduce anion interference at higher
concentrations, a lipophilic salt, such as potassium tetrakis(4-chlorophenyl) borate,
160 DO PHUC QUAN ET AL.

Figure 3. Charge transfer process occurring in (A) a conventional internal electrolyte selective
electrode; and (B) in a solid-contact conducting polymer based electrode.

was added to the membrane. In the following section, we describe a solid-contact

sensor that was fabricated with the optimal AM4 mixture composition.
Figure 3 compares the charge transfer process occurring in a conventional in-
ternal electrolyte selective electrode with that in a solid-contact conducting poly-
mer based electrode. Comparisons of the charge transfer between the sensing mem-
brane and inner element of both ammonium electrodes showed similar trends.
The potential response of the solid-contact electrode was very stable in the meas-
ured ammonium concentration range. Calibration curves for a conventional internal
electrolyte electrode and the solid-contact electrode in ammonium solutions, are
shown in Figure 4. This result demonstrates that the response was linear over the
investigated range of 10−5 to 10−1 M L−1 of ammonium with a slope of 56.3 mV
dec−1 .
Response time was also investigated, because it is a very important factor in
terms of the practical use of solid-contact sensors. The time taken for the both
electrodes to attain 90% of the steady-state response was typically a few seconds,
suggesting that this electrode is ideal for flow injection measurement.
 A CONDUCTIVE POLYPYRROLE BASED AMMONIUM ION SELECTIVE ELECTRODE 161

Figure 4. Comparison of ammonium ion concentration calibration curves for the internal electro-
lyte ammonium ISE and the solid-contact ammonium electrode in 2 mM NaCl, to adjust the ionic
strength.

The selectivity of solvent polymeric membrane electrodes in the presence of in-

terfering cations were determined by the separateg solution method (SSM) (Morf,
1981) and calculated using Equation (1).


pot (Ej − E) zi
log Ki,j = + 1− lg ai , (1)
S zj

where Ki,j is the selectivity coefficient, i is the primary ion (NH+

pot
4 ), j is the in-
terfering ion, E is the measured potential (mV), S is the Nernstian slope factor
(mV/decade), z is the electrical charge of the ion, and a is the activity calculated
from the activity coefficients. The selectivity coefficient values obtained by the
separate solution method are given in Figure 5 and are compared to the selectivity
coefficients reported for ammonium electrodes in previous studies (Thomas et al.,
1988). Comparison of the selectivity coefficients of interfering ions showed that
the potassium ion is the most notable interference ion of the ions tested.
The solid-contact ammonium ion selective electrode AM4SCS was mounted in
the FIA system described in the Experimental Section. Typical FIA signals ob-
162 DO PHUC QUAN ET AL.

pot
Figure 5. Selectivity coefficients, logKNH ,j for the ammonium selective electrodes made during this
4
work, compared to a previously reported ammonium ISE. Results were obtained by the separate solu-
tion methods in Tris buffered solutions of 0.1 M chloride salts at pH 7.1. AM (1–4): four conventional
internal electrolyte ammonium selective electrodes; ISE∗ : ammonium ion selective microelectrode
(Thomas et al., 1988); and AM4SCS: solid-contact ammonium ion selective electrode.

tained for series injection of different ammonium solutions are shown in Figure 6,
which demonstrates the high reproducibility of the observed peak heights. The
potentiometric response was linear over the range investigated i.e., between 10−5
and 10−1 M L−1 of ammonium.

3.3. WATER ANALYSIS

Finally the analytical performance of the solid-contact ammonium ion selective

electrode was tested in terms of the determination of ammonium in natural water.
The samples of natural water used were representative complexes of real matrices
containing high concentrations of inorganic and organic substrates. Moreover, the
concentration of ammonium in these samples represented an important quality
level determining factor. In order to verify the analytical results obtained using this
 A CONDUCTIVE POLYPYRROLE BASED AMMONIUM ION SELECTIVE ELECTRODE 163

Figure 6. Potentiometric responses of solid-contact ammonium selective electrode in an FIA system.

Flow injection conditions were as reported in the Experimental Section.

electrode, the same samples were analyzed using an ammonia gas sensor, and the
results obtained using the two techniques were found to be close agreement. These
results demonstrate clearly the benefits of the features of the ammonium solid-
contact electrode in a flow injection system for the determination of ammonium
levels in real complex matrices.

4. Conclusions

The solid-contact ion selective electrode, based on a conductive polypyrrole mem-

brane, showed good sensitivity in the linear pNH+ 4 range 1–5 with a Nernstian
slope of 56.3 mV dec−1 . This sensor exhibited a fast response (5 sec) and relat-
ively high robustness in both batch-mode measurements and flow injection sys-
tems, using a wall-jet flow cell. It is hoped that this study will contribute to the
design and construction of an ammonium selective solid-contact electrode based
164 DO PHUC QUAN ET AL.

on integrated planar sensor technology. Further investigations to improve the elec-

trode, involving lowering the detection limit and lengthening the life-time of the
solid-contact sensor will be conducted in our laboratory.
The use of this conceptual approach for development of solid-contact selective
sensors for other relevant environmental ions, such as nitrite and potassium remains
challenging work.

Acknowledgements

This work was supported by the Vietnam National University, Hanoi (Grant
QGTD.99.02) and partly supported by the SDC (Swiss Agency for Development
and Cooperation, Switzerland) in framework of the co-operation Project ESTNV
between CEC, VNU Hanoi and EAWAG, Switzerland in the field of Environ-
mental Chemistry. Do Phuc Quan express his deep gratitude to Prof. Dr. Gordon
G. Wallace, Director of the Intelligent Polymer Research Institute (University of
Wollongong, Australia) for the effective support during his former academic stay
in the Gordon G. Wallace’s Laboratory and for many challenging discussions.
The authors also express their thankfulness to thank Dr. Beat Müller (EAWAG,
Switzerland) for his kind donation of the nonactin/monactin ionophore.

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