Talanta 80 (2010) 10681072

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Talanta
journal homepage: www.elsevier.com/locate/talanta

The electrochemical determination of phenolic derivates using multiple pulsed

amperometry with graphite based electrodes
Adriana Bebeselea a, , Florica Manea a , Georgeta Burtica a , Livia Nagy b , Geza Nagy b
a
b

Politehnica University of Timisoara, P-ta Victoriei no. 2, 300006 Timisoara, Romania

Department for General and Physical Chemistry, University of Pecs, Ifjusag u.6, H-7624 Hungary

a r t i c l e

i n f o

Article history:
Received 13 March 2009
Received in revised form 17 July 2009
Accepted 20 July 2009
Available online 25 July 2009
Keywords:
Carbon-based electrodes
4-Chlorophenol
4-Nitrophenol
Electrochemical detection
Pulsed amperometry

a b s t r a c t
The electrochemical determinations of 4-chlorophenol (4-CP) and 4-nitrophenol (4-NP) by chronoamperometry (CA) and multiple pulsed amperometry (MPA) using expanded graphite-epoxy composite
(EG-Epoxy) and rotating spectral graphite disc (SG) electrodes are reported. The electrochemical
behaviours of both electrodes in the presence of organics informed about oxidation peak potential and the electrode fouling with organics concentration increasing. Setting up the oxidation peak
potential as detection potential, only SG gave good electroanalytical performance using CA. However, by MPA applying both electrodes exhibited the capability to assess electrochemically and
quantitatively the pollutants from aqueous solutions. UV spectrometric method detecting 4-CP and
4-NP at  = 280 nm and  = 398 nm wavelength, respectively was used for validation and parallel
determinations.
2009 Elsevier B.V. All rights reserved.

1. Introduction
Priority phenols consist of a number of substituted phenolic compounds including halogenated and nitrated phenols, e.g.,
chlorophenols (CPs) and respective, nitrophenols (NPs). Priority
phenols are used/produced in several industrial processes, being
commonly used as preservatives, disinfectants, in pulp processing,
in pesticides and their intermediars manufacturing. Many priority
phenols are known for their toxicity, carcinogenetic and environmental persistence character [13]. They are common pollutants
found in water, sediments and soil. Due to their toxicity, stability and bioaccumulation, the European Union has set the black
list of the dangerous substances that should be monitored in
waters [4]. The phenols were included in that list that was later
accepted in Water Framework Directive [5]. The severe toxicity of
4-chlorophenol (4-CP) and 4-nitrophenol (4-NP) requires the development of simple, sensitive and reliable determination method.
Various methods have been employed for the measurement of phenol derivates, e.g., method using HPLC [6,7], gas chromatography
[8,9], biosensors [10,11]. However, these methods require expensive and most often laboratory locked complicated instruments.

Corresponding author. Tel.: +40 256 403069.

E-mail addresses: adriana.bebeselea@chim.upt.ro (A. Bebeselea),
orica.manea@chim.upt.ro (F. Manea), georgeta.burtica@chim.upt.ro (G. Burtica),
lnagy@ttk.pte.hu (L. Nagy), g-nagy@ttk.pte.hu (G. Nagy).
0039-9140/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.talanta.2009.07.036

The specic cost of analysis can be high, and the methods are not
suitable for in situ measurements.
Electrochemical methods present a growing interest because of
high sensitivity, good selectivity, rapid response, and the instruments are relatively simple with the possibility of miniaturization
for in situ measurement. Successful application of chemically modied electrodes [1215] and boron-doped diamond electrodes
in combination with different electrochemical methods [1618]
was reported for the determination of phenol derivates. Recently
carbon-based materials such as graphite, carbon bers, etc. have
been used most often as the conductive phase in preparing composite working electrodes [1922].
Although phenol derivates in general, can be oxidized at many
electrode materials, the oxidation at carbon-based solid electrodes
produces phenoxy radicals which couple to form an insulating polymeric lm fouling the surfaces of the electrodes. A simple method
of renewing the electrode surface is based on the anodic treatment. This relies on adjusting the working electrode potential high
enough to oxidize the insulating lm and making it water soluble
without damaging the electrode.
In different working programs applied in practice of the
well-known pulsed amperometric detection (PAD) the measurement potential is kept for a short time (measurement pulse)
after the electrode cleaning pulse and conditioning potential
pulse. Among presently used electroanalytical techniques, multiple
pulsed amperometry (MPA) has proved to be extremely sensitive
for the detection of organic molecules because of the advantage of

A. Bebeselea et al. / Talanta 80 (2010) 10681072

1069

in situ cleaning and reactivating the electrode surface during the

electroanalytical detection [23].
The purpose of this work is to evaluate comparatively the
application of the multiple pulsed amperometry (MPA) technique
for determination of 4-chlorophenol and 4-nitrophenol in water
samples. The performances of the rotating spectral graphite disc
(SG) and expanded graphite-epoxy composite (EG-Epoxy) electrodes were compared. The development and optimization of a
MPA method for the determination of 4-CP and 4-NP in aqueous solution using both graphite based electrodes are described.
Finally, the proposed method applied to determine either 4-CP
or 4-NP in drinking water using EG-Epoxy electrode was found
advantageous.
2. Materials and methods
All measurements were carried out using an Autolab potentiostat/galvanostat PGSTAT 12 (Eco Chemie, The Netherlands)
controlled with GPES 4.9005 software and a three-electrode cell,
with a Ag/AgCl reference electrode and a platinum counter electrode. In the study of the detection properties ED/101 disc electrode
(Radiometer Analytical S.A., France) was applied. The spectral
graphite and EG-Epoxy composite electrodes were used as working
electrodes. The spectral graphite (SG) was an OD 3 mm disc electrode (ED), purchased from Electrocarbon Topolcany (Bratislava,
Slovakia).
The EG-Epoxy composite electrode was prepared from twocomponent epoxy resin (LY5052, Araldite) mixed with conductive
expanded graphite (EG) llers powder (Conductograph, SGL Carbon). To prepare EG-Epoxy composite electrode, the two parts of the
epoxy were mixed together and the full amount of the EG was added
in steps forming a thick paste. Then the epoxy was cured in a hot
press at 80 C for 40 min. Simultaneously the material was shaped
in a plate of 1 mm thickness. The plate was slowly cooled down
(for about 12 h) to the room temperature without removing the
applied pressure. The prepared carbon-based composite showed
good mechanical strength and low electrical resistance [22].
Prior to use, the working electrode with the surface area of 4 cm2
was gradually cleaned, rst polished with abrasive paper and then
on a felt-polishing pad by using 0.6 and 0.3 m alumina powder
(Metrohm, Switzerland) in distilled water for 5 min and rinsing
with distilled water. The electrode was sonicated to clean from the
alumina powder.
0.1 mol L1 stock solutions of 4-chlorophenol (4-CP) and 4nitrophenol (4-NP) were prepared using distilled water. The
supporting electrolyte was 0.1 M sodium sulphate freshly prepared
with distilled water. All reagents were analytical grade. Analytical
curves were obtained by the standard addition method.

Fig. 1. Cyclic voltammograms recorded at EG-Epoxy electrode in 0.1 M Na2 SO4 supporting electrolyte (curve 1) and in the presence of different concentrations of
4-CP: 2-0.2 mM; 3-0.4 mM; 4-0.6 mM; 5-0.8 mM; starting potential: 0 V vs. Ag/AgCl;
potential range: 0.5 V +1.25 V 0.5 V vs. Ag/AgCl; scan rate: 0.1 V s1 .

after the rst scanning in the presence of 4-CP (curves 35 from

Figs. 1 and 2). Compared with EG-Epoxy electrode behaviour, the
rotating SG electrode exhibited the higher background current, and
4-CP concentration increasing did not lead to signicant electrode
fouling. This aspect could be attributed to the avoidance of the
adsorption effect by rotating.
The similar results regarding the behaviours of the electrodes
in the presence of 4-NP subjected to the electrode fouling were
found (the results are not shown here). Based on these results, the
chronoamperometry as the easiest electrochemical technique used
for detection was applied for two detection potential values for each
using the standard addition method. The two detection potential
values were chosen based on the different considerations, the rst
was in line with the cyclic voltammetry, i.e., +0.8 V vs. Ag/AgCl for
EG-Epoxy electrode and +0.9 V vs. Ag/AgCl for SG electrode, and the
second one had to be higher even under oxygen evolution process
to assure a faster oxidation rate (+1.1 V vs. Ag/AgCl). As example,

3. Results and discussion

Examples of cyclic voltammetric curves of different concentrations of 4-CP at EG-Epoxy and SG electrodes recorded at scan rate
of 0.1 V s1 are shown in Figs. 1 and 2. From such curves it is determined the peak potential, e.g., ca. +0.8 V vs. Ag/AgCl for EG-Epoxy
and ca. +0.9 V vs. Ag/AgCl for SG electrode. The different curves
were obtained using standard addition method, without electrode
cleaning between additions. For both electrodes 4-CP concentration increasing led to the electrode fouling, because of the complex
oxidation process on graphite electrodes. The oxidation process of
phenols involves both the adsorption of reactant/intermediate or
phenols oxidation products and the formation of passive, nonconductive layer of oligomer products of oxidation process on their
surface by electropolymerization [24]. The electropolymerization
process is proven by changing the shape of the voltammogram

Fig. 2. Cyclic voltammograms recorded at SG electrode in 0.1 M Na2 SO4 supporting electrolyte (curve 1) and in the presence of different concentrations of 4-CP:
2-0.2 mM; 3-0.4 mM; 4-0.6 mM; 5-0.8 mM; starting potential: 0 V vs. Ag/AgCl;
potential range: 0.5 V +1.25 V 0.5 V vs. Ag/AgCl; scan rate: 0.1 V s1 .

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A. Bebeselea et al. / Talanta 80 (2010) 10681072

(0.22 mA mM1 vs. 0.14 mA mM1 obtained at +0.8 V vs. Ag/AgCl),

and the correlation coefcient higher than 0.99 (Fig. 4b).
In Fig. 5 is presented a typical batch chronoamperometry
obtained by CA and adding 4-CP to 0.1 M Na2 SO4 using rotating
disc spectral graphite electrode. The applied potential was set at
+1.1 V vs. Ag/AgCl and the response time was about 50 s. The calibration plots of current vs. 4-CP concentration was linear over
the concentration range of 0.10.5 mM, with the electrode sensitivity of 0.12 mA mM1 , and correlation coefcient higher than
0.99. The similar multiple pulsed amperograms in the presence of
different concentrations of 4-CP on rotating disc spectral graphite
for the same concentration range at the potential value and the
cleaning potential value of 1.4 V vs. Ag/AgCl are presented in Fig. 6.
The amperograms recorded at the cleaning potential value is also
shown. Under these last conditions, a better electrode sensitivity
was obtained as 0.25 mA mM1 . Even the relationships between
current recorded at +1.4 V vs. Ag/AgCl and 4-CP concentration is
linear, the abundant oxygen evolution occurred and this aspect is
undesired for electroanalysis.

Fig. 3. (a) Chronoamperograms (CAs) recorded at EG-Epoxy electrode in 0.1 M

Na2 SO4 supporting electrolyte and in the presence of different 4-NP concentrations
recorded at E = 0.8 V vs. Ag/AgCl (curve 1) and E = 1.1 V vs. Ag/AgCl (curve 2). (b)
The calibration plots of the densities of the currents vs. 4-NP concentrations of the
chronoamperograms recorded at E = 0.8 V vs. Ag/AgCl and E = 1.1 V vs. Ag/AgCl.

Fig. 3a shows the results obtained for EG-Epoxy electrode used for
4-NP detection using chronoamprometry technique.
Based on the two continuous chronoamperograms recorded at
the two detection potential values, the calibration plots of current
vs. 4-NP concentration was linear for the detection potential value
of +1.1 V vs. Ag/AgCl, while for the detection potential value of +0.8 V
vs. Ag/AgCl the amperometric current did not depend linear on the
4-NP concentrations, over the concentration range of 0.10.6 mM
(Fig. 3b). Under the detection potential of +1.1 V vs. Ag/AgCl, the
electrode sensitivity for 4-NP detection was 0.046 mA mM1 , with
the correlation coefcient of 0.98.
In Fig. 4a are presented the results of MPA applying to test the
detection of 4-NP at the two detection potential at which CA was
applied. For both situations, potential value for cleaning was +1.4 V
vs. Ag/AgCl.
It can be concluded that MPA applying allowed the detection of
4-NP on EG-Epoxy electrode at the detection potential of +0.8 V vs.
Ag/AgCl, which corresponds only to 4-NP oxidation, without oxygen
evolution involving. For both detection potential, the linear relationships between amperometric current and 4-NP concentrations
were obtained, with better electrode sensitivity at +1.1 V vs. Ag/AgCl

Fig. 4. (a) Multiple pulsed amperograms (MPAs) recorded at EG-Epoxy electrode in

0.1 M Na2 SO4 supporting electrolyte and in the presence of different 4-NP concentrations; Edet was +0.8 V (curve 1), respective +1.1 V (curve 2) and Eclean was +1.4 V vs.
Ag/AgCl; tdet was 0.05 s and tclean was 0.15 s. (b) The calibration plots of the currents
densities vs. 4-NP concentrations of the multiple pulsed amperograms recorded
at the detection potential: Edet = +0.8 V, respective Edet = +1.1 V vs. Ag/AgCl; tdet was
0.05 s.

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Table 1
Electroanalytical detection performance of EG-Epoxy and rotating SG disc electrode for the detection of 4-NP and 4-CP using CA and MPA.
Electrode

Pollutant

EG-Epoxy electrode

4-NP

Sensitivity (mA mM1 )

Technique
CA parameters

MPA parameters

CA

MPA

Edet = +1.1 V

Edet = +1.1 V; tdet = 0.05 s

Eclean = +1.4; tclean = 0.15 s
Edet = +0.8 V; tdet = 0.05 s
Eclean = +1.4; tclean = 0.15 s
Edet = +1.1 V; tdet = 0.05 s
Eclean = +1.4; tclean = 0.15 s

0.046

0.22

Edet = +0.8 V

Rotating SG disc electrode

4-CP

Edet = +1.1 V

4-NP

Edet = +1.1 V

4-CP

Edet = +1.1 V

0.14

Edet = +1.1 V; tdet = 0.05 s

Eclean = +1.4; tclean = 0.15 s
Edet = +1.1 V; tdet = 0.05 s
Eclean = +1.4; tclean = 0.15 s

0.042

0.24

0.17

0.28

0.12

0.25

Table 2
Recoveries of 4-CP and 4-NP in drinking water samples using continuous MPA
method at EG-Epoxy electrode.
Spiked (mg L1 )

40
120

Fig. 5. Chronoamerogram (CA) recorded at the rotating disc SG electrode in 0.1 M

Na2 SO4 supporting electrolyte and in the presence of different 4-CP concentrations
recorded at E = +1.1 V vs. Ag/AgCl.

The performance of both electrodes for the detection of 4-NP and

4-CP is summarized in Table 1. It can be concluded that rotating SG
disc electrode showed a better sensitivity for the detection of both
organic pollutants due to the adsorption effect was diminished by
rotating. MPA applying improved signicantly the detection per-

Recovery, % (n = 3)
4-CP

4-NP

96.0
93.5

94.6
92.4

formance of the electrode, owing the electrode cleaning during

the detection experiments. Under the conditions of MPA applying (Edet = + 1.1 V, tdet = 0.05 s and Eclean = + 1.4 V, tclean = 0.15 s), the
detection limits of 0.01 mM for both organics were determined
using a 3/slope ratio [14], where  is the standard deviation of the
mean value for three MPAs of the blank. The repeatability expressed
as the relative standard deviation (R.S.D.) was 2.8% for 4-CP and 3.1%
for 4-NP at three replicates.
The electroanalytical performance for the detection of 4-CP and
4-NP using EG-Epoxy electrode and MPA technique exhibited the
advantage of a simple and fast method with the results comparable to those published by us [25,26], which require the electrode
renewing after each measurement and the use of specic voltammetric techniques.
A recovery test was also performed by analyzing three parallel tap water samples for two spiked levels of each pollutant. This
test was run in 0.1 M Na2 SO4 solution as supporting electrolyte and
the results are summarized in Table 2. Finally, the results obtained
by this method were compared with that obtained by means of a
conventional UV spectrometric determination method at two certain wavelengths ( = 280 nm for 4-CP and  = 398 nm for 4-NP). By
comparison the results in order to evaluate the precision of this
electrochemical method using EG-Epoxy electrode by continuous
application MPA, it can be concluded that the results obtained by
the two methods are very closely and the accuracy of the proposed
amperometric method is good.
4. Conclusions

Fig. 6. Multiple pulsed amperogram (MPA) recorded at the rotating SG disc electrode in 0.1 M Na2 SO4 supporting electrolyte and in the presence of different 4-CP
concentrations; Edet was +1.1 V (curve 1) and Eclean was +1.4 V vs. Ag/AgCl (curve 2);
tdet was 0.05 s and tclean was 0.15 s.

In this paper the oxidation of 4-CP and 4-NP at the EG-Epoxy

and the rotating SG electrodes studied by CV showed the loss of
the electrode activity because of the electrode fouling effect. This
phenomenon did not allow the application of CA, the easiest electrochemical technique for the detection of phenol derivates. The
use of MPA technique improved the electroanalytical performance
for the detection of 4-CP and 4-NP. The optimization of the experimental condition for MPA applying yielded to the detection results
comparable to those obtained under the conditions of the electrode
renewal and voltammetric techniques.
The good recovery degrees for both organic pollutants from
drinking water suggested that this proposed method has good accuracy.

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A. Bebeselea et al. / Talanta 80 (2010) 10681072

Acknowledgements
Funding for this project was provided by the Romanian Excellence Research for Young Researcher CEEX-ET Program: Smart
sensors for waste water quality monitoring, and Romanian National
Research of Excellence Program CEEX, Grant 62/03.10.2005
Advanced Treatment Technologies for Recycling Industrial Wastewater/RIWATECH.
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