In the Laboratory
edited by
The Microscale Laboratory
Laboratory-Made Electrochemical Sensors
for Adsorptive Stripping Voltammetry
Teresa Goscinska
School of Biological and Chemical Sciences, Deakin University, Geelong, Victoria 3217, Australia
There is a need to develop sensitive electrochemical
sensors for the selective and quantitative determination of
organic and organometallic compounds at trace levels in small
samples. Research into sensitive electrochemical sensors has
been conducted by many laboratories around the world and
has branched in several directions. One of these is the devel-
opment of novel sensors by modifying (1–3) or miniaturizing
existing electrodes to create microelectrodes (4, 5). A second
direction is the production of disposable screen-printed sensor
strips used widely in medicine (6 ). A third is the integration
of chemically sensitive membranes with solid-state electron-
ics to create ion-sensitive field-effect transistors known as
ISFETs (7 ).
One field that offers great potential for future applications
is that of chemically modified electrodes. Because carbon paste
electrodes (CPEs) provide a convenient matrix for modifiers,
CPEs have become a flourishing field of research (2). Interest
in the CPE has also been revived because of the usefulness of
this type of electrode in adsorptive stripping voltammetry
(AdSV). The theoretical and practical aspects of AdSV follow-
ing non-Faradaic preconcentration with a medium exchange
have been reported by Wang (8). It is expected that at low
concentrations this analytical method will provide better
performance than traditional polarography.
As was shown in previous papers (9, 10), electrochemis-
try is a convenient method for testing and analyzing small
amounts of product. The purpose of this paper is to (i) de-
scribe the construction of sensitive electrochemical sensors
in the chemistry lab by students and (ii) illustrate the ben-
efits of AdSV with a medium exchange preconcentration pro-
cedure in chemical analysis of small samples of organic or
organometallic compounds. A facile procedure for the incor-
poration of clay (kaolin) into the carbon paste electrode is
described and the advantage of the sensor for the particular
purpose over the conventional carbon paste electrode is em-
phasized.
1038 Journal of Chemical Education • Vol. 75 No. 8 August 1998 • JChemEd.chem.wisc.edu
Arden P. Zipp
SUNY-Cortland
Cortland, NY 13045
Experimental Procedure
Electrode Preparation
The carbon paste electrode was prepared, as was reported
previously (11), by packing the carbon paste into Teflon tub-
ing (3-mm diameter) with a copper wire on the opposite side.
Clay–carbon paste was prepared by thoroughly mixing 2 g
of 1.5-µm graphite powder (Aldrich), 1 g of hydrated kaolin
(Riedel-de Haen), and 1 mL of Nujol (Merck). For hydration,
2 g of kaolin was immersed in 15 mL of double-distilled water
for two hours, after which the excess of water was decanted.
The clay-modified carbon-paste electrode (a sensor) was pre-
pared in exactly the same way as the CPE (11). The working
surface of each electrode was smoothed on a piece of filter
paper before the test. A fresh surface was revealed each time
by cutting off a piece of the electrode with a scalpel.
Apparatus
Electrochemical tests were performed on a BAS 100B
electrochemical analyzer with a printer. A three-electrode cell
with a platinum wire as the counter electrode and the refer-
ence electrode (Ag/AgCl in a 0.5 M aqueous solution of so-
dium perchlorate) was used. The CPE or the sensor was used
as the working electrode. For all experiments, a 0.5 M aque-
ous solution of NaClO4 was used as the electrolyte. All solu-
tions were prepared using double-distilled water. Each test
was performed under a nitrogen blanket.
Preconcentration and Analysis Procedure
Ferrocene solutions were prepared by dissolving the re-
quired weight of ferrocene (AR Aldrich) in absolute ethanol
(Aldrich). For the preconcentration the electrode was im-
mersed for the desired time (1, 5, 15 or 50 min) in the small
vial with 1 mL of the analyte solution. During this interval,
the solution was stirred at a constant rate by a magnetic stir-
rer. After preconcentration, the immobilized electrode was
Continued on page 1039

Figure 1. Cyclic voltammograms of 10᎑4 M ferrocene at (1) CPE,
(2) sensor. Scan rate was 250 mV/s.
rinsed thoroughly with double-distilled water to remove ex-
cess organic solvent and immersed in the electrochemical cell,
and the potential was scanned in either cyclic (CV) or differ-
ential pulse (DPV) mode. For DPV, a 50-mV pulse ampli-
tude, 50-ms pulse width, and 200-ms pulse period were used.
Blank experiments were performed by the same procedure as
above, except that the electrode was not immersed in the
analyte solution.
Results and Discussion
An increase of the electrochemical signal from ferrocene
at the modified electrode was seen by comparing the cyclic volt-
ammograms at the two electrodes. Figure 1 presents cyclic
voltammograms of 10᎑4 M ferrocene at the CPE and the
sensor (the analyte was preconcentrated for 1 min). At the
sensor the electrochemical response increased strikingly. In
addition, this electrode became saturated and produced a
broad oxidation peak and a broad reduction peak, which were
shifted in the positive and negative directions, respectively,
giving the impression that the process is irreversible.
Saturation is a particularly severe problem. When the
electrode becomes saturated, the analytical signal no longer bears
any relation to the concentration of the species of interest.
In some cases shorter preconcentration times can eliminate
the saturation problem. If this does not help, a more dilute
sample should be used.
Figure 2 compares the electrochemical signals for 10᎑5 M
ferrocene at the CPE and the sensor. The table illustrates an
influence of the preconcentration time on the electrochemi-
cal signal for 10᎑5 M ferrocene at the sensor.
Influence of Preconcentration Time on Electrochemical
Signal for 10 –5 M Ferrocene at the Sensor
Preconcentration time/min 1 5 15 50
Current/µA 0.8 1.0 1.2 1.25
The mechanism by which kaolin increases the electro-
chemical signal is unclear and was not tested. Clays repre-
sent an important class of solid inclusion compounds (12)
that can function as catalyst supports and cation exchangers.
They can also discriminate among analytes on the basis of
size and charge. The most important fact here is that the addi-
tion of kaolin increased the electrochemical response from
JChemEd.chem.wisc.edu • Vol. 75 No. 8 August 1998 • Journal of Chemical Education
In the Laboratory
Figure 2. The oxidation peak (DPV) for 10᎑5 M ferrocene at (1)
baseline, (2) CPE, (3) sensor. Scan rate was 50 mV/s.
ferrocene strongly and extended the detection level from 10᎑5
M down to 10᎑7 M (not shown). The electrochemical response
increased minimally with the extending of the preconcen-
tration time (see table). It appears that 15 min is the optimal
preconcentration time for this case.
Conclusions
Carbon paste was shown to be a convenient matrix for
the incorporation of modifiers in a suitable and responsive
form. The clay-modified sensors show sensitivity enhanced
100-fold. These sensors are inexpensive and simple to make in
the laboratory. A wide variety of analytical possibilities exists,
based on the choice of modifier and control of experimental
conditions.
The experiment is simple and enhances student interest
in modern electrochemistry. Using a medium exchange for
absorbing organic compounds by the sensor and coupling it
with stripping voltammetry is a promising approach in ana-
lyzing small samples in microscale chemistry.
Acknowledgments
This work was supported by Deakin University Fellow-
ship Scheme. I am grateful to Enrico Mocellin for providing
access to the electrochemical instrumentation, to Simon Lewis
for the constructive comments on the first version of the paper,
and to Richard Russell for his encouragement.
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