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In the Laboratory

edited by
The Microscale Laboratory Arden P. Zipp
SUNY-Cortland
Cortland, NY 13045

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 Experimental Procedure


sensors for the selective and quantitative determination of
organic and organometallic compounds at trace levels in small Electrode Preparation
samples. Research into sensitive electrochemical sensors has The carbon paste electrode was prepared, as was reported
been conducted by many laboratories around the world and previously (11), by packing the carbon paste into Teflon tub-
has branched in several directions. One of these is the devel- ing (3-mm diameter) with a copper wire on the opposite side.
opment of novel sensors by modifying (1–3) or miniaturizing Clay–carbon paste was prepared by thoroughly mixing 2 g
existing electrodes to create microelectrodes (4, 5). A second of 1.5-µm graphite powder (Aldrich), 1 g of hydrated kaolin
direction is the production of disposable screen-printed sensor (Riedel-de Haen), and 1 mL of Nujol (Merck). For hydration,
strips used widely in medicine (6 ). A third is the integration 2 g of kaolin was immersed in 15 mL of double-distilled water
of chemically sensitive membranes with solid-state electron- for two hours, after which the excess of water was decanted.
ics to create ion-sensitive field-effect transistors known as The clay-modified carbon-paste electrode (a sensor) was pre-
ISFETs (7 ). pared in exactly the same way as the CPE (11). The working
One field that offers great potential for future applications surface of each electrode was smoothed on a piece of filter
is that of chemically modified electrodes. Because carbon paste paper before the test. A fresh surface was revealed each time
electrodes (CPEs) provide a convenient matrix for modifiers, by cutting off a piece of the electrode with a scalpel.
CPEs have become a flourishing field of research (2). Interest
in the CPE has also been revived because of the usefulness of Apparatus
this type of electrode in adsorptive stripping voltammetry Electrochemical tests were performed on a BAS 100B
(AdSV). The theoretical and practical aspects of AdSV follow- electrochemical analyzer with a printer. A three-electrode cell
ing non-Faradaic preconcentration with a medium exchange with a platinum wire as the counter electrode and the refer-
have been reported by Wang (8). It is expected that at low ence electrode (Ag/AgCl in a 0.5 M aqueous solution of so-
concentrations this analytical method will provide better dium perchlorate) was used. The CPE or the sensor was used
performance than traditional polarography. as the working electrode. For all experiments, a 0.5 M aque-
As was shown in previous papers (9, 10), electrochemis- ous solution of NaClO4 was used as the electrolyte. All solu-
try is a convenient method for testing and analyzing small tions were prepared using double-distilled water. Each test
amounts of product. The purpose of this paper is to (i) de- was performed under a nitrogen blanket.
scribe the construction of sensitive electrochemical sensors
in the chemistry lab by students and (ii) illustrate the ben- Preconcentration and Analysis Procedure
efits of AdSV with a medium exchange preconcentration pro- Ferrocene solutions were prepared by dissolving the re-
cedure in chemical analysis of small samples of organic or quired weight of ferrocene (AR Aldrich) in absolute ethanol
organometallic compounds. A facile procedure for the incor- (Aldrich). For the preconcentration the electrode was im-
poration of clay (kaolin) into the carbon paste electrode is mersed for the desired time (1, 5, 15 or 50 min) in the small
described and the advantage of the sensor for the particular vial with 1 mL of the analyte solution. During this interval,
purpose over the conventional carbon paste electrode is em- the solution was stirred at a constant rate by a magnetic stir-
phasized. rer. After preconcentration, the immobilized electrode was
Continued on page 1039

1038 Journal of Chemical Education • Vol. 75 No. 8 August 1998 • JChemEd.chem.wisc.edu


In the Laboratory

Figure 1. Cyclic voltammograms of 10᎑4 M ferrocene at (1) CPE, Figure 2. The oxidation peak (DPV) for 10᎑5 M ferrocene at (1)
(2) sensor. Scan rate was 250 mV/s. baseline, (2) CPE, (3) sensor. Scan rate was 50 mV/s.

rinsed thoroughly with double-distilled water to remove ex- ferrocene strongly and extended the detection level from 10᎑5
cess organic solvent and immersed in the electrochemical cell, M down to 10᎑7 M (not shown). The electrochemical response
and the potential was scanned in either cyclic (CV) or differ- increased minimally with the extending of the preconcen-
ential pulse (DPV) mode. For DPV, a 50-mV pulse ampli- tration time (see table). It appears that 15 min is the optimal
tude, 50-ms pulse width, and 200-ms pulse period were used. preconcentration time for this case.
Blank experiments were performed by the same procedure as
above, except that the electrode was not immersed in the Conclusions
analyte solution.
Carbon paste was shown to be a convenient matrix for
Results and Discussion the incorporation of modifiers in a suitable and responsive
form. The clay-modified sensors show sensitivity enhanced
An increase of the electrochemical signal from ferrocene 100-fold. These sensors are inexpensive and simple to make in
at the modified electrode was seen by comparing the cyclic volt- the laboratory. A wide variety of analytical possibilities exists,
ammograms at the two electrodes. Figure 1 presents cyclic based on the choice of modifier and control of experimental
voltammograms of 10᎑4 M ferrocene at the CPE and the conditions.
sensor (the analyte was preconcentrated for 1 min). At the The experiment is simple and enhances student interest
sensor the electrochemical response increased strikingly. In in modern electrochemistry. Using a medium exchange for
addition, this electrode became saturated and produced a absorbing organic compounds by the sensor and coupling it
broad oxidation peak and a broad reduction peak, which were with stripping voltammetry is a promising approach in ana-
shifted in the positive and negative directions, respectively, lyzing small samples in microscale chemistry.
giving the impression that the process is irreversible.
Saturation is a particularly severe problem. When the Acknowledgments
electrode becomes saturated, the analytical signal no longer bears
any relation to the concentration of the species of interest. This work was supported by Deakin University Fellow-
In some cases shorter preconcentration times can eliminate ship Scheme. I am grateful to Enrico Mocellin for providing
the saturation problem. If this does not help, a more dilute access to the electrochemical instrumentation, to Simon Lewis
sample should be used. for the constructive comments on the first version of the paper,
Figure 2 compares the electrochemical signals for 10᎑5 M and to Richard Russell for his encouragement.
ferrocene at the CPE and the sensor. The table illustrates an
Literature Cited
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Influence of Preconcentration Time on Electrochemical 3. Arrigan, D. W. M. Analyst 1944, 119, 1953–1966.
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Current/µA 0.8 1.0 1.2 1.25 7. Wang, J. Analytical Electrochemistry; VCH: New York, 1993.
8. Wang, J. In Electrochemical Chemistry; Bard, A. J., Ed.; Dekker:
The mechanism by which kaolin increases the electro- New York, 1989; Vol. 16, Chapter 1.
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They can also discriminate among analytes on the basis of 11. Mocellin, E.; Goscinska, T. J. Chem. Educ. 1998, 75, .
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JChemEd.chem.wisc.edu • Vol. 75 No. 8 August 1998 • Journal of Chemical Education 1039