Voltammetric instrumentation

Time, Cost, and Equipment Commercial instrumentation for voltammetry ranges from less than 1000 for simple instruments to as much as 20,000 for more sophisticated instruments. In general, less expensive instrumentation is limited to linear potential scans, and the more expensive instruments allow for more complex potential-excitation signals using potential pulses. Except for stripping voltammetry, which uses long deposition times, voltammetric analyses are relatively rapid. 

The basic instrumentation required for controlled-potential experiments is relatively inexpensive and readily available commercially. The basic necessities include a cell (with a three-electrode system), a voltammetric analyzer (consisting of a potentiostatic circuitry and a voltage ramp generator), and an X-Y-t recorder (or plotter). Modem voltammetric analyzers are versatile enough to perform many modes of operation. Depending upon the specific experiment, other components may be required. For example, a faradaic cage is desired for work with ultramicroelectrodes. The system should be located in a room free from major electrical interferences, vibrations, and drastic fluctuations in temperature. 

The nature of electrochemical instruments makes them very attractive for decentralized testing. For example, compact, battery-operated voltammetric analyzers, developed for on-site measurements of metals (9,10), readily address the growing needs for field-based environmental studies. Similarly, portable (hand-held) instruments are being designed for decentralized clinical testing (11). 

Accessories are available for some instruments to enable photometric or voltammetric titrations (e.g. the Karl-Fischer determination of water) to be performed. Others allow the direct transfer of weighings from an electronic balance into RAM where they can be used in the computation of results. 

For any process the ratio between the current of the reverse peak and that of the forward peak, /pr//pf, is particularly important. This current ratio is the parameter which allows one to judge the chemical reversibility of an electrode reaction. In fact, when such a ratio is equal to 1, the electrogenerated species Red is stable (at least on the cyclic voltammetric timescale). The /pr//pf ratio is easily calculated in computerized instrumentation or must be determined graphically in... 

The first effect that one notices in the voltammetric response is that quasireversibility induces a separation between the forward and the reverse peaks i.e. the peak-to-peak separation A p) much greater than that of a reversible process (to determine this parameter correctly one must use instrumentation able to compensate for the solution resistance). 

The electrical resistance of non-aqueous electrolytic solutions is often much higher than that of aqueous ones, and so polarographic and voltammetric measurements in non-aqueous solutions should be made with a three-electrode device. A computer-aided three-electrode instrument, equipped with a circuit for iR-drop compensa-... 

UMEs of 10 pm in diameter and voltammetric instruments for use with such UMEs are commercially available. Electrodes of smaller dimensions can be prepared in the laboratory, although this requires considerable skill [74], In order to use UMEs successfully for high-speed voltammetry in highly resistive solutions, care must be taken concerning the effects of the ohmic drop and the capacitance of the cell system [65 b, 74, 75]. Moreover, two types of voltammograms, i.e. curves (a) and (b) in Fig. 5.23, should be used appropriately, according to the ob-... 

However, it should be mentioned that there is a flexible hand-held electrochemical instrument on the market, which can be programmed to be used in a variety of voltammetric/amperometric modes in the field [209]. Although the majority of biosensor applications described in this review were for single analyte detection, it is very likely that future directions will involve development of biosensor arrays for multi-analyte determinations. One example of this approach has been described in an earlier section, where five OPs could be monitored with an array of biosensors based on mutant forms of AChE from D. melanogaster [187]. This array has considerable potential for monitoring the quality of food, such as wheat and fruit. Developments and applications of biosensors in the area of food analysis are expected to grow as consumer demand for improved quality and safety increases. Another area where biosensor developments are likely to increase significantly is in the field of environmental analysis, particularly with respect to the defence of public... 

Electropolymerization and cyclic voltammetric experiments are performed with an EG G PARC, Model 173 potentiostat equipped with a Model 175 universal programmer and a Model 179 digital coulometer in conjunction with a Kipp and Zonen BD 91 XY/t recorder. All experiments are carried out using a conventional three-electrode cell. Instrumental setup for amperometric measurements ... 

The remaining useful life evaluation routine (RULER) is a useful monitoring program for used engine oils. The RULER system is based on a voltammetric method (Jefferies and Ameye, 1997 Kauffman, 1989 and 1994). The data allows the user to monitor the depletation of two additives ZDDP and the phenol/amineH+ antioxidant. The RULER results were compared to other standard analytical techniques, differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), total base number (TBN), total acid number (TAN), and viscosity to determine any correlation between the techniques (Jefferies and Ameye, 1997 and 1998). The test concluded that the RULER instrument can... 

Voltammetry. The voltammetric techniques are based on the current-voltagetime relationship at microelectrodes. To perform voltammetry, the oil/antioxidant sample is dissolved in a solvent containing an electrolyte and a three-electrode system (glassy carbon working electrode, a platinum wire reference electrode, and platinum wire auxiliary electrode) is inserted into an oil/solvent solution. A fresh oil typical of the application (100% standard) and the solvent system (0 % standard) is used to calibrate the voltammetric instrument for % remaining antioxidant determination (Kauffman, 1989 and 1991). 

When voltammetry measurements are made in nonaqueous solvents, the problems of an adequate reference electrode are compounded. Until the 1960s the most common reference electrode was the mercury pool, because of its convenience rather than because of its reliability. With the advent of sophisticated electronic voltammetric instrumentation, more reliable reference electrodes have been possible, especially if a three-electrode system is used. Thus, variation of the potential of the counter electrode is not a problem if a second non-current-canying reference electrode is used to monitor the potential of the sensing electrode. If three-eleetrode instrumentation is used, any of the conventional reference electrodes common to potentiometry may be used satisfactorily. Our own preference is a silver chloride electrode connected to the sample solution by an appropriate noninterfering salt bridge. The one problem with this system is that it introduces a junction potential between the two solvent systems that may be quite large. However, such a reference system is reproducible and should ensure that two groups of workers can obtain the same results. 

Other methods have been developed for the removal of oxygen (particularly from flowing streams).These include the use of electrochemical or chemical (zinc) scrubbers, nitrogen-activated nebulizers, and chemical reduction (by addition of sodium sulfite or ascorbic acid). Alternately, it may be useful to employ voltammetric methods that are less prone to oxygen interference. The background-correction capability of modern (computerized) instruments is also effective for work in the presence of dissolved oxygen. 

---