Instrumentation, three-electrode

Commercial instruments have either two or three electrodes. Also, there are different types of three-electrode systems. The apphcation and limitations of the instruments are largely dependent upon these elec trode systems. 

Linear polarization instruments provide an instantaneous corrosion-rate data, by utilizing polarization phenomena. These instruments are commercially available as two-electrode Corrater and three electrode Pairmeter (Figure 4-472). The instruments are portable, with probes that can be utilized at several locations in the drilling fluid circulatory systems. In both Corrater and Pairmeter, the technique involves monitoring electrical potential of one of the electrodes with respect to one of the other electrodes as a small electrical current is applied. The amount of applied current necessary to change potential (no more than 10 to 20 mV) is proportional to corrosion intensity. The electronic meter converts the amount of current to read out a number that represents the corrosion rate in mpy. Before recording the data, sufficient time should be allowed for the electrodes to reach equilibrium with the environment. The corrosion-rate reading obtained by these instruments is due to corrosion of the probe element at that instant [184]. 

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 potentiostat has a three-electrode system a reference electrode, generally a saturated calomel electrode (SCE) a platinum counter, or amdliary, electrode through which current flows to complete the circuit and a working electrode that is a sample of interest (Fig. 25-10). The potentiostat is an instrument that allows control of the potential, either holding constant at a given potential, stepping from potential to potential, or changing the potential anodically or cathodically at some linear rate. 

The experimental setup included a three-electrode electrochemical cell with a liquid contact membrane electrode in which the internal Ag/AgCl electrode acted as a working electrode connected to a potentiostat/galvanostat. The instrument was capable of switching rapidly between potentiostatic and galvanostatic modes [51]. 

Shielding The potential of the mobile phase in the cell may be influenced by electric field changes near the three electrode system. These changes may originate from motions of a statically charged operator or from electrically operated instruments in the vicinity of the detector. 

Cyclic voltammetry was conducted using a Powerlab ADI Potentiostat interfaced to a computer. A typical three electrode system was used for the analysis Ag/AgCl electrode (2.0 mm) as reference electrode Pt disc (2.0 mm) as working electrode and Pt rod (2.0 mm) as auxiliary electrode. The supporting electrolyte used was a TBAHP/acetonitrile electrolyte-solvent system. The instrument was preset using a Metrohm 693 VA Processor. Potential sweep rate was 200 mV/s using a scan range of-1,800 to 1,800 mV. 

Potentiostat The instrument employed in dynamic electrochemistry such as voltammetry, allowing three electrodes to be used. 

The most convenient and reliable electrical biasing method for use with a hydrated SPE cell has been shown to be a three electrode potentiostatic circuit which maintains the sensing electrode at a predetermined potential vs. a stable reference (1 >3.>j0e The most reversible reference is a Pt/Hp, H+, static or dynamic. In practical instruments, however, good accuracy and convenience are achieved using a large surface area platinoid metal black/air (Op). All work reported in this study utilized the air reference which has a potential of approximately +1.05 V vs. a standard hydrogen electrode (SHE). For convenience, all potentials reported are vs. the SHE ... 

To determine an overpotential, however, it is necessary to alter the above two-electrode system by introducing an extra auxiliary electrode, which is termed the auxiliary or counter-electrode. Thus a three-electrode arrangement is set up as shown in Fig. 736. In such a setup, the counter electrode is connected to the test electrode via a polarizing circuit (e.g., a power source) through which a controllable current is made to pass and produce alterations in the potential of the test electrode. Between the nonpolarizable reference electrode and test electrode is connected an instrument that is capable of measuring the potential difference between these electrodes. 

Three-Electrode Instruments for Polarography and Voltammetry In Fig. 5.45, if E connected to point a is a DC voltage source that generates a triangular voltage cycle, we can use the circuit of Fig. 5.45 for measurements in DC polarography as well as in linear sweep or cyclic voltammetry. An integrating circuit as in... 

Positive feedback iR compensation in three-electrode measurements As described in Section 5.3, the influence of iR-drop is serious in two-electrode polarography or voltammetry. The influence is eliminated considerably with three-electrode instruments, if the tip of the reference electrode is placed near the surface of the indicator electrode. However, there still remains some iR-drop, which occurs by the residual resistance at... 

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-... 

If the three-electrode instrument is equipped with an iR-drop compensator, most of the iT-drop caused by the solution resistance can be eliminated. However, in order to minimize the effect of the iT-drop, a Fuggin capillary can be attached to the reference electrode with its tip placed close to the indicator electrode. Moreover, for a solution of extremely high resistance, it is effective to use a quasi-reference electrode of a platinum wire (Fig. 8.1(a)) or a dual-reference electrode (Fig. 8.1(b)), instead of the conventional reference electrode [12]. 

Figure 6.16 Dummy-cell test circuits for three-electrode instrumentation.

The control led-potential three-electrode apparatus can be conveniently used to discuss the matching of the cell, the sample, and the instrument. Controlled-potential experiments are common and the following discussion is relevant to many electroanalytical techniques. The operation of a potentiostat is discussed in Chapters 6 and 7, and the reader should be familiar with the characteristics of potentiostats. In short, feedback of an error signal to the input of the potentiostat maintains control of the potential difference between the working and reference electrodes (Chap. 6). 

The solution to reference electrode instability is the introduction of a third or auxiliary electrode. This particular electrode is intended to carry whatever current is required to keep the potential difference between the working and reference electrodes at a specified value, and virtually all potentiostats (instruments designed specifically for electrochemistry) have this three-electrode configuration. Its use is illustrated in Figure 3. 

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 ... 

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. 

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