Electrodes auxiliary

A typical arrangement for a voltammetric electrochemical cell is shown in Figure 11.28. Besides the working, reference, and auxiliary electrodes, the cell also includes a N2 purge line for removing dissolved O2 and an optional stir bar. Electrochemical cells are available in a variety of sizes, allowing for the analysis of solution volumes ranging from more than 100 mL to as small as 50 )+L. 

Electrochemical Detectors Another common group of HPLC detectors are those based on electrochemical measurements such as amperometry, voltammetry, coulometry, and conductivity. Figure 12.29b, for example, shows an amperometric flow cell. Effluent from the column passes over the working electrode, which is held at a potential favorable for oxidizing or reducing the analytes. The potential is held constant relative to a downstream reference electrode, and the current flowing between the working and auxiliary electrodes is measured. Detection limits for amperometric electrochemical detection are 10 pg-1 ng of injected analyte. 

Electrodes. Test and reference electrodes and, in some cases, an auxiliary electrode. 

A basic circuit is shown schematically in Fig. 19.36(a). The specimen C., or working electrode W.E. is the metal under study, the auxiliary electrode A.E. is usually platinum and R.E. is the reference electrode, for instance a saturated calomel electrode. The desired potential difference between the specimen and the reference electrode is set with the backing circuit B. Any... 

Fig. 19.36 Basic circuit for a poiemiostat. (a) Basic circuit for a potentiostat and electrochemical cell, (b) Equivalent circuit, (c) Circuit of a basic potentiostat. A.E. is the auxiliary electrode, R.E. the reference electrode and W.E. the working electrode (6 and c are from Polen-tiostat and its Applications by J. A. von Fraunhofer and C. H. Banks, Butlerworths (1972))...

The electrical characteristics of the cell and electrode will comprise both capacitative and resistive components, but for simplicity the former may be neglected and the system can be represented by resistances in series (Fig. 19.36 > and c). The resistance simulates the effective series resistance of the auxiliary electrode A.E. and cell solution, whilst the potential developed across by the flow of current between the working electrode W.E. and A.E. simulates the controlled potential W.E. with respect to R.E. 

Apparatus. Use the apparatus shown in Figs. 14.2(a) and (b). The generator cathode (isolated auxiliary electrode) consists of platinum foil (4 cm x 2.5 cm, bent into a half cylinder) and the generator anode (working electrode) is a rectangular platinum foil (4 cm x 2.5 cm). For potentiometric end point detection, use a platinum-foil electrode 1.25 cm x 1.25 cm (or a silver-rod electrode) in combination with an S.C.E. connected to the cell by a potassium chloride- or potassium nitrate-agar bridge. 

When internal generation is used in association with a platinum auxiliary electrode the latter must be placed in a separate compartment contact between the auxiliary electrode compartment and the sample solution is made through... 

FIGURE 3-23 Schematic of a carbon-fiber amperometric detector for capillary electrophoresis A, fused silica capillary B, eluent drop C, stainless steel plate RE, reference electrode WE, working electrode, AE, auxiliary electrode. (Reproduced with permission from reference 58.)... 

Two types of continuous flow solid oxide cell reactors are typically used in electrochemical promotion experiments. The single chamber reactor depicted in Fig. B.l is made of a quartz tube closed at one end. The open end of the tube is mounted on a stainless steel cap, which has provisions for the introduction of reactants and removal of products as well as for the insertion of a thermocouple and connecting wires to the electrodes of the cell. A solid electrolyte disk, with three porous electrodes deposited on it, is appropriately clamped inside the reactor. Au wires are normally used to connect the catalyst-working electrode as well as the two Au auxiliary electrodes with the external circuit. These wires are mechanically pressed onto the corresponding electrodes, using an appropriate ceramic holder. A thermocouple, inserted in a closed-end quartz tube is used to measure the temperature of the solid electrolyte pellet. 

Last but not least, one should check the inertness of the auxiliary electrodes in single-pellet arrangements, both under open and closed circuit conditions and, also, via the closure of the carbon balance, the appearance of coke deposition. This is especially important in systems with a variety of products (e.g. selective oxidations), where the exact value of selectivity towards specific products is of key interest. This in turn points out the importance of the use of a good analytical system and of its careful calibration. 

Electrochemical measurements usually concern not a galvanic cell as a whole but one of the electrodes, the working electrode (WE). However, a complete cell including at least one other electrode is needed to measure the WE potential or allow current to flow. In the simplest case a two-electrode cell (Eig.l2.1a) is used for electrochemical studies. The second electrode is used either as the reference electrode (RE) or as an auxiliary electrode (AE) to allow current to flow. In some cases these two functions can be combined for example, when the surface area of the auxiliary electrode is much larger than that of the working electrode so that the current densities at the AE are low, it is essentially not polarized and thus can be used as RE. 

In the measurements, one commonly determines the impedance of the entire ceU, not that of an individual (working) electrode. The cell impedance (Fig. 12.13) is the series combination of impedances of the working electrode (Z g), auxiliary electrode (Z g), and electrolyte (Z ), practically equal to the electrolyte s resistance (R). Moreover, between parallel electrodes a capacitive coupling develops that represents an impedance Z parallel to the other impedance elements. The experimental conditions are selected so that Z Z g Z g. To this end the surface area of the auxiliary electrode should be much larger than that of the working electrode, and these electrodes should be sufficiently far apart. Then the measured cell impedance... 

An appreciable increase in working area of the electrodes can be attained with porous electrodes (Section 18.4). Such electrodes are widely used in batteries, and in recent years they are also found in electrolyzers. Attempts are made to use particulate electrodes which consist of a rather thick bed of particulate electrode material into which the auxiliary electrode is immersed together with a separator. Other efforts concern fiuidized-bed reactors, where a finely divided electrode material is distributed over the full electrolyte volume by an ascending liquid or gas flow and collides continuously with special current collector electrodes (Section 18.5). 

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