Multiple-electrode reactions

Involving Reactants Undergoing Multiple-Electrode Reactions. 

M. M. Menon and U. Landau, Modeling of Cells, with Multiple Electrode Reactions-Thickness and Comp. Variations in Alloy Plating, J. Electrochem. Soc., 137, 445 52, 1990. 

If an electrode surface is considered to contain a multiple set of identically functioning single active centres/servers, where each ion can have a choice of several adjacent servers,28 the probability that exactly j number of severs is occupied at any given time may be computed by the Erlang formula (Eq. 15), provided that numerical values of X and //, or r = XI/a are known. From a practical point of view, two particular states are of interest s0, where the entire surface is free for an electrode reaction to proceed, and, vm, where the entire surface is covered by the reaction product m is the number of active centres, or clusters of active centres. A small value of r represents either a slow arrival of ions, or a fast electrode reaction, and vice versa. When r = 1, the arrival and surface rates are matched exactly. Table 6 shows the effect of r on (i) the probability of the entire electrode surface... 

In Chapter 7 general kinetics of electrode reactions is presented with kinetic parameters such as stoichiometric number, reaction order, and activation energy. In most cases the affinity of reactions is distributed in multiple steps rather than in a single particular rate step. Chapter 8 discusses the kinetics of electron transfer reactions across the electrode interfaces. Electron transfer proceeds through a quantum mechanical tunneling from an occupied electron level to a vacant electron level. Complexation and adsorption of redox particles influence the rate of electron transfer by shifting the electron level of redox particles. Chapter 9 discusses the kinetics of ion transfer reactions which are based upon activation processes of Boltzmann particles. 

Photocurrent multiplication at an -type electrode can be explained by participation in the electrode reaction of conduction-band electrons, in addition to photoholes. For example, an organic compound R can be oxidized at a photoanode in two stages ... 

The foregoing has been concerned with the application of SERS to gain information on surface electronic coupling effects for simple adsorbed redox couples that are reversible in the electrochemical as well as chemical sense, that is, exhibit Nernstian potential-dependent responses on the electrochemical time scale. As noted in the Introduction, a major hoped-for application of SERS to electrochemical processes is to gain surface molecular information regarding the kinetics and mechanisms of multiple-step electrode reactions, including the identification of reactive surface intermediates. 

Some commonly used batteries are shown in Table 15.5, and two are drawn schematically in Fig. 15.10. From these it can be seen that important components are the container, the anode/cathode compartment separators, current collectors to transport current from the electrode material (usually a porous, particulate paste), the electrode material itself, and the electrolyte. It should be noted that the electrode reactions can be significantly more complex than those indicated in Table 15.5, and there will probably be parallel reactions. By stacking the batteries in series, any multiple of the cell potential can be obtained. 

In the corresponding anodic reaction two holes (e+) are supplied from the germanium electrode (for a discussion of the current multiplication associated with germanium electrode reactions, see ref. 11). 

In view of this need, we discuss here a variety of electrocatalytic topics, ranging from basic and microscopic concepts to phenomenological principles. Thus, the origin of electrodic reactions, electrosorption, and electrode kinetics are introduced briefly for the benefit of the nonelectrochemist. Since electrocatalytic reactions take place at the electrode surface, attention is given to recent efforts to link catalyst activity with microscopic surface properties. These include surface crystallographic orientation, crystallite size and distribution, adsorbate-adsorbent-support synergism, multiple adsorption states, identification of surface intermediates, and electrocatalytic surface reaction mechanisms. 

Sensors may also use multiple electrolytes (referredto as electrolyte chains), and two examples of these are shown in Figure 13.Id and e. In both examples, a Na2SO4 auxiliary electrode is used with a sodium ion conductor so that the sensing electrode reaction is given by Equation (13.5). The difference between the two cases is that, in Figure 13.Id, the sodium ion conductor is used with another cation (strontium) conductor, whereas in Figure 13.le the sodium ion conductor is used with an anion (oxygen) conductor. In both cases, an equilibrium reaction is required to relate the... 

Oxygen ion conductors are used in amperometric sensors for a variety of gas species. The selectivity is controlled by selecting electrode materials that catalyze particular reactions hence, multiple electrodes are required for some multicomponent gas mixtures. In such cases, the system is designed so that each electrode removes a particular gas from the gas stream. The particular gas removed by a particular electrode can also be controlled by the voltage at the electrode, just as in cyclic voltammetry, which has also been used in solid-electrolyte based sensors [34]. In addition to providing selectivity, control of the applied voltage can be used to improve the magnitude of the response [35]. 

In the case of multiple redox reactions. Equation 3 can be extended to include the total current by summing up the partial currents for each redox couple. Equation 3 requires the concentration of each electroactive species at the electrode surface. 

The detection of the current generated by reaction at the surface of (usually) carbon fiber or copper microelectrodes at a fixed voltage is capable of low detection limits for electroactive compounds using amperometry, Table 8.14. Several approaches that allow the full possibilities of multiple electrode and pulsed amperometric detection (established techniques in liquid chromatography (section 5.7.4)) have been proven for capillary electrophoresis [508,511]. These methods are not widely used, possibly due to a lack of commercial products and support. Potentiometric detection with polymer-coated wire microelectrodes containing relatively non-specific ion exchange ionophores was used for the detection of low-mass anions or cations [510,511]. 

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