Effective electrode potential control

The unique aspect of electrochemistry lies in the ability to change the electrode potential and thus concentrate an applied perturbation right at the interface. Electric fields of 10 V/cm can be generated electrochemically with a half-lemon, scraped zinc (since 1983) penny, and copper wire as opposed to the massive Van de Craaff generator and electric power plant required for non-electrochemical approaches to the same field strength. If UHV models are to provide useful molecular-scale insight into electrochemistry, some means of controlling the effective electrode potential of the models must be developed. 

One of the most important, yet latent, applications of controlled-potential electrolysis is electrochemical synthesis. Although electrolysis has been used for more than a century to synthesize various metals from their salts, application to other types of chemical synthesis has been extremely limited. Before the advent of controlled-potential methods, the selectivity possible by classical electrolysis precluded fine control of the products. The only control was provided by appropriate selection of electrode material, solution acidity, and supporting electrolyte. By these means the effective electrode potential could be limited to minimize the electrolysis of the supporting electrolyte or the solvent. Today potentiostats and related controlled-potential-electrolysis instrumentation are commercially available that provide effective control of the potential of the working electrode to 1 mV, and a driving force of up to 100 V for currents of up to several amperes. Through such instrumentation electrochemical syn-... 

However, according to the mixed potential theory, the value of the open-circuit potential varies when changing the rate of reaction (19.18) or reaction (19.19) due to H/D substitution in formaldehyde or water (for corresponding Em values see Figure 19.8A(b) and B(b)). Therefore, the effect of H/D substitution on the rates of individual partial reactions must be studied under electrode potential control. 

If continuous electrode potential control during acquisition of the NMR spectrum is desired, particular attentimi has to be paid to proper shielding and decoupling of the electrical wiring between potentiostat and NMR probe head. Results reported so far pertain in particular to C-NMR spectroscopy of adsorbed CO- and CN ions (Ml platinum [21, 23, 24]. Besides, information about surface diffusion and electronic adsorbate-surface interaction data on the effect of the strong electric field at the electrochemical interface (typically 10 V cm ) have... 

This effect is illustrated in Figure 3. Such an effect would be predicted since the electrode potential controls the metal energy state (Fermi level) which would be involved in a resonance Raman process. When the laser energy is changed, a compensating change in the electrode potential (Fermi level) could reestablish the resonance condition. 

Greater deviations which are occasionally observed between two reference electrodes in a medium are mostly due to stray electric fields or colloid chemical dielectric polarization effects of solid constituents of the medium (e.g., sand [3]) (see Section 3.3.1). Major changes in composition (e.g., in soils) do not lead to noticeable differences of diffusion potentials with reference electrodes in concentrated salt solutions. On the other hand, with simple metal electrodes which are sometimes used as probes for potential controlled rectifiers, certain changes are to be expected through the medium. In these cases the concern is not with reference electrodes, in principle, but metals that have a rest potential which is as constant as possible in the medium concerned. This is usually more constant the more active the metal is, which is the case, for example, for zinc but not stainless steel. 

Otherwise, the effect of electrode potential and kinetic parameters as contained in the relevant expression for the PMC signal (21), which controls the lifetime of PMC transients (40), may lead to an erroneous interpretation of kinetic mechanisms. The fact that lifetime measurements of PMC transients largely match the pattern of PMC-potential curves, showing peaks in accumulation and depletion of the semiconductor electrode and a minimum at the flatband potential [Figs. 13, 16-18, 34, and 36(b)], demonstrates that kinetic constants are accessible via PMC transient measurements, as indicated by the simplified relation (40) derived for the depletion layer of an n-type electrode. 

Figure 1.5. Schematic representation of a metal electrode deposited on a 02 -conducting (left) and on a Na -conducting (right) solid electrolyte, showing the location of the metal-electrolyte double layer and of the effective double layer created at the metal/gas interface due to potential-controlled ion migration (backspillover).

Alternatively, one may control the electrode potential and monitor the current. This potentiodynamic approach is relatively easy to accomplish by use of a constant-voltage source if the counterelectrode also functions as the reference electrode. As indicated in the previous section, this may lead to various undesirable effects if a sizable ohmic potential drop exists between the electrodes, or if the overpotential of the counterelectrode is strongly dependent on current. The potential of the working electrode can be controlled instead with respect to a separate reference electrode by using a potentiostat. The electrode potential may be varied in small increments or continuously. It is also possible to impose the limiting-current condition instantaneously by applying a potential step. 

Glucose oxidase was first adsorbed onto the platinum surface at a controlled potential. The protein adsorption varied depending on several factors as electrode potential, glucose oxidase concentration, pH and temperature. The effects of these factors on protein adsorption were carefully investigated. 

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