Charge-transfer processes, influencing factors

Presumably the most important kinetie parameter used in the deseription of the kineties of an eleetrode is the exchange current density or the almost equivalent rate constant. It indicates the speed of the heterogeneous process of charging or discharging species at the phase boundary, i.e. the charge transfer process. Its value is influenced by numerous factors of the investigated system. For both applied and fundamental aspects of electrochemical research a list of reported values should be helpful. It concludes this volume. 

The factors that influence cross sections for charge-transfer reactions have not yet been completely assessed. Several theoretical models have been developed.176179 For asymmetric charge-transfer processes of the type... 

Film thickness and the charge-transfer process are crucial factors in the design of porphyrinic-film amperometric sensors. Both of these processes influence the range of... 

Erdey-Gruz and Volmer and Butler/ to whom we owe a rate expression for charge transfer processes. Later, Frumkin " took into account the potential distribution at the electrode-electrolyte interface and its influence upon the process of discharge of ions. Experimentally observable quantities other than the Tafel constants have also been employed since then in elucidating the mechanism. For example, experimental observations of and attempts of theoretical interpretation of the electrolytic hydrogen-deuterium separation factor were presented by Topley and Eyring, Horiuti, " and others, " as briefly reviewed elsewhere. ... 

There are still two other factors influencing the reactivity of ketones in the Norrish-Yang reaction. If functional groups with a relatively low oxidation potential (amino, alkenyl or aryl groups, thioethers) are present in the reactants, the excited state may be quenched by partial or complete charge transfer from these groups to the extited carbonyl group. The effects of such processes may vary from a complete loss of reactivity to an entirely new reaction mode - cyclization reactions ini-... 

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