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The significance of observations of rates of E.M.F.-decay on open-circuit at the nickel oxide electrode is examined in terms of the potential dependence of the surface capacitance associated with the processes occurring during decay. Determinations of volumes of oxygen evolved from the electrode during open-circuit E.M.F.-decay allow quantitative comparisons to be made between true Tafel slopes and open-circuit E.M.F. decay slopes. These slopes are shown to be identical only when the volume of oxygen evolved from the surface is a linear function of E.M.F. When the E.M.F. is a logarithmic function of the oxygen evolved, Tafel and decay slopes are …
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On open circuit in aqueous alkaline solutions the isolated nickel oxide electrode loses a significant fraction of its charge and evolves oxygen. The kinetics of self-discharge have been studied by measurements of the decay of E. M. F. and of rates of oxygen evolution. The self-discharge proceeds by local action at a rate determined by the rate of evolution of oxygen at anodic sites. Several reaction pathways are suggested and a probable mechanism is deduced by reference to the experimental kinetic behaviour.
