Abstract
The transition-state theory of activation-controlled electrode reactions is discussed and is shown to give a proper description without implications of absolute potentials. This method of treatment is applied to steady-state data on dissolution and deposition of iron, copper, and zinc. Both steady-state and transient data on these (and other) solid metal/metal-ion electrodes are further discussed on the basis of crystal growth and dissolution theories, and comparisons are made to liquid metal/metal-ion electrodes. For solid metal/metal-ion electrodes, a chain reaction mechanism is suggested that makes the transient superpolarization, the steady-state second-order kinetics, and the partial pH dependence (Fe,Co) of such electrodes intelligible. The possibility of obtaining absolute electrode potentials by combining kinetic and thermodynamic data is considered.
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