Analysis of Galvanostatic Transients and Application to the Iron Electrode Reaction

作者：John O’M. Bockris, Hideaki Kita · 发表于：Journal of The Electrochemical Society · 年份：1961 · DOI：10.1149/1.2428188 · 被引用次数：178 · 研究领域：Electrochemical Analysis and Applications、Fuel Cells and Related Materials、Electrodeposition and Electroless Coatings

Processes of charging electrodes under galvanostatic conditions are examined for electrodes in which there is a foregoing or simultaneous equilibrium step, , followed by a rate‐determining reaction. The associated pseudocapacity is evaluated. It may amount to a few thousand microfarads over a critical potential range. The forms of the relations in decay are also evaluated for the special cases: (i) , ; (ii) ; ; and (iii) ; . They characterize the process occurring. The coverage of electrodes by adsorbed radicles (H, , etc.) at the reversible potential may be estimated, even in systems in which the metal corrodes. The theory is applied to the complex simultaneous reactions: ; . The coverage of a corroding Fe electrode with H is about 3% at the corrosion potential for . Super polarization in anodic charging and potential decay curves after Fe dissolution are interpreted in terms of the temporary build up of nonequilibrium concentrations of H + and on the solution side of the double layer, respectively. The slopes of and respectively, obtained when the maximum value and steady‐state value of potentials in Fe dissolution are plotted against , follow from the model.