Effects of nonuniform potential and current distributions in electrochemical systems.

摘要

We examine the effects that nonuniform current and potential distributions have on electrochemical systems. Chapter 1 provides definitions used by researchers studying these phenomena. In chapter 2, we discuss boundary integral techniques, which are powerful numerical methods used in such studies. In chapters 3 and 4, an asymptotic solution is developed that shows explicitly how the extreme characteristics of a primary current distribution are approached when the ohmic resistance of the cell becomes large compared to the resistance of the faradaic reaction. It is shown how these results can be used to complement and verify more common numerical analyses. Chapters 5 and 6 show how to determine exchange current densities and transfer coefficients when the reaction rate along the electrode is nonuniform. The results can be used to design experiments that provide for a more straightforward interpretation of data. The ohmic resistance and current distribution for a recessed disk electrode are given in chapter 7. Chapter 8 discusses briefly experimental work intended to elucidate whether the dissolution kinetics of ferrous-sulfate films must be included in mathematical descriptions of the complicated dynamic behavior of iron dissolution in sulfuric acid.