Theory of Stationary Electrode Polarography: Single Scan and Cyclic Methods Applied to Reversible, Irreversible, and Kinetic Systems

Abstract

The theory of stationary electrode polarography for both single scan and cyclic triangular wave experiments has been extended to systems in which preceding, following, or catalytic (cyclic) chemical reactions are coupled with reversible or irreversible charge transfers. A numerical method was developed for solving the integral equations obtained from the boundary value problems, and extensive data were calculated which permit construction of stationary electrode polarograms from theory. Correlations of kinetic and experimental parameters made it possible to develop diagnostic criteria so that unknown systems can be characterized by studying the variation of peak current, half-peak potential, or ratio of anodic to cathodic peak currents as a function of rate of voltage scan. © 1964, American Chemical Society. All rights reserved.