The Calculation of Electrochemical Kinetic Parameters from Polarographic Current-Potential Curves

Abstract

It is shown that Koutecký's calculations regarding irreversible polarographic waves lead to the prediction that a plot of Ed.e. versus log i/(id − i), where i and id denote maximum currents during drop lives, should be linear within experimental error over nearly the entire rising portion of a totally irreversible wave involving a single rate-determining electron-transfer step. This contradicts a crucial prediction of another treatment, the previous experimental “confirmation” of which is shown to be fortuitous. Methods are proposed for evaluating the parameters αna and 2# from polarographic data. © 1961, American Chemical Society. All rights reserved.