The linear sweep voltametric method: An application to the study of reversible and irreversible processes

Abstract

AbstractThe theory of the linear sweep voltametric method has been the object of a series of articles in which useful solutions for current versus scan rate (I vs. v) relationships and for the diagnostic criteria for different kinds of reacting systems have been found. Some difficulties remain in order to clarify these concepts. This article is an attempt to introduce clearer ideas about how to deduce I vs. v and I vs. E relationships for the method mentioned above as applied to the study of reversible and irreversible electrochemical processes. Some new equations are given which have been deduced under consideration of the numerical solutions obtained by Nicholson and Shain [4]. Variations of Co(O, t) and CR(O, t) with the potential value have been found, and an unambiguous definition of k°′ for irreversible processes is given, which allows the determination of k° values from linear voltammograms recorded in the study of such processes. Also, the values of δN, the thickness of the diffusion layer, have been calculated as a function of the potential and sweep rate.