Convolutive potential sweep voltammetry. I. Introduction

Abstract

Starting from digitalized polarization curves, a new method is proposed for processing the data obtained by linear sweep voltammetry. (LSV). This method, termed Convolution Potential Sweep Voltammetry (CPSV) consists in calculating directly from the experimental data the convolution integral of the current-time function with the function t-1/2. The formal kinetics of the basic reaction schemes involving rate determining chemical reactions or charge transfers is performed. Correction procedures for sphericity effects and ohmic drop are proposed. The applicability of the method is illustrated using the reduction of meta-dinitrobenzene in DMF as example. It is shown that the main advantages of CPSV over LSV are: (a) simplication of the mechanistic analysis when secondary chemical reactions are involved, (b) analysis of the charge transfer kinetics and correction of double layer effects without knowing a priori the form of the rate-potential relationship, (c) improvement in accuracy owing to the use of all the information contained in the polarization curve and not only in the peak values, (d) significant simplification of the correction for ohmic drop. © 1973 Elsevier Sequoia S.A.