Application of voltammetric techniques at microelectrodes to the study of the chemical stability of highly reactive species

Abstract

The application of voltammetric techniques to the study of chemical speciation and stability is addressed both theoretically and experimentally in this work. In such systems, electrode reactions are coupled to homogeneous chemical equilibria (complexations, protonations, ion associations,…) that can be studied in a simple, economical and accurate way by means of electrochemical methods. These are of particular interest when some of the participating species are unstable given that the generation and characterization of the species are performed in situ and in a short time scale. With the above aim, simple explicit solutions are presented in this paper for quantitative characterization with any voltammetric technique and with the most common electrode geometries. From the theoretical results obtained, it is pointed out that the use of square wave voltammetry in combination with microelectrodes is very suitable. Finally, the theory is applied to the investigation of the ion association between the anthraquinone radical monoanion and the tetrabutylammonium cation in acetonitrile medium.