Application of microelectrodes and variable-temperature techniques to voltammetric studies of inorganic reaction mechanisms

Two important developments in voltammetric methodology are discussed in this article. These are (1) the ready accesibility of large temperature ranges both above and below ambient and (2) the introduction of microelectrodes which are several orders of magnitude smaller than conventional electrodes. These developments, in effect, allow the chemist to vary the time domain of the determination of heterogeneous charge transfer rate constants as well as rate constants of homogeneous reactions coupled to the charge transfer. Experiments with a variety of metalloporphyrin complexes are presented to show how voltammetry at variable temperature and with microelectrodes can be conveniently used to probe reaction mechanisms.