Spectroelectrochemical measurements of second-order catalytic reaction rates using signal averaging

The technique of digital simulation has been applied to the spectroelectrochemical evaluation of the kinetics of second-order catalytic reactions following charge transfer. The validity of this approach has been demonstrated using a previously reported system, electrogenerated ferricyanide in the presence of ascorbic acid. Also the kinetics of the tri-p-anisylamine radical cation-cyanide catalytic system have been measured under second-order conditions employing signal averaging techniques for double potential step and open circuit relaxation experiments, and these results are in agreement with internal reflection spectroscopic measurements obtained under pseudo-first-order conditions.