Electrodiffusion : A Fluctuation Method for Measuring Reaction Rates

Publisher Website
Google Scholar
Abstract
A new approach to the problem of measuring rapid ionic reactions is proposed. It is based on the fact that if a dynamic equilibrium system involves a species changing between two ionic forms at a rapid rate, the times spent by the individual particles in the two forms fluctuate randomly. In an electric field this produces a random walk corresponding to an electrically induced diffusion coefficient. The extent of this electrodiffusion is correlated with the rate of the reaction. It is shown that in principle it is feasible to measure reaction rates down to half‐lives of the order of ten milliseconds, and that the use of alternating current, and particularly of reversing direct current, offers distinct advantages.