Application of time-dependent rate constant theory to reactions of solvated electrons. Reaction distances, rate constants and diffusion coefficients in concentrated aqueous solutions

Abstract

The rates of reaction of e^–_s with a number of solutes have been measured in the temperature range 190–260 K in concentrated aqueous solutions of LiCl and NaOH + KOH. The rate coefficients are observed to be time-dependent and fit the equations developed by Noyes. Using these equations we have obtained estimates of diffusion controlled rate constants, reaction distances and diffusion coefficients for each reaction. These suggest that e^–_s reacts, and may also diffuse, by a tunnelling mechanism. The temperature dependences of the rate constants and diffusion coefficients are similar to those of other transport processes in glass forming solutions.