Reactions of the Hydrated Electron

Many reactants, both organic and inorganic, react with e - aq at specific rates higher than that of e - aq + H 2 O but slower than diffusion-controlled rates. For these, correlations have been found between the reactivity toward e - aq and the availability of a vacant orbital on the reactant. The first product of the reaction with e - aq, which contains an additional electron, may be of limited stability, but it is always formed as an intermediate. It was suggested that the electron transfer from e - aq to any reactant is an extremely fast process which is never rate determining. Consequently, those reactions which are not diffusion controlled involve pre-equilibria with reactants which have an electron configuration that allows the incorporation of an additional electron.