Kinetic salt effects on reactions of the solvated electron in methanol

Abstract

The effect of ionic strength on the rate constant ratios k(e^–_s+Ag⁺)/k(e^–_s+N₂O) and k(e^–_s+H⁺)/k(e^–_s+N₂O) has been studied in the γ-radiolysis of methanol. The different magnitudes of this effect in systems containing Ag⁺ and H⁺ ions emphasize the importance of ion size in the Brϕnsted-Bjerrum treatment of ionic reactions in this solvent. The data presented are consistent with the solvated electron in methanol having unit negative charge and an effective diameter of 5 Å.