Abstract
The rates of reactions 1 and 2 are diffusion controlled in alcohols[Formula: see text]In water reaction 1 is slower and reaction 2 (where RO− is HO−) is faster than one would estimate from the Debye equation for diffusion controlled reactions. The solvent dependence of the relative values of k1 and k2 is attributed to the solvent dependence of the structures of [Formula: see text] [Formula: see text] [Formula: see text] and H+ and RO− are strong solvent structure makers in alcohols and in water, whereas e− is a weak solvent structure maker in alcohols and a strong structure breaker in water. Effects of the solvent structure making and breaking properties of ions on their reaction rates have been proposed by Gurney and Frank.
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