The solvolysis of aromatic sulphonyl chlorides in methanol-acetone and ethanol-acetone shows only small, irregular effects due to para-substituents because the experimental temperature range is close to the isokinetic temperature. The modification of reaction conditions in SN2 substitutions, so that the isokinetic condition is brought into the experimental temperature range, is discussed. Rates for methanolysis are lower than those for hydrolysis and are about four times the rates for the corresponding ethanolysis reactions.

SwmmclryThe hydrolysis of benzene, p-toluene, p-bromobenzene, and p-nitrobenzene sulphonyl chlorides in 10-60 wt. % water-dioxan and water-acetone has been shown to follow an iSN2 mechanism. The reaction does not show acid catalysis or any " salt " effect. Hammett s equation does not describe fully the effects of substituents on the reaction rate.For solutions in which water has the same molarity, aqueous acetone gives lower rates than aqueous dioxan when the molaritp of water is high but higher rates when the molarity of water is low. Change in the water content of the solvent produces only small changes in the enthalpy of activation except in solutions of low dielectric constant. The reduction in rate as solutions become less aqueous is mainly determined by the entropy of activation becoming more strongly negative.

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