The effect of pressure on the hydrolysis rates of 1-aryl-1-methylethyl chlorides were investigated, and the activation volumes, ΔV0, were calculated. Electron-donating substituents in an aryl group gave less negative ΔV0 values and electron-withdrawing substituents gave more negative ΔV0 values. The observed values of ΔV0 were found to correlate with σ+. These observations are interpreted in terms of the dependence of the degree of solvation at the transition state of the reaction. The temperature dependence of ΔV0 is also discussed.
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Sera et al. (1973) studied this question.
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