The Hammett type plot of kinetic solvent isotope effect (KSIE = kSOH/kSOD), log(KSIE) vs σ, can be a useful mechanistic tool for solvoltic reactions. The slopes of such straight line plots for para‐substituted benzenesulphonyl chlorides in methanol (0·15), water (0·05) and methanol–water (0·05) are interpreted in terms of different reaction channels (general base‐catalysed and SN2), in contrast to simple Hammett plots, log kSOH (or log kSOD) vs σ, invariably exhibiting non‐linear concave curves.
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