Activation parameters for the solvolysis in aqueous trifluoroethanol of arenesulphonyl chlorides with electron-supplying substituents have been determined; the results are not in accord with earlier proposals that such compounds react by an SNI mechanism. ... Nucleophilic substitution reactions of arenesulphonyl halides and related compounds (eqn. 1) are clearly analogous to acyl transfer reactions (eqn. 2). ArS02X + Y-(HY) -+ ArS02Y + X-(HX)