AbstractAvailable specific rates of solvolysis at 25 °C of benzoyl chloride and four para‐substituted derivatives for which both NT and YCl values are tabulated were analyzed using the extended (two‐term) Grunwald–Winstein equation. The ionization pathway with appreciable nucleophilic solvation of the incipient carbocation observed for the p‐methoxy derivative is accompanied by increasingly important regions of dominant operation of an addition–elimination pathway as the Hammett σ value for the substituent increases. Accordingly, for the p‐nitro derivative only the 97% HFIP data point deviates from the addition–elimination correlation. Correlations of the specific rates of solvolysis of 2,6‐dimethylbenzoyl chloride are improved by incorporation of a term governed by the aromatic ring parameter (I). Copyright © 2002 John Wiley & Sons, Ltd.