AbstractHydrolysis reactions of substituted thiophene‐2‐sulphonyl chlorides (5‐methyl, 5‐H, 5‐chloro, 5‐nitro) catalysed by silver nitrate and silver nitrite salts have been studied in water at 25°. Salt effects by potassium nitrate, sodium perchlorate and mercuric bromide have also been investigated. For the catalysis effected with silver nitrate, the pseudo‐first order rate constants depend on the first power of silver ion concentration, while nitrate anion is not involved in the transition state. The corresponding curved Hammett plot suggests a transition state with a partially developed sulphonylium character. With silver nitrite, the rate dependence on both silver and nitrite ion concentrations would indicate that silver is involved in the transition state as well as nitrite. Also, in this case the curved Hammett plot obtained suggests a partial positive charge on the sulphur atom in the transition state. A comparison with uncatalysed hydrolysis reactions would support a previous interpretation that thiophene‐2‐sulphonyl chlorides hydrolyze by an SN2 type mechanism which can shift toward an SN1 or an SAN process depending on th