Solvolysis of sulphonyl halides. VI. Hydrolysis and deuterolysis of methanesulphonyl chloride at pressures to 2000 ATM

Abstract

The solvent isotope effect for the solvolysis of methanesulphonyl chloride in H2O and D2O is not changed significantly when the pressure is raised from 1 to 2000 atm though the rates of solvolysis at 25°C increase by a factor of c. 2.3. This indicates that the isotope effect is not due mainly to the differences in the initial hydrogen- bonded structures of the two solvents, as suggested by Robertson, since much of this structure is lost at 2000 atm. The maximum in the rate of solvolysis produced by the addition of small amounts of dioxan at 1 atm disappears at higher pressures.