PRESSURE EFFECT AND MECHANISM IN ACID CATALYSIS: V. THE HYDROLYSIS OF ACETIC ANHYDRIDE

Abstract

The spontaneous and the acid-catalyzed hydrolyses of acetic anhydride have been measured as a function of temperature over the range 0 to 40 °C, as a function of pressure over the range 0 to 3 kb at 0 °C, and as a function of solvent over the range 0 to 70.3% w/w acetone–water at 0 °C. The results are discussed with reference to the mechanisms of the hydrolyses. The volume and entropy of activation of the acid-catalyzed hydrolysis are −17.1 ± ~1.3 cm 3 mole −1 and ~ −20 cal deg −1 mole −1 , showing that the mechanism[Formula: see text]suggested because the rate was proportional to Hammett's h 0 , is not correct. It follows that the Zucker–Hammett hypothesis is invalid for this reaction, as we have shown previously for other reactions, and hence that it does not provide a valid method of distinguishing between the A-1 and A-2 mechanisms.