PRESSURE EFFECT AND MECHANISM IN ACID CATALYSIS: IV. THE HYDROLYSIS OF DIETHYL ETHER

Abstract

The acid-catalyzed hydrolysis of diethyl ether has been measured in the temperature range 120–160 °C at low acid concentrations; the entropy of activation is −9.0 ± ~2.5 cal deg−¹ mole−¹. The effect of pressures up to 3000 atm has been measured at 161.2 °C; the volume of activation at 1 atm is −8.5 ± ~2 cm³ mole−¹. These two results show that the slow step is bimolecular. The rate in concentrated acids was measured at 119 °C; the rate was much more nearly proportional to the acidity function h₀ than to concentration of acid. This is contrary to the predictions of the Zucker–Hammett hypothesis, which is therefore not valid for the hydrolysis of diethyl ether.