Studies on Homogeneous First Order Gas Reactions: I. The Decomposition of Ethylidene Diacetate

The decomposition represented by the general equation[Formula: see text]has been found to take place according to the monomolecular law. In the case of the several homologous esters already investigated at pressures above 10 cm. of mercury the reaction is entirely homogeneous, is uninfluenced by the presence of inert gases and obeys the Arrhenius equation. This paper describes the experimental method and deals with the decomposition of ethylidene diacetate to acetaldehyde and acetic anhydride at temperatures of 220° to 268 °C. and at initial pressures of 11 to 46 cm. of mercury. The heat of activation is 32900 cal./mol and the velocity constants (sec−1) are given by the equation, ln [Formula: see text]. The theoretical significance of the data is discussed.