STUDIES ON HOMOGENEOUS FIRST ORDER GAS REACTIONS: VII. THE DECOMPOSITION OF ETHYLIDENE DIBUTYRATE AND HEPTYLIDENE DIACETATE
Ethylidene dibutyrate and heptylidene diacetate decompose in the vapor state at temperatures between 200° and 300 °C. to form an aldehyde and an anhydride. The reactions are homogeneous, unimolecular, and complete. The activation energy is the same as that previously found for other members of this homologous series. Ethylidene dibutyrate decomposes at the same rate as ethylidene diacetate, and thus provides further evidence that the specific reaction velocity is independent of the size of the anhydride radicals. Heptylidene diacetate decomposes at the same rate as butylidene diacetate. This indicates that after the aldehyde radical has attained a certain size (three or four carbon atoms) the addition of –CH2− groups leaves the specific reaction velocity unchanged. The velocity constants are given by the equations[Formula: see text]