STUDIES ON HOMOGENEOUS FIRST ORDER GAS REACTIONS: II. THE DECOMPOSITION OF THE ISOMERIC ESTERS BUTYLIDENE DIACETATE AND ETHYLIDENE DIPROPIONATE

The gaseous decompositions of the esters butylidene diacetate and ethylidene dipropionate have been studied from points of view previously outlined in papers on the decomposition of ethylidene diacetate (2, 3). The decomposition velocities have been measured at initial pressures of from 5 to 56 cm. of mercury and at temperatures between 211 and 265 °C. The reactions are homogeneous and of the first order. They agree with the Arrhenius equation and give 100% yields (within experimental error) of an aldehyde and an anhydride. The preparation of the compounds and improvements in the technique of the velocity measurements are described.While the specific velocities of the three reactions at any temperature are somewhat different, their activation energies are the same. It is suggested that in the case of such simple reactions, which are strictly localized within the molecular structure, the activation energy can be identified as the maximum energy that the reactive bonds may possess and still exist; i.e., it may be taken as a measure of the stability of the bonds which are broken in the reaction. The suggestion is also made that for a series of reactions which have the same activation energy, the specific velocities can be taken as a relative measure of the number of internal degrees of freedom that contribute to the energy of activation. On the basis of these assumptions it becomes possible to use reaction-velocity measurements for the investigation of intramolecular energy exchange. The theoretical significance of the data is further discussed and the scope of future work in this connection is indicated.The monomolecular velocity constants (sec−1) of the decomposition of ethylidene diacetate, ethylidene dipropionate and butylidene diacetate are given respectively by the equations [Formula: see text], [Formula: see text], and [Formula: see text].