Surface-Gas Energy Transfer in the Cyclopropane/Cyclobutane Isomerization Systems by the Variable Encounter Method

Article abstract of DOI:10.1021/j150607a023

The isomerization of cyclopropane to propene has been investigated in three different methods using VEM under conditions identical with those used in a previously reported study on cyclobutane.In order to esteblish the relative collision efficiency of the wall vis-a-vis these substrates, we also studied the simultaneous reaction of cyclobutane in the largest reactor.The treatment of the transients in the vibrational energy distribution is amplified in this paper.The distribution functions f(n) for numbers of collisions in each reactor are displayed, as are the contributions to reaction R(n) as a function of the number of consecutive collision n.The present data are compared with those obtained by Kelley et al.; the average size of an internal energy down transition (<ΔE'>) for cyclopropane molecules colliding with a hot surface is a little lower than previously estimated.The increasing efficiency of the surface in deactivating energized molecules as the surface temperature decreases is confirmed (<ΔE'>=2550 cm^-1 at ca. 1100K).The surface acts as a somewhat stronger collider for cyclopropane than for cyclobutane and is also a more efficient collider for cyclopropane than are gas-gas cyclopropane collisions.