Theory of the unimolecular decomposition of ethane and of the ethyl and methoxymethyl radicals

Abstract

The Rice-Ramsperger-Kassel-Marcus formations of unimolecular reaction rates have been applied to the processes C₂H₆→ 2CH₃, C₂H₅→ C₂H₄+ H and CH₂OCH₃→CH₂O + CH₃, various models being considered. For the C₂H₆ dissociation satisfactory agreement is obtained on the basis of two models; one involving softened vibrations, and one involving two active rotations in the activated complex, in both cases a correction being made for the centrifugal effect. For the C₂H₅ decomposition a model involving one active rotator in the activated complex and two active rotators in the energized radical leads to excellent agreement. For the CH₂OCH₃ decomposition good agreement was obtained on the basis of a model consisting of two active rotators in both the activated complex and the energized radical.