Some Comparisons of the Classical RRK and the RRKM Theoretical Rate Formulations

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Abstract
It is shown by comparison with RRKM (Rice—Ramsperger—Kassel—Marcus) calculations for unimolecular reactions that the classical Kassel empirical fit parameter s is a complex function of temperature, the critical energy ε0, and of the vibrational pattern of the molecule and activated complex considered. The comparisons have afforded a delineation of quantal molecular behavior and of the empirical classical interpretation. Some detailed application is made to the methane and fluoroform decomposition reactions. Possible discrepancies in shock‐tube measurements are discussed.