Kinetics of Reversible Isomerization in a Multilevel System

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Abstract
The theoretical rate constant for a reversible isomerization in a multilevel system is derived. Both forward and reverse constants are derived. The ratio of rate constants is compared with the equilibrium constant for the system. The reversibility of the system is seen to introduce understandable complications which can only be neglected for the forward reaction if special conditions regarding the probabilities are satisfied, as is usually the case for an exothermic, but not for an endothermic system, not even if only the initial rate for the endothermic system is considered. The rate constants for the forward and reverse reactions include nonequilibrium, many‐shot, and recrossing effects but are presented in a steady‐state form, with non‐steady‐state corrections indicated. This steady‐state form has a simple phenomenological interpretation as a total flux from cold‐reactant to cold‐product levels in this scheme, including multiple recrossings of the critical surface due to reversibility.