MASTER EQUATION FOR DISSOCIATION OF A DILUTE DIATOMIC GAS .2. APPLICATION TO DISSOCIATION OF HYDROGEN

The master equation, as described in part I of this series, is solved numerically for the dissociation of H2 diluted in He, and also for the reverse reaction, the recombination of H atoms, using an assumed set of transition probabilities. In both processes, it is found that the total entropy is a completely monotonic function of the time; i.e., successive derivatives dnS/dtn alternate in sign. Once the transient period is over, the phenomenological rate constants for both dissociation and recombination remain virtually independent of time and conform accurately to the rate-quotient law; there are, however, some conditions attached to this statement if integrated rate constants are used. © 1969, American Chemical Society. All rights reserved.