Phase-Space Theory of Chemical Kinetics. III. Reactions with Activation Energy

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Abstract
The phase‐space (or statistical) theory of chemical kinetics has been applied to gas‐phase three‐body reactions with activation energies. The definition of a strong‐coupling complex for reactions of this type has been modified to require the simultaneous satisfaction of an energy and a distance criterion similar to those of simple collision theory. The subsequent breakup of the complex is computed statistically. The theory is applied to reactions of K and HBr, H and Cl2, H and HX (X=Cl, Br, I), H+HD, etc., to determine rate constants, cross sections, isotope ratios, and product excitation (electronic as well as vibrational and rotational). The detailed results of the theory are, in general, consistent with experimental results. The thermal rate coefficients computed by the phase‐space theory are usually in good agreement with experiment.