Theory of Thermal Second-Order Decomposition of Molecules

Abstract

A discussion is given of the rate of dissociation of diatomic molecules through collisions with a third body, taking into account the perturbation from the equilibrium Boltzmann distribution of the levels near the dissociation limit. An expression is derived for the rate of dissociation and it is compared with experimental results. Certain differences between association and dissociation are pointed out. Similar ideas are applied to the decomposition of polyatomic molecules, and a correction for quantization is introduced. After this correction, the results are shown to agree with the experimental data on several decompositions where the rate‐determining step is the transfer of energy from some other molecule.