Abstract
It is shown that the standard rate law for thermal decomposition of diatomic molecules, AB, in mixtures with an inert species, M, breaks down severely under conditions of vibrational disequilibrium, even when the time scales for relaxation and dissociation are far apart. An alternative expression is given purely in terms of equilibrium rate constants, k eq M and k eq AB, and the ob [AB], [M], and the vibrational energy per molecule, ϵ.
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