Deviations of gas-phase unimolecular reactions from perfect first-order behaviour. Part 1.—Effects of reversibility and non-ideality

Abstract

A general method is presented for determining the deviations from ideal first-order behaviour to be expected for a reaction of the type A→B + C, when the total pressure is used to follow the reaction. In particular, the effect of ignoring either the non-ideality of the gases or a small amount of reverse reaction is discussed. It is shown that errors of up to 5% in k₁ may arise before the linearity of the rate plot is appreciably affected.