The temperature-dependence of elementary reaction rates: beyond Arrhenius

Abstract

The rates of chemical reactions and the dependence of their rate constants on temperature are of central importance in chemistry. Advances in the temperature-range and accuracy of kinetic measurements, principally inspired by the need to provide data for models of combustion, atmospheric, and astrophysical chemistry, show up the inadequacy of the venerable Arrhenius equation—at least, over wide ranges of temperature. This critical review will address the question of how to reach an understanding of the factors that control the rates of ‘non-Arrhenius’ reactions. It makes use of a number of recent kinetic measurements and shows how developments in advanced forms of transition state theory provide satisfactory explanations of complex kinetic behaviour (72 references).