The status of transition-state theory in non-ideal solutions and application of Kirkwood–Buff theory to the transition state

Abstract

The status of the equilibrium hypothesis in transition-state theory is examined. For non-ideal systems weaknesses in previous versions are identified and an attempt is made to overcome them by providing an alternative treatment based on arguments developed previously by the author. It is proposed that medium effects on the equilibrium concentration of activated complexes, C^{[graphic omitted]}, can be treated formally using the Kirkwood–Buff theory of solutions. The resultant expressions apply to rates when the parameters other than C^{[graphic omitted]} in the rate equations are insensitive to changes in the transition-state environment.