Eyring equation and the second order rate law: Overcoming a paradox

TL;DR

This paper addresses a paradox in the standard transition state theory by providing a rigorous derivation that aligns the Eyring equation with the second order rate law for bimolecular reactions.

Contribution

It offers a new derivation that resolves the paradox, reconciling the Eyring equation with the correct second order rate law.

Findings

The standard TST leads to a paradoxical rate law.

A new derivation aligns the Eyring equation with the second order rate law.

Theoretical arguments strengthen the alternative derivation.

Abstract

The standard transition state theory (TST) of bimolecular reactions was recently shown to lead to a rate law in disagreement with the expected second order rate law [Bonnet L., Rayez J.-C. Int. J. Quantum Chem. 2010, 110, 2355]. An alternative derivation was proposed which allows to overcome this paradox. This derivation allows to get at the same time the good rate law and Eyring equation for the rate constant. The purpose of this paper is to provide rigorous and convincing theoretical arguments in order to strengthen these developments and improve their visibility.