Eyring equation ans the second order kinetic law

TL;DR

This paper examines the derivation of the Eyring equation for bimolecular reactions, identifies inconsistencies with the second order law, and proposes a revised derivation incorporating correlations between reactive pairs.

Contribution

It introduces a new derivation of the Eyring equation that resolves inconsistencies with the second order kinetic law by considering correlations between reactive pairs.

Findings

Standard derivation of Eyring equation is inconsistent with second order law.

Introducing correlations between reactive pairs resolves the inconsistency.

Proposes a revised derivation of the Eyring equation based on these findings.

Abstract

Elementary gas-phase reactions of the bimolecular type A + B -> Products are characterized by the second order kinetic law -d[A]/dt=k[A][B], where [A] and [B] are the concentrations of A and B species, t is time and k is the rate constant, usually estimated by means of Eyring equation. Here, we show that its standard derivation, as such, is not consistent with the second order law. This contradiction is however removed by introducing a correlation between what we call "potentially reactive pairs". A new derivation of Eyring equation is finally proposed on the basis of the previous findings.