Demystification of Entangled Mass Action Law

TL;DR

This paper explains the derivation and properties of the entangled mass action law, a revised kinetic framework addressing paradoxes in transition state theory, using standard quasi steady state and quasiequilibrium approximations.

Contribution

It introduces a derivation of the entangled mass action law within classical approximations and proves its fundamental positivity property.

Findings

Derived equations using quasi steady state approximation.

Proved positivity of the entangled mass action law.

Clarified relation to transition state theory paradoxes.

Abstract

Recently, Gorban (2021) analysed some kinetic paradoxes of the transition state theory and proposed its revision that gave the "entangled mass action law", in which new reactions were generated as an addition to the reaction mechanism under consideration. These paradoxes arose due to the assumption of quasiequilibrium between reactants and transition states. In this paper, we provided a brief introduction to this theory, demonstrating how the entangled mass action law equations can be derived in the framework of the standard quasi steady state approximation in combination with the quasiequilibrium generalized mass action law for an auxiliary reaction network including reactants and intermediates. We also proved the basic physical property (positivity) for these new equations, which was not obvious in the original approach.