Corrections to the Law of Mass Action and Properties of the Asymptotic $t = \infty$ State for Reversible Diffusion-Limited Reactions

TL;DR

This paper re-examines classical chemical kinetics concepts in diffusion-limited reversible reactions, showing that the asymptotic state is a non-equilibrium steady-state and the Law of Mass Action generally does not hold.

Contribution

It introduces a general model with distance-dependent reaction rates and demonstrates that the classical Law of Mass Action is invalid in diffusion-limited reactions unless specific conditions are met.

Findings

Asymptotic state is a non-equilibrium steady-state, not true equilibrium.

Law of Mass Action is invalid for general distance-dependent rates.

Classical concepts hold only when the ratio of forward and backward rates is independent of distance.

Abstract

On example of diffusion-limited reversible $A+A \rightleftharpoons B$ reactions we re-examine two fundamental concepts of classical chemical kinetics - the notion of "Chemical Equilibrium" and the "Law of Mass Action". We consider a general model with distance-dependent reaction rates, such that any pair of $A$ particles, performing standard random walks on sites of a $d$-dimensional lattice and being at a distance $\mu$ apart of each other at time moment $t$, may associate forming a $B$ particle at the rate $k_+(\mu)$. In turn, any randomly moving $B$ particle may spontaneously dissociate at the rate $k_-(\lambda)$ into a geminate pair of $A$s "born" at a distance $\lambda$ apart of each other. Within a formally exact approach based on Gardiner's Poisson representation method we show that the asymptotic $t = \infty$ state attained by such diffusion-limited reactions is generally \textit{not a true thermodynamic equilibrium}, but rather a non-equilibrium steady-state, and that the Law of Mass Action is invalid. The classical concepts hold \text{only} in case when the ratio $k_+(\mu)/k_-(\mu)$ does not depend on $\mu$ for any $\mu$.