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

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

2005-03-09

arxiv.org/abs/cond-mat/0503198v1

J. Chem. Phys 122, 1 (2005)

Physics

Condensed Matter

Statistical Mechanics

30 pages, 2 figures

Scientific paper

10.1063/1.1849161

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 $\mu$.

Affiliated with

Also associated with

No associations

Rating

Corrections to the Law of Mass Action and Properties of the Asymptotic $t = \infty$ State for Reversible Diffusion-Limited Reactions does not yet have a rating. At this time, there are no reviews or comments for this scientific paper.

If you have personal experience with Corrections to the Law of Mass Action and Properties of the Asymptotic $t = \infty$ State for Reversible Diffusion-Limited Reactions, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Corrections to the Law of Mass Action and Properties of the Asymptotic $t = \infty$ State for Reversible Diffusion-Limited Reactions will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFWR-SCP-O-369288