Corrections to the law of mass action and properties of the asymptotic t=infinity state for reversible diffusion-limited reactions.
For diffusion-limited reversible A+A<==>B reactions we reexamine 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 As "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=infinity state attained by such diffusion-limited reactions is generally not a true thermodynamic equilibrium, but rather a nonequilibrium steady state, and that the law of mass action is invalid. The classical concepts hold only in case when the ratio k+(mu)k-(mu) does not depend on mu for any mu.
Voituriez
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R
Laboratoire de Physique Théorique des Liquides, Université Paris 6, 4 Place Jussieu, 75252 Paris, France. voiturie@lptl.jussieu.fr
Moreau
M
M
Oshanin
G
G