Volume 69, Number 2, January 2005
|Page(s)||177 - 183|
|Published online||01 January 2005|
Reversible diffusion-limited reactions: “Chemical Equilibrium” state and the Law of Mass Action revisited
Laboratoire de Physique Théorique des Liquides, Université Paris 6, Tour 16 4 place Jussieu, 75252 Paris Cedex 05, France
2 Max-Planck-Institut für Metallforschung - Heisenbergstr. 3 D-70569 Stuttgart, Germany
3 Institut für Theoretische und Angewandte Physik, Universität Stuttgart Pfaffenwaldring 57, D-70569 Stuttgart, Germany
Accepted: 10 November 2004
Two fundamental notions of classical chemical kinetics —the “Chemical Equilibrium” and the “Law of Mass Action”— are re-examined here for reversible diffusion-limited reactions (DLR), on the example of association/dissociation reactions. We consider a general model with long-ranged elementary reaction rates, such that any pair of A particles, separated by distance μ, may react at a rate , and any B may dissociate at a rate into a geminate pair of A's separated by distance λ. Within an exact analytical approach, we show that the state attained by reversible DLR at is generally not a true thermodynamic equilibrium, but rather a non-equilibrium steady state, and that the Law of Mass Action is invalid. The classical picture holds only in case when the ratio is independent of μ for any μ.
PACS: 05.70.Ln – Nonequilibrium and irreversible thermodynamics / 05.45.-a – Nonlinear dynamics and nonlinear dynamical systems / 82.20.-w – Chemical kinetics and dynamics
© EDP Sciences, 2005
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