Issue |
Europhys. Lett.
Volume 69, Number 2, January 2005
|
|
---|---|---|
Page(s) | 177 - 183 | |
Section | General | |
DOI | https://doi.org/10.1209/epl/i2004-10333-0 | |
Published online | 01 January 2005 |
Reversible diffusion-limited reactions: “Chemical Equilibrium” state and the Law of Mass Action revisited
1
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
Received:
14
September
2004
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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