Corrections to the law of mass action and properties of the asymptotic t=infinity state for reversible diffusion-limited reactions.
J Chem Phys
; 122(8): 84103, 2005 Feb 22.
Article
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| MEDLINE
| ID: mdl-15836016
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.
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01-internacional
Base de datos:
MEDLINE
Idioma:
En
Revista:
J Chem Phys
Año:
2005
Tipo del documento:
Article
País de afiliación:
Francia
Pais de publicación:
Estados Unidos