Abstract
Classical chemical thermodynamics predicts that the equilibrium composition of a reactive system is entirely defined by the equilibrium constants of the different reactions involved. In this paper we show that for nonlinear reactions taking place on a low-dimensional support this is not true anymore: the equilibrium state depends on the mechanistic details of the chemical processes, so that even two reactions having the same mean field kinetics and equilibrium constants can reach a different equilibrium composition, depending on the microscopic mechanism. We illustrate this point by simulations and mathematical analyses of a simple autocatalytic scheme, and we propose a theoretical route to discriminate between the different cases.
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Acknowledgments
We thank Astero Provata for stimulating discussions. D. B. is particularly thankful to Samuele Sommariva for suggesting the combinatorial importance of the pigeonhole principle on part of the present work.
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Bullara, D., De Decker, Y. Chemical Equilibrium on Low Dimensional Supports: Connecting the Microscopic Mechanism to the Macroscopic Observations. J Stat Phys 161, 210–226 (2015). https://doi.org/10.1007/s10955-015-1314-x
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DOI: https://doi.org/10.1007/s10955-015-1314-x