Chemical Equilibrium on Low Dimensional Supports: Connecting the Microscopic Mechanism to the Macroscopic Observations

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.