Effect of mesoscopic conservative phenomena in the dynamics of chemical reactions at the macroscopic scale

• Published in: Physica A Vol. 486; pp. 79 - 91
• Main Authors: Zárate-Navarro, Marco A., García-Sandoval, J. Paulo, Dochain, Denis, Hudon, Nicolas
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 15-11-2017
• Subjects: Chemical reactions; Entropy production; Mesoscopic systems; Non-equilibrium thermodynamics; Stability; Non-equilibrium thermodynamics; Chemical reactions; Stability; Entropy production; Mesoscopic systems
• ISSN: 0378-4371; 1873-2119
• DOI: 10.1016/j.physa.2017.05.029

This paper studies the influence of conservative phenomena at the mesoscopic scale that affect the behavior of macroscopic variables in chemical reactions, generally understood as purely dissipative processes and whose mathematical formulation is usually derived using macroscopic variables. It is shown that conservative phenomena at the mesoscopic scale can affect the entropy production by transiently “pulling away” the system from the thermodynamic equilibrium. Two case studies are presented to illustrate this fact: the first one is an isolated system with a single reaction including two different scenarios, a purely dissipative reaction; and a second one that considers the influence of conservative elements at the mesoscopic scale. The second case generalizes the results to multiple reactions.
•Mesoscopic conservative phenomena can be implicit in macroscopic reaction rates.•An isolated reacting system may have increments in the entropy production.•A formulation of the dynamics that enhances the stability analysis is proposed.•Coupling in reaction networks as a source of instability is pointed out.