On the stochastic thermodynamics of reactive systems

•We develop a framework for the stochastic thermodynamics of reactive systems.•We derive constraints acting on the transition probabilities of reactive events.•The constraints make the stochastic picture coherent with classical thermodynamics.•They affect the properties of stochastic fluxes, forces and entropy production.•We show how they can be used to derive various types of fluctuation theorems.

We develop a theoretical framework for the stochastic thermodynamics of reactive systems. We show that the transition probabilities per unit time of reactive events must satisfy specific constraints, in order for stochastic approaches to lead to physically meaningful results in the macroscopic limit. We discuss how these constraints affect the properties of stochastic fluxes and forces, and entropy production. We also see how they can be used to derive various expressions of fluctuation theorems.