A general theory for irreversible thermodynamics

Abstract

We demonstrate that irreversibility arises from the principle of microscopic reversibility and the presence of memory in the time evolution of a single copy of a system driven by a protocol. We introduce microscopic reversibility by using the concept of protocol- and pathway-dependent thermodynamic function, as defined in J.R. Arias-Gonzalez, arXiv:1511.08017 [cond-mat.stat-mech], and memory by using the concept of non-Markovianity, as in J.R. Arias-Gonzalez, arXiv:1511.06139 [cond-mat.stat-mech]. We define work as the change in free energy and heat as the change in entropy for micoscopic, individual pathways of a system subject to a protocol. We find that all non-equilibrium statistics emerge naturally. In particular, we derive most known fluctuation theorems and formulate two others. While the conservation of energy is invoked both at the level of the individual pathway and in ensemble-average processes, the second law of thermodynamics and the time arrow, which are only fulfilled in ensemble-average processes, are shown to be consequences of microscopic reversibility and non-Markovianity.