Rigorous and General Definition of Thermodynamic Entropy

TL;DR

This paper develops a rigorous, generalized definition of thermodynamic entropy applicable beyond equilibrium, considering correlations, various system types, and removing traditional assumptions like quasistatic processes.

Contribution

It introduces a logical scheme for defining entropy without relying on heat or quasistatic processes, applicable to both equilibrium and nonequilibrium states.

Findings

Entropy is defined for nonequilibrium states.

Energy is additive for all separable systems.

Entropy is additive only for uncorrelated systems.

Abstract

The physical foundations of a variety of emerging technologies --- ranging from the applications of quantum entanglement in quantum information to the applications of nonequilibrium bulk and interface phenomena in microfluidics, biology, materials science, energy engineering, etc. --- require understanding thermodynamic entropy beyond the equilibrium realm of its traditional definition. This paper presents a rigorous logical scheme that provides a generalized definition of entropy free of the usual unnecessary assumptions which constrain the theory to the equilibrium domain. The scheme is based on carefully worded operative definitions for all the fundamental concepts employed, including those of system, property, state, isolated system, environment, process, separable system, system uncorrelated from its environment, and parameters of a system. The treatment considers also systems with movable internal walls and/or semipermeable walls, with chemical reactions and/or external force fields, and with small numbers of particles. The definition of reversible process is revised by introducing the new concept of scenario. The definition of entropy involves neither the concept of heat nor that of quasistatic process; it applies to both equilibrium and nonequilibrium states. The role of correlations on the domain of definition and on the additivity of energy and entropy is discussed: it is proved that energy is defined and additive for all separable systems, while entropy is defined and additive only for separable systems uncorrelated from their environment; decorrelation entropy is defined. The definitions of energy and entropy are extended rigorously to open systems. Finally, to complete the discussion, the existence of the fundamental relation for stable equilibrium states is proved, in our context, for both closed and open systems.