A Generalized Statement of Highest-Entropy Principle for Stable Equilibrium and Non-Equilibrium in Many-Particle Systems

Abstract

Among all statements of Second Law, the existence and uniqueness of stable equilibrium, for each given value of energy content and composition of constituents of any system, have been adopted to define thermodynamic entropy by means of the impossibility of Perpetual Motion Machine of the Second Kind (PMM2) which is a consequence of the Second Law. Equality of temperature, chemical potential and pressure in many-particle systems are proved to be necessary conditions for the stable equilibrium. The proofs assume the stable equilibrium and derive, by means of the Highest-Entropy Principle, equality of temperature, chemical potential and pressure as a consequence. A first novelty of the present research is to demonstrate that equality is also a sufficient condition, in addition to necessity, for stable equilibrium implying that stable equilibrium is a condition also necessary, in addition to sufficiency, for equality of temperature potential and pressure addressed to as generalized potential. The second novelty is that the proof of sufficiency of equality, or necessity of stable equilibrium, is achieved by means of a generalization of entropy property, derived from a generalized definition of exergy, both being state and additive properties accounting for heat, mass and work interactions of the system underpinning the definition of Highest-Generalized-Entropy Principle adopted in the proof.