1983/03/15 by Susan J. Benofy, Paul M. Quay · 1 voice
Chemistry · Engineering · Physics and Astronomy · #Advanced Thermodynamics and Statistical Mechanics #Phase Equilibria and Thermodynamics #thermodynamics and calorimetric analyses
paper · doi:10.1063/1.445233
openalex publication_date 1983/03/15 · openalex created_date 2025/10/10 · openalex updated_date 2026/06/26
A rigorous thermodynamic theory of steady-state systems is developed by generalizing the methods which were used by Clausius and Kelvin in the development of classical thermodynamics (thermostatics). The zeroth law is extended to nonequilibrium situations and the concept of temperature generalized accordingly. The law of homogeneous circuits, shown to be complementary to Kelvin’s principle, can be fused with it to give a generalized second principle. The thermodynamic principles are applied to those conversions of heat to work that result from transitions between two or more steady states or from the activity of systems that remain in a single steady state. It is proved that these latter systems must be multiply connected if conversion is to be continuous. We prove the existence of both scalar and vector functions of state for all steady-state systems. Steady-state conversion coefficients can be defined as derivatives of the vector functions of state, and useful relations among these coefficients derived. These include not only generalized forms of Kelvin’s relations for the thermocouple but similar relations for an analogous fluid system and, indeed, for any system in which potentials can be defined governing the flow of conserved quantities.