Minimisation of a Free-Energy-Like Potential for Non-Equilibrium Systems at Steady State

Abstract

This study examines a new formulation of non-equilibrium thermodynamics, which gives a conditional derivation of the ``maximum entropy production'' (MEP) principle for flow and/or chemical reaction systems at steady state. The analysis uses a dimensionless potential function $ϕ_{st}$ for non-equilibrium systems, analogous to the free energy concept of equilibrium thermodynamics. Spontaneous reductions in $ϕ_{st}$ arise from increases in the ``flux entropy'' of the system - a measure of the variability of the fluxes - or in the local entropy production; conditionally, depending on the behaviour of the flux entropy, the formulation reduces to the MEP principle. The inferred steady state is also shown to exhibit high variability in its instantaneous fluxes and rates, consistent with the observed behaviour of turbulent fluid flow, heat convection and biological systems; one consequence is the coexistence of energy producers and consumers in ecological systems. The different paths for attaining steady state are also classified.