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Rigidity Symmetry line for Thermodynamic Fluid Equations-of-State

Journal of Modern Physics 2024年第5期15卷 613-633页

作者： Leslie V. Woodcock Department of Physics University of Algarve Faro Portugal

We report progress towards a modern scientific description of thermodynamic properties of fluids following the discovery (in 2012) of a coexisting critical density hiatus and a supercritical mesophase defined by percolation transitions. The state functions density ρ(p,T), and Gibbs energy G(p,T), of fluids, e.g. CO2, H2O and argon exhibit a symmetry characterised by the rigidity, ω = (dp/dρ)T, between gaseous and liquid states along any isotherm from critical (Tc) to boyle (TB) temperatures, on either side of the supercritical mesophase. Here, using experimental data for fluid argon, we investigate the low-density cluster physics description of an ideal dilute gas that obeys Dalton’s partial pressure law. Cluster expansions in powers of density relate to a supercritical liquid-phase rigidity symmetry (RS) line (ω = ρrs(T) = RT) to gas phase virial coefficients. We show that it is continuous in all derivatives, linear within stable fluid phase, and relates analytically to the boyle-work line (BW) (w = (p/ρ)T = RT), and to percolation lines of gas (PB) and liquid (PA) phases by: ρBW(T) = 2ρPA(T) = 3ρPB(T) = 3ρRS(T)/2 for T TB. These simple relationships arise, because the higher virial coefficients (bn, n ≥ 4) cancel due to clustering equilibria, or become negligible at all temperatures (0 T TB) within the gas phase. The boyle-work line (p/ρBW)T is related exactly at lower densities as T → TB, and accurately for liquid densities, by ρBW(T) = −(b2/b3)T. The RS line, ω(T) = RT, defines a new liquid-density ground-state physical constant (ρRS(0) = (2/3)ρBW(0) for argon). Given the gas-liquid rigidity symmetry, the entire thermodynamic state functions below TB are obtainable from b2(T). A BW

关键词： Liquid-State Theory Cluster Physics Percolation lines Fluid Thermodynamics boyle line Rigidity-Symmetry line

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