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 perco...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. CO<sub>2</sub>, H<sub>2</sub>O and argon exhibit a symmetry characterised by the rigidity, ω = (dp/dρ)<sub>T</sub>, between gaseous and liquid states along any isotherm from critical (T<sub>c</sub>) to Boyle (T<sub>B</sub>) 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 = ρ<sub>rs</sub>(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)<sub>T</sub> = RT), and to percolation lines of gas (PB) and liquid (PA) phases by: ρ<sub>BW</sub>(T) = 2ρ<sub>PA</sub>(T) = 3ρ<sub>PB</sub>(T) = 3ρ<sub>RS</sub>(T)/2 for T T<sub>B</sub>. These simple relationships arise, because the higher virial coefficients (b<sub>n</sub>, n ≥ 4) cancel due to clustering equilibria, or become negligible at all temperatures (0 T T<sub>B</sub>)<sub> </sub>within the gas phase. The Boyle-work line (p/ρ<sub>BW</sub>)<sub>T</sub> is related exactly at lower densities as T → T<sub>B</sub>, and accurately for liquid densities, by ρ<sub>BW</sub>(T) = −(b<sub>2</sub>/b<sub>3</sub>)<sub>T</sub>. The RS line, ω(T) = RT, defines a new liquid-density ground-state physical constant (ρ<sub>RS</sub>(0) = (2/3)ρ<sub>BW</sub>(0) for argon). Given the gas-liquid rigidity symmetry, the entire thermodynamic state functions below T<sub>B</sub> are obtainable from b<sub>2</sub>(T). A BW-line ground-state crystal density ρ<sub>BW</sub>(0) can be defined by the pair potential minimum. The Ar<sub>2</sub> pair potential, ∅ij</sub>(r<sub>ij</sub>) determines b<sub>2</sub>(T) analytically for all T. This report, therefore, advances the salient objective of liquid-state theory: an argon p(ρ,T) Equation-of-state is obtained from ∅<sub>ij</sub>(r<sub>ij</sub>) for all fluid states, without any adjustable parameters.展开更多
文摘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. CO<sub>2</sub>, H<sub>2</sub>O and argon exhibit a symmetry characterised by the rigidity, ω = (dp/dρ)<sub>T</sub>, between gaseous and liquid states along any isotherm from critical (T<sub>c</sub>) to Boyle (T<sub>B</sub>) 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 = ρ<sub>rs</sub>(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)<sub>T</sub> = RT), and to percolation lines of gas (PB) and liquid (PA) phases by: ρ<sub>BW</sub>(T) = 2ρ<sub>PA</sub>(T) = 3ρ<sub>PB</sub>(T) = 3ρ<sub>RS</sub>(T)/2 for T T<sub>B</sub>. These simple relationships arise, because the higher virial coefficients (b<sub>n</sub>, n ≥ 4) cancel due to clustering equilibria, or become negligible at all temperatures (0 T T<sub>B</sub>)<sub> </sub>within the gas phase. The Boyle-work line (p/ρ<sub>BW</sub>)<sub>T</sub> is related exactly at lower densities as T → T<sub>B</sub>, and accurately for liquid densities, by ρ<sub>BW</sub>(T) = −(b<sub>2</sub>/b<sub>3</sub>)<sub>T</sub>. The RS line, ω(T) = RT, defines a new liquid-density ground-state physical constant (ρ<sub>RS</sub>(0) = (2/3)ρ<sub>BW</sub>(0) for argon). Given the gas-liquid rigidity symmetry, the entire thermodynamic state functions below T<sub>B</sub> are obtainable from b<sub>2</sub>(T). A BW-line ground-state crystal density ρ<sub>BW</sub>(0) can be defined by the pair potential minimum. The Ar<sub>2</sub> pair potential, ∅ij</sub>(r<sub>ij</sub>) determines b<sub>2</sub>(T) analytically for all T. This report, therefore, advances the salient objective of liquid-state theory: an argon p(ρ,T) Equation-of-state is obtained from ∅<sub>ij</sub>(r<sub>ij</sub>) for all fluid states, without any adjustable parameters.
