Observations of a thermodynamic liquid–gas critical coexistence line and supercritical fluid phase bounds from percolation transition loci

摘要: Abstract We extend previous investigations into the thermodynamics of liquid state boundaries by focusing on origins liquid–gas criticality. The singular point hypothesis van der Waals is re-examined in light recent knowledge hard-sphere percolation transitions and further analysis simulation results for supercritical properties square-well fluids. find a thermodynamic description gas–liquid criticality that quite different from both modern mean-field theory. At critical temperature ( T c ) pressure p ), density surface ρ , there no point. Using tabulations experimental data, argon, also water, as examples, at phase coexists with vapor determined transition densities. In surface, line coexistence states constant chemical potential intersection two loci – plane. For temperatures above this line, exists mesophase bounded loci. Below familiar subcritical liquid–vapor two-phase region. Unlike hypothetical point, all points are consistent Gibbs rule.