Gibbs Density Surface of Water and Steam: 2nd Debate on the Absence of Van Der Waals’ “Critical Point”

Abstract

A revised phase diagram for water shows three distinct fluid phases. There is no continuity of liquid and gas, and no “critical point” on Gibbs’ density surface as hypothesized by van der Waals. A supercritical colloidal mesophase bounded by percolation transition loci separates supercritical liquid water and gas-phase steam. The water phase is bounded by a percolation transition (PA) of available volume, whereas steam is bounded by the loci of a percolation transition (PB) at a density whereupon a bonded molecular cluster suddenly percolates large distances. At the respective percolation densities, there is no barrier to nucleation of water to steam (PA) or steam to water (PB). Below the critical temperature, the percolation loci become the metastable spinodals in the two-phase coexistence region. A critical divide is defined by the interception of PA and PB the p-T plane. Critical parameters are obtainable from slopes and intercepts of pressure-density supercritical isotherms within the mesophase. The supercritical mesophase is a fourth equilibrium state besides ice, water and steam. A thermodynamic state function rigidity (dp/dρ) T defines a distinction between liquid and gas, and shows a remarkable symmetry due to an equivalence in number density fluctuations, arising from available volume and molecular clusters, in liquid and gas respectively. Following an earlier debate in these pages [“ Fluid phases of argon: A debate on the absence of van der Waals’ critical point” Natural Science 5 (2) 194-206 (2013)], we here report further debate on a science of criticality applied to water and steam (APPENDIX 1).