Thermodynamics of Criticality: Percolation Loci, Mesophases and a Critical Dividing Line in Binary-Liquid and Liquid-Gas Equilibria

作     者：Leslie V. Woodcock Leslie V. Woodcock

作者机构：Department of Physics University of Algarve Faro Portugal 

出 版 物：《Journal of Modern Physics》 (现代物理（英文）)

年 卷 期：2016年第7卷第8期

页      面：760-773页

学科分类：080704[工学-流体机械及工程] 080103[工学-流体力学] 08[工学] 0807[工学-动力工程及工程热物理] 0801[工学-力学（可授工学、理学学位）] 

主　　题：Thermodynamics Criticality Percolation Transition Ideal Gas: Liquid State 

摘      要：High-temperature and pressure boundaries of the liquid and gas states have not been defined thermodynamically. Standard liquid-state physics texts use either critical isotherms or isobars as ad hoc boundaries in phase diagrams. Here we report that percolation transition loci can define liquid and gas states, extending from super-critical temperatures or pressures to “ideal gas states. Using computational methodology described previously we present results for the thermodynamic states at which clusters of excluded volume (VE) and pockets of available volume (VA), for a spherical molecule diameter σ, percolate the whole volume (V = VE + VA) of the ideal gas. The molecular-reduced temperature (T)/pressure(p) ratios ( ) for the percolation transitions are = 1.495 ± 0.015 and = 1.100 ± 0.015. Further MD computations of percolation loci, for the Widom-Rowlinson (W-R) model of a partially miscible binary liquid (A-B), show the connection between the ideal gas percolation transitions and the 1st-order phase-separation transition. A phase diagram for the penetrable cohesive sphere (PCS) model of a one-component liquid-gas is then obtained by analytic transcription of the W-R model thermodynamic properties. The PCS percolation loci extend from a critical coexistence of gas plus liquid to the low-density limit ideal gas. Extended percolation loci for argon, determined from literature equation-of-state measurements exhibit similar phenomena. When percolation loci define phase bounds, the liquid phase spans the whole density range, whereas the gas phase is confined by its percolation boundary within an area of low T and p on the density surface. This is contrary to a general perception and opens a debate on the definitions of gaseous and liquid states.