On the Empirical Determination of a Gas–Liquid Supercritical Mesophase and its Phenomenological Definition

Abstract

We respond to recent articles (Int. J. Thermophysics 39 139 2018, ibid.40 21 2019) that seek to deny the veracity of the empirical discovery and thermodynamic description of a gas–liquid supercritical mesophase. These IJT articles are misleading because they are based upon a false premise that the mesophase is a hypothetical concept. There is no “mesophase hypothesis” as wrongly stated in the title of article IJT, 40 21, 2019. Unlike the critical point continuity hypothesis of van der Waals (1873), or the universal critical point scaling hypothesis advocated by Anisimov and Sengers, and others since 1965, the supercritical mesophase is an empirical entity. If a hypothetical van der Waals fluid with the properties of a critical-state point with divergent isochoric heat capacity, and with the scaling properties of “universality” theory, were to exist, it could be used to vitiate the second law of thermodynamics. By contrast, the supercritical mesophase, discovered originally from computer experiments, is an empirically established equilibrium fluid region, of two-state systems of gas plus liquid, within a single Gibbs phase; the properties of which are determined by the laws of thermodynamics. Here, we provide a phenomenological definition of the gas–liquid supercritical mesophase that accords with the body of compelling experimental results over a 150-year period since van der Waals including modern computer experiments.