Supercritical heterogeneous nanostructure of fluids. Part 1. Diagram of fluctuation transitions in non-gibbsian phases

Abstract

New concept of a supercritical fluid (SCF) region is proposed to recognize the set of the recent experimental observations and the numerical model results, in which the conventional asymptotic scaling theory and its crossover extension achieve the limit of applicability. An existence of the heterogeneous steady lattice-type nanostructure in the wide ranges of supercritical parameters termed the non-gibbsian fluid (NGF)-phase was hypothesized by one of authors (V.B.R.) in the framework of FT (fluctuational thermodynamics)-model. It was argued by FT-model that the similar NGF-phase exists also below the critical temperature in any real finite-volume VLE-transition. The present work establishes the location of exact boundaries for the supercritical lattice-type NGF-phase confirmed by the set of recently published experimental results and simulations. In brief, the total supercritical region consists of the dilute gas-like (gl) gibbsian (homogeneous) phase (GPh) and the dense liquid-like (ll) gibbsian (homogeneous) phase (GPh) separated one from another by the heterogeneous (at least, in nanoscales of a finite volume) vapor-like (vl) NGF-phase. The practical usage of a such structure may be quite promising in many areas of applications. It is certainly non-restricted by only the known advances of a supercritical extraction processing.