Can the Boyle's and critical parameters be unambiguously correlated for polar and associating fluids, liquid metals, ionic liquids?

Rogankov, Oleg V.; Роганков, В. Б.

doi:10.1016/j.fluid.2016.11.034

Cited by 12 publications

(18 citation statements)

References 31 publications

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“…The aim is to emphasize their principle difference, since both FT-ones: FT1 and FT2 admit the existence of heterogeneous fluctuational NGF-phases at both sub-and supercritical states. Below c T , the presence of a such subcritical NGF-phase termed the interphase was confirmed for many substances by our previous investigations [8,9,17,18]. We have used for its presence the term of congruent vapor-liquid (CVL)-diagram to distinct it from the traditional VLE-diagram constructed, exclusively, for GPhs i.e.…”

Section: Global Congruent Fluctuation Diagram Of Vdw/lj-fluid аNd Locmentioning

confidence: 89%

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

Роганков¹,

Швець²,

Rogankov³

et al. 2019

ФАС

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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.

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Section: Global Congruent Fluctuation Diagram Of Vdw/lj-fluid аNd Locmentioning

confidence: 89%

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

Роганков¹,

Швець²,

Rogankov³

et al. 2019

ФАС

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“…The restrictions of the hardly available accurate knowledge of the third virial co- It was shown recently [15] that such model-dependent uncertainty including that arisen due to the fit of empirical data is inherent for the prescribed linearity of Zenoline. This feature makes the related Zeno-line with the other prescribed line of rectilinear diameter to be the rather ambiguous methodology.…”

Section: Lmentioning

confidence: 99%

“…One should know CP-parameters and two main PCS-factors ( c c Z ,A Ri ≡ ) of similarity to predict the standard pair ( , f f ε σ ) of molecular characteristics in any f-phase for any simple or complicated substance[11,12,14,15]:…”

mentioning

confidence: 99%

Classic origin of mesoscopic critical and boyle’s singularities simulated by fluctuational potential

Роганков¹,

Rogankov²,

Швець³

2020

ФАС

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Classic origin of mesoscopic critical and boyle's singularities simulated by fluctuational potential We have used the developed recently methodology of the congruent vapor-liquid (CVL) diagram for prediction, in particular, of the entire vapor-liquid equilibrium (VLE) diagram in the test-fluid argon. The former is based on the proposed earlier principle of the global fluid asymmetry (GFA) which rejects the conventional concept of a unified fluid equation of state (EOS) in both sub-and supercritical regions. In contrast to the traditional VLE-locus applicable in the restricted (subcritical) range between critical (c T) and triple (t T) temperatures, the CVL-locus spans the much more wide ranges of fluid states located between the generalized Boyle's (B) points (0, FT B T ρ → ], (0, FT B T → ρ ] predicted by FT-model of fluctuational thermodynamics. The new shape, location and the opposite sign of curvature for the boundary of metastable liquid which does not pass over CP (critical point) have been revealed in the global fluid (f) temperature range (0, FT B T) including its supercritical segment. The classical GFA-origin of the asymptotic criticality is unambiguously established without any appeals to the non-classical scaling phenomenology but in accordance with its main findings, at least, in the regions of stable and metastable liquid. Since the fundamental concept of a homogeneous equilibrium Gibbsian phase achieves the limit of its applicability in the simulated discrete N,V-systems of the Lennard-Jones' particles, their metastable, at best, states are highlyprobable in the conventional scales of VLE-simulation.

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“…This natural admission leads to the novel concept of a congruent zero-order (0) phase transition [17][18][19][20][21]   at the forcedly adopted Gibbsian equality for ij-pressures ij i j P P P . Vice versa, the same is true for the small disbalance:…”

Section: Second Law and Zero-order (0) Vle-transition In Non-gibbsian F-phasesmentioning

confidence: 99%

“…Its further investigation and application to the wide set of problems[5,6,[18][19][20][21] has corroborated its universality and high level of accuracy. The latter is achievable at the description of any i-phase and/or ij-phase states if the coexistence curve (CXC) data of I-phase transition are known from the reliable experiment More accurately, such information is necessary and enough to evaluate the T-,c of f-phase without any adjustable parameters.…”

mentioning

confidence: 99%

New Non-Stationary Gradient Model of Heat-Mass-Electric Charge Transfer in Thin Porous Media

Роганков

Швець

Rogankov³

2017

ХТТ

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The well-known complicated system of non-equilibrium balance equations for a continuous fluid (f) medium needs the new non-Gibbsian model of f-phase to be applicable for description of the heterogeneous porous media (PMs). It should be supplemented by the respective coupled thermal and caloric equations of state (EOS) developed specially for PMs to become adequate and solvable for the irreversible transport f-processes. The set of standard assumptions adopted by the linear (or quasi-linear) non-equilibrium thermodynamics are based on the empirical gradient-caused correlations between flows and forces. It leads, in particular, to the oversimplified stationary solutions for PMs. The most questionable but typical modeling suppositions of the stationary gradient (SG) theory are: 1) the assumption of incompressibility accepted, as a rule, for f-flows; 2) the ignorance of distinctions between the hydrophilic and hydrophobic influence of a porous matrix on the properties; 3) the omission of effects arising due to the concomitant phase intra-porous transitions between the neighboring f-fragments with the sharp differences in densities; 4) the use of exclusively Gibbsian (i.e. homogeneous and everywhere differentiable) description of any f-phase in PM; 5) the very restrictive reduction of the mechanical velocity field to its specific potential form in the balance equation of f-motion as well as of the heat velocity field in the balance equation of internal energy; 6) the neglect of the new specific peculiarities arising due to the study of any non-equilibrium PM in the meso- and nano-scales of a finite-size macroscopic (N,V)-system of discrete particles. This work is an attempt to develop the alternative non-stationary gradient (NSG) model of real irreversible processes in PM. Another aim is to apply it without the above restrictions 1)-6) to the description of f-flows through the obviously non-Gibbsian thin porous medium (TPM). We will suppose that it is composed by two inter-penetrable fractal sf-structures of f-phase (formed by the “mixture” of g- and l-phases termed, in total, interphase) and solid (s) porous matrix termed below s-phase. The permanent influence of humidity and the respective increase of the moisture content in TPM including the unavoidable phenomenon of capillary condensation are the main factors to occur the non-stationary transport f-flows through its texture.

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Can the Boyle's and critical parameters be unambiguously correlated for polar and associating fluids, liquid metals, ionic liquids?

Cited by 12 publications

References 31 publications

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

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

Classic origin of mesoscopic critical and boyle’s singularities simulated by fluctuational potential

New Non-Stationary Gradient Model of Heat-Mass-Electric Charge Transfer in Thin Porous Media

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