Ideality contours and thermodynamic regularities in supercritical molecular fluids

Desgranges, Caroline; Margo, Abigail; Delhommelle, Jérôme

doi:10.1016/j.cplett.2016.06.021

Cited by 26 publications

(41 citation statements)

References 50 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The value taken by the ratio T c :T B is characteristic of the asymmetry of the binodal [17], and, like the similarity parameter S, is closely connected to the type of intermolecular interactions. We therefore assume that this ratio remains the same for all alkali halides.…”

Section: Resultsmentioning

confidence: 99%

Similarity law and critical properties in ionic systems.

Desgranges

Delhommelle

2017

Chemical Physics Letters

Self Cite

View full text Add to dashboard Cite

Using molecular simulations, we determine the locus of ideal compressibility, or Zeno line, for a series of ionic compounds. We find that the shape of this thermodynamic contour follows a linear law, leading to the determination of the Boyle parameters. We also show that a similarity law, based on the Boyle parameters, yields accurate critical data when compared to the experiment. Furthermore, we show that the Boyle density scales linearly with the sizeasymmetry, providing a direct route to establish a correspondence between the thermodynamic properties of different ionic compounds.

show abstract

Section: Resultsmentioning

confidence: 99%

Similarity law and critical properties in ionic systems.

Desgranges

Delhommelle

2017

Chemical Physics Letters

Self Cite

View full text Add to dashboard Cite

show abstract

“…To determine the conditions for coexistence, we first vary the molar Gibbs free energy (or chemical potential µ) to obtain equal probabilities for the two coexisting phases Π v = Π l with the probability for the vapor being defined as EWL simulations are run using the same parameters as discussed in previous work. 19,26 Specifically, the number of stages is set to 100 for the expanded ensemble approach, the starting value of the convergence factor f is set to e and the final value of f is fixed to 10 −8 , with a minimum number of visits of 1000 per interval for the number of molecules. EWL simulations are carried out within a Monte Carlo framework.…”

Section: Simulation Methodsmentioning

confidence: 99%

Benchmark Free Energies and Entropies for Saturated and Compressed Water

Desgranges

Delhommelle

2017

J. Chem. Eng. Data

Self Cite

View full text Add to dashboard Cite

We use molecular simulation to compute the thermodynamic properties of 7 rigid models for water (SPC/E, TIP3P, TIP4P, TIP4P/2005, TIP4P/Ew, TIP5P, OPC) over a wide range of temperature and pressure. Carrying out Expanded Wang-Landau simulations, we obtain a high accuracy estimate for the grand-canonical partition function which, in turn, provides access to all properties, including the free energy and entropy, both at the vapor-liquid coexistence and for compressed water. The results at coexistence highlight the close connection between the behavior of the statistical functions and the thermodynamic properties. They show that the subgroup {SPC/E,TIP4P/2005,TIP4P/Ew} provides the most accurate account of the vaporliquid equilibrium properties. For compressed water, the comparison of the simulation results to the experimental data establishes that the TIP4P/Ew model performs best among the 7 models considered here, and captures the experimental trends for the dependence of entropy and molar Gibbs free energy on pressure.

show abstract

“…The latter is the widely discussable in the context of ZL-contour [13][14][15][16]. The used long ago by Nedostup [15] concept of the so-called ideal curves was extended, then, by Ben-Amotz and Hershbach [13] as well as by other authors, in particular [14,16], for the CP-predictive aims. We represented ZL-contour of the pseudo-ideal-gas behavior ( ) 23] and many others) in any detail within this brief Section.…”

Section: Contours For Definition Of Ft2-region In Scf-areamentioning

confidence: 99%

“…∆ -contours following from Eqs. (12)(13)(14) and represented in (Table 1). Namely, these curves segregate the wide segment of SCF-plane identified by FT-diagram as the NGF-phase and FT-2 region, respectively.…”

Section: The Comparison Of Ftmentioning

confidence: 99%

“…. These results are written for the simple approximate caloric EOSs based on the knowledge of ( ) h T P e T P ≈ + ρ with that predicted by Nedostup [15] and simulated by Desgranges and co-authors [14] for the LJ-fluid (including the additional electrostatic interactions adopted between the point-atom charges). While such comparison (it is not shown in Fig.…”

Section: Can Ngf-concept Be Trusted For Real Scfs -? Ft-eos Introducementioning

confidence: 99%

See 1 more Smart Citation

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

Роганков¹,

Швець²,

Rogankov³

et al. 2019

ФАС

View full text Add to dashboard Cite

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.

show abstract

Ideality contours and thermodynamic regularities in supercritical molecular fluids

Cited by 26 publications

References 50 publications

Similarity law and critical properties in ionic systems.

Similarity law and critical properties in ionic systems.

Benchmark Free Energies and Entropies for Saturated and Compressed Water

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

Contact Info

Product

Resources

About