Fluctuational parameters based on the Bhatia–Thornton theory for supercritical solutions: Application to a supercritical aqueous solution of  n -pentane

Shibuta, Satoshi; Imamura, Hiroshi; Nishikawa, Keiko; Morita, Takeshi

doi:10.1016/j.chemphys.2017.02.003

Cited by 10 publications

(7 citation statements)

References 67 publications

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“…This can be attributed to the larger density difference between shorter alkane diluents and the extractant than for longer alkanes (DMDBPMA has a mass density of 0.935 g cm À3 compared to 0.750 g cm À3 for dodecane and 0.655 g cm À3 for hexane 93 ), which contributes to I Q=0 but not x. 94,95 Decreasing diluent chain length reduces the correlation length of fluctuations less and less at smaller chain lengths, but the decrease in diluent density remains roughly linear with chain length. Therefore, the contribution to I Q=0 from the increasing difference in density between the two components out-competes the decrease in concentration fluctuations at sufficiently low diluent chain length.…”

Section: Resultsmentioning

confidence: 99%

Critical fluctuations in liquid–liquid extraction organic phases controlled by extractant and diluent molecular structure

Bonnett

Sheyfer

Wimalasiri

et al. 2023

Phys. Chem. Chem. Phys.

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Section: Resultsmentioning

confidence: 99%

Critical fluctuations in liquid–liquid extraction organic phases controlled by extractant and diluent molecular structure

Bonnett

Sheyfer

Wimalasiri

et al. 2023

Phys. Chem. Chem. Phys.

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“…Maximum in ⟨(δN 1 ) 2 ⟩/⟨N 1 ⟩ = S(0) wrt p along an isotherm. 39 pseudocritical line Maximum in C p wrt T along an isobar. 13 Widom line Maximum in the correlation length.…”

Section: Nishikawa Linementioning

confidence: 99%

“…The first was the so-called “Widom line.” − Although the exact origin is somewhat obscure, it is now generally agreed to correspond to a maximum in the correlation length characterizing the range of the molecular interactions . An alternative is provided by Nishikawa and co-workers, who have studied the behavior of density fluctuations in fluids. ,− The “Nishikawa line” or “ridge” is associated with a maximum in the structure factor along an isotherm. − Unfortunately, an experimental determination of the correlation length and/or structure factor requires scattering studies, and, in particular, it is not provided by typical equations of state (EOS) used to correlate fluid properties. Consequently, many studies have used the response functions as a substitute.…”

Section: Introductionmentioning

confidence: 99%

Gas or Liquid? The Supercritical Behavior of Pure Fluids

Ploetz

Smith

2019

J. Phys. Chem. B

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By definition, the distinction between a gas and a liquid ceases to exist beyond the critical point for pure fluids. Nevertheless, there remains a strong desire to attribute gas-like or liquid-like behavior to fluids corresponding to different parts of the supercritical region, especially as this becomes important for understanding and designing the properties of supercritical fluids. Here, we use a combination of fluctuation solution theory and accurate equation of state data to elucidate an easily accessible dividing line and corresponding transition regime between liquid-like and gas-like behavior in the supercritical region of all pure fluids. Liquid-like behavior in the supercritical region is characterized by a negative skewness in the particle number distribution for an equivalent open system, indicating that particle deletion is favored for liquids, whereas gas-like behavior is characterized by a positive skewness, indicating that particle insertion is favored for gases. Identical behavior is observed either side of the liquid–vapor line. The possible consequences for the behavior of fluids at the critical point are also discussed.

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“…As density fluctuation forms a ridge in the 𝜌 − 𝑇 map. Later, the "Nishikawa line" or "Nishikawa-Widom line" [27][28][29]. This line co the rectilinear line in the 𝜌 − 𝑇 phase diagram and with the exten coexistence curve in the P-T phase diagram [20] in the same ma CO2 [17,18] and CF3H [19].…”

Section: Density Fluctuationsmentioning

confidence: 90%

Structure and Properties of Supercritical Water: Experimental and Theoretical Characterizations

Yoshida

Matsugami

Harano

et al. 2021

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Water in the supercritical region of the phase diagram exhibits a markedly different structure and properties from that at ambient conditions, which is useful in controlling chemical reactions. Nonetheless, the experimental, as well as theoretical, characterization of the substance is not easy because the region is next to the critical point. This article reviews the experimental as well as theoretical studies on water in the supercritical region and its properties as a solvent for chemical reactions, as carried out by the authors and based on small-angle X-ray scattering and the statistical mechanics theory of molecular liquids, also known as reference interaction-site model (RISM) theory.

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Fluctuational parameters based on the Bhatia–Thornton theory for supercritical solutions: Application to a supercritical aqueous solution of n -pentane

Cited by 10 publications

References 67 publications

Critical fluctuations in liquid–liquid extraction organic phases controlled by extractant and diluent molecular structure

Critical fluctuations in liquid–liquid extraction organic phases controlled by extractant and diluent molecular structure

Gas or Liquid? The Supercritical Behavior of Pure Fluids

Structure and Properties of Supercritical Water: Experimental and Theoretical Characterizations

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