Mixing Schemes in Aqueous Solutions of Nonelectrolytes

Koga, Yoshikata

doi:10.1016/b978-0-444-63629-4.00006-7

Cited by 2 publications

(3 citation statements)

References 90 publications

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“…Hence, it is possible to obtain new insights into fluid behavior not provided by the examination of the traditional thermodynamic derivatives themselves. Similar thermodynamic derivatives have been used by Koga and co-workers to study the properties of pure liquids and liquid mixtures. , However, these studies correspond to different derivatives than those considered here and have generally not involved the supercritical region.…”

Section: Theorymentioning

confidence: 99%

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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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Section: Theorymentioning

confidence: 99%

“…Similar thermodynamic derivatives have been used by Koga and co-workers to study the properties of pure liquids and liquid mixtures. 81,82 However, these studies correspond to different derivatives than those considered here and have generally not involved the supercritical region.…”

Section: Nishikawa Linementioning

confidence: 99%

Gas or Liquid? The Supercritical Behavior of Pure Fluids

Ploetz

Smith

2019

J. Phys. Chem. B

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“…The density fluctuations are thermodynamically related to the isothermal compressibility, which is the second derivative of the Gibbs free energy, G. Using the small-angle scattering method, this higher-order derivative can be obtained directly from the zero-angle scattering-intensity evaluated from the small-angle scattering signals. [16][17][18][19] Density fluctuations in supercritical states have been investigated for various substances. Nishikawa et al have investigated the density fluctuations for various types of molecular liquids.…”

Section: Introductionmentioning

confidence: 99%

A method for determining the density fluctuations of supercritical fluids absolutely based on small-angle scattering experiments and application to supercritical methanol

Morita

Kadota

Kusano

et al. 2023

Jpn. J. Appl. Phys.

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Density fluctuation is a vital concept for understanding disordered systems. A supercritical fluid is a typical disordered system having extremely large inhomogeneity. To determine the density fluctuations using a scattering method, the key physical quantities are the fluid density and the normalized scattering intensity, as well as the small-angle scattering signals. Here, we propose a methodology to obtain all of these quantities absolutely from a scattering experiment. Normalization of scattering intensity relating to the number of molecules per unit volume was performed using fluid density evaluated directly from in situ measurements of the X-ray absorption coefficients. Conversion of scattering intensity to absolute value concerning scattering volume was achieved utilizing the value of the density fluctuation in the ideal state. An analysis of supercritical carbon dioxide confirmed the validity of the present method. By applying this method, the density fluctuations of supercritical methanol were quantitatively determined for the first time.

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Mixing Schemes in Aqueous Solutions of Nonelectrolytes

Cited by 2 publications

References 90 publications

Gas or Liquid? The Supercritical Behavior of Pure Fluids

Gas or Liquid? The Supercritical Behavior of Pure Fluids

A method for determining the density fluctuations of supercritical fluids absolutely based on small-angle scattering experiments and application to supercritical methanol

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