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The critical-point conditions for classical polydisperse fluids (1985)

Johnson, K. A. ; Jonah, D. A. ; Kincaid, J. M. ; [weitere]

College Park, Md. : American Institute of Physics (AIP)

The Journal of Chemical Physics 82 (1985), S. 5178-5183

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Details

ISSN: 1089-7690

Quelle: AIP Digital Archive

Thema: Physik , Chemie und Pharmazie

Notizen: The critical-point conditions for a polydisperse mixture are shown to be equivalent to those for the existence of nontrivial solutions to two homogeneous integral equations of the Fredholm type. This mathematically rigorous treatment is not dependent on the form of any particular model free energy and hence shows that there is no formal distinction between the critical-point conditions of a polydisperse fluid and those conditions derived by Gibbs for the critical point of a mixture with a finite number of components. Using the method of Fredholm, we express the critical-point conditions in terms of the zeros of two absolutely convergent expansions, and demonstrate how the expansions may be used to determine the shifts in critical density and temperature caused by changes in the composition of the fluid.

Materialart: Digitale Medien

URL: http://dx.doi.org/10.1063/1.448642

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Digitale Medien

Consideration of some dilute-solution phenomena based on an expression for the Gibbs free energy (1986)

Jonah, D. A.

Springer

International journal of thermophysics 7 (1986), S. 935-948

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ISSN: 1572-9567

Schlagwort(e): activity coefficient ; dilute solution ; Henry's constant ; LennardJones potential ; mixture ; solubilities ; supercritical extraction ; virial coefficients

Quelle: Springer Online Journal Archives 1860-2000

Thema: Physik

Notizen: Abstract Rigorous expressions based on the Lennard-Jones (6–12) potential, are presented for the Gibbs and Helmholtz free energy of a dilute mixture. These expressions give the free energy of the mixture in terms of the thermodynamic properties of the pure solvent, thereby providing a convenient means of correlating dilute mixture behavior with that of the pure solvent. Expressions for the following dilute binary solution properties are derived: Henry's constant, limiting activity coefficients with their derivatives, solid solubilities in supercritical gases, and mixed second virial coefficients. The Henry's constant expression suggests a linear temperature dependence; application to solubility data for various gases in methane and water shows a good agreement between theory and experiment. In the thermodynamic modeling of supercritical fluid extraction, we have demonstrated how to predict new solubility-pressure isotherms from a given isotherm, with encouraging results. The mixed second virial coefficient expression has also been applied to experimental data; the agreement with theory is good.