Analytical Perturbed Hard Sphere Models Based on Solubility and Volumetric Studies of Organic Solids Interacting With Supercritical Fluids
Johnston, Keith Paul
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Permalink
https://hdl.handle.net/2142/66649
Description
Title
Analytical Perturbed Hard Sphere Models Based on Solubility and Volumetric Studies of Organic Solids Interacting With Supercritical Fluids
Author(s)
Johnston, Keith Paul
Issue Date
1981
Department of Study
Chemical Engineering
Discipline
Chemical Engineering
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Engineering, Chemical
Language
eng
Abstract
Solubility data were measured by a new flow technique for naphthalene, phenanthrene, anthracene, triphenylmethane, hexamethylbenzene, fluorene, and pyrene in ethylene, and the latter three in carbon dioxide at temperatures from 298 to 358 K and pressures up to 50 MPa. These data suggested that partial molar volume data of the solute v(,2) would benefit enormously the modelling of the supercritical phase. An expression was derived that indicates the solubility data or gas chromatography data are not well suited for obtaining v(,2); therefore, a new experimental technique was designed. The solubility data were well correlated by perturbed hard sphere equations of state in a new way that does not require the use of critical properties, which are often unavailable, and if available, difficult to apply to these highly asymmetric systems. The crucial unlike pair energy parameter cross-correlated well with the heat of vaporization of the solid. The addition of a second order term, based on square well molecular dynamics results, increased the range of applicability of the model significantly.
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