Analytical Perturbed Hard Sphere Models Based on Solubility and Volumetric Studies of Organic Solids Interacting With Supercritical Fluids

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.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemical Engineering

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2014

Author dc:creator

• Johnston, Keith Paul

• Engineering, Chemical

Language dc:language

eng

Identifier

(UMI)AAI8203496

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/66649