Experimental and Theoretical Studies of Supercritical Fluid Behavior
Gilbert, Samuel Wade
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https://hdl.handle.net/2142/69775
Description
Title
Experimental and Theoretical Studies of Supercritical Fluid Behavior
Author(s)
Gilbert, Samuel Wade
Issue Date
1987
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
Abstract
A dynamic flow column apparatus is built and used to measure the solubilities of two decarboxylated amino acids, tryptamine and histamine, in supercritical ammonia (supercritical in pressure only) at 50(DEGREES)C. Solubilities are obtained for the pure solids and mixtures of the solids in 1:1 mole ratio. The solubilities of the mixed solids are determined using thin-layer chromatography. The feasibility of a partial isothermal separation of the two solids is investigated. The solubilities of the pure solids at three pressures, 1000, 2000 and 5000 psig and ideal solution theory as applied to mixtures of solids in a fluid suggest that a separation could be affected. However, the mixed solid solubility data indicate that no separation at 50(DEGREES)C is possible.
The Mermin decorated lattice-gas is used to describe supercritical solution solubilities and infinite dilution partial molar volumes. To date, no model has been shown to predict both solubilities and partial molar volumes in the critical region using the same model parameters for both sets of data. Lattice-gas models are superior to classical equations-of-state and hard-sphere perturbation systems because they can be used to characterize the non-analyticities of the critical point. The Mermin lattice is especially suited for modeling mixtures of different sized molecules since the cell volumes can be adjusted independently. Binary mixtures in which one component is slightly supercritical and the other component is subcritical are modeled with a solvent-analog parametric equation-of-state and the intermolecular potentials. The model is solved for dilute systems so that the crucial unlike potential is isolated. Results for several systems are compared to experimental data taken in our labs and from the literature. Relationships between lattice configurations and fluid structure are presented.
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