Supercritical Fluids: Kinetic Solvent Effect and the Correlation of Solid-Fluid Equilibria

Kinetic data for the dimerization of cyclopentadiene at 373, 378, 388, and 398 K in a supercritical propane solvent at pressures from 42 to 136 bar are presented. Data are presented for the cracking of dicyclopentadiene in supercritical butane at 433 K in the pressure range of 42-169 bar. Both reactions were studied in a supercritical chromatograph packed with Porasil A. The dimerization slows with increasing density whereas the cracking reaction is complicated by the dimerization of the product and appears to approach equilibrium. The dimerization results were analyzed in terms of transition state theory using the Peng-Robinson equation. The slowing of the dimerization and the implications of this result for the general case of a reactive system in a supercritical solvent are discussed in terms of the relative sizes and energies of the reactive solutes and the fluid solvent.

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

• Ellison, Timothy Kirk

• Chemistry, General
• Engineering, Chemical

Identifier

(UMI)AAI8610922

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/69766