Studies of the solvation thermodynamics of isomerization reactions: Experimental and theoretical approaches
Abstract
This thesis describes experimental and theoretical studies that use Raman spectroscopy to develop new chemical imaging technologies and to probe the fundamental effects of solvation on chemical reaction thermodynamics. Part One focuses on a new method for chemical imaging utilizing fiber-bundle image compression. Fluorescence and Raman imaging results obtained using this method are used to develop a Near-Infrared Raman Imaging Microscope (NIRIM). After describing the NIRIM instrument in detail, several applications are described, including fast image collection, chemical identification and separation based on vibrational contrast, and a survey-and-zoom method for rapid defect detection. Part Two begins with the description of an undergraduate laboratory experiment demonstrating the complimentary nature of vibrational spectroscopies, including a discussion of symmetry selection rules and a comparison with semi-empirical and ab initio quantum predictions. Finally, Raman spectroscopy is used to study quantitatively the effects of pressure, temperature, and solvation on the thermodynamics of two isomerization reactions. These reactions illustrate the subtle influence of molecular size, shape, and cohesive interactions on solvation thermodynamics. The results are used to test a molecular model based on the separation of solvation free energy into repulsive (cavity formation) and cohesive (van der Waals mean field) contributions.
Degree
Ph.D.
Advisors
Ben-Amotz, Purdue University.
Subject Area
Chemistry|Analytical chemistry
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