Applications of Raman spectroscopy in the area of instrument development and solvent effects on chemical reactions
Abstract
This thesis is a compilation of work in the areas of experimental Raman spectroscopy and the theoretical analysis of fluids. The first two chapters describe the design, performance and applications of a near-infrared Raman imaging microscope (NIRIM), the first Raman instrument of its type. The heart of the NIRIM is a fiber bundle, which allows for the simultaneous collection of spectral and spatial information in one scan of the charge coupled device. The key design features are discussed in detail, including the fiber bundle and the optical coupling required between the microscope and the fiber bundle. Also, the chemical imaging performance is demonstrated with regard to the speed and the ability to classify different chemical components in a sample. The third chapter is a reinvestigation of the principle of corresponding states for simple fluids. Classical corresponding states scaling, based on critical point constants, is found to produce weaker universal behavior than a new scaling procedure linked to the two intermolecular interaction potential parameters of a Lennard-Jones fluid. The last two chapters describe solvent effects on chemical reactions. The complete set of reaction thermodynamic functions (ΔG, ΔH, ΔS, ΔV, ΔU, ΔA) obtained for the reaction of acetone and methanol to form a hemiketal (2-methoxy-2-propanol) in two different solvents, diethyl ether and tetrahydrofuran. The results are used to test predictions of the perturbed hard fluid model and extract attractive (cohesive) and repulsive (cavity formation) interactions from the solvation thermodynamic functions.
Degree
Ph.D.
Advisors
Ben-Amotz, Purdue University.
Subject Area
Chemistry|Analytical chemistry
Off-Campus Purdue Users:
To access this dissertation, please log in to our
proxy server.