High-Resolution ENDOR Studies on Vanadyl Porphyrins and Crude-Oil Petroporphyrins

Thesis (Ph.D.)--University of Washington, 2020An open area of inquiry in chemistry research is the chemical environment surrounding vanadyl ions and particularly vanadyl porphyrins in crude oil. This is of interest due to the deleterious effect vanadyl has upon the catalytic efficiency of the chemical processes used to “upgrade” oil through contemporary refining practices. This dissertation describes the first steps towards developing a new method of non-destructive separation-free speciation of vanadyl porphyrins in crude oil through high-resolution electron nuclear double resonance (ENDOR) spectroscopy. The first two chapters describe the physical parameters of interest that are measured with Electron Paramagnetic Resonance (EPR), and a review of the research into vanadyl in crude oil. The development of the new method begins in Chapter 3 with the introduction of chemically relevant vanadyl porphyrins, and the complete analysis of their experimentally determined magnetic parameters. Chapter 4 describes the effort of combining the high-resolution ENDOR spectra with a series of mathematical models that allow analysis of these complicated mixtures of vanadyl porphyrins in crude oil