Thermochemical properties of fluorinated alanes and boranes
Abstract
The discovery of LiAlH4 and NaBH4 as hydride reducing agents has opened many doors the exploration of research in this area. Initially, the hydrides were used as reducing agents for various functional groups. The discovery of those two compounds has led to research in hydrogen storage and fuel cell energy. Recent studies in the gas phase have led to the determination of the hydride affinities of AlH3 or BH3. Those studies above were the foundational building blocks for the work presented in this thesis. Gas phase studies provide a fundamental understanding into the behavior of Lewis acids and how they can modify the reactivity and its properties. For example, it has been proven that the binding affinity for fluoride (strong Lewis base) interaction with a Lewis acid is much stronger than any other halide revealing covalent character. In this research, we were able to build from the foundation set before by fluorinating the alanes and boranes. The fluoride affinity of XHm F4-m−, where X is equal to Al or B and m is equal to 0, 1, 2, and 3, were determined using energy-resolved collision induced dissociation. Hydride affinities were attempted but unsuccessful. Experimental fluoride affinities were combined with theoretical hydride affinities in a thermochemical cycle to determine the enthalpies of formation.
Degree
Ph.D.
Advisors
Wenthold, Purdue University.
Subject Area
Chemistry|Analytical chemistry|Physical chemistry
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