ASU Electronic Theses and Dissertations
This collection includes most of the ASU Theses and Dissertations from 2011 to present. ASU Theses and Dissertations are available in downloadable PDF format; however, a small percentage of items are under embargo. Information about the dissertations/theses includes degree information, committee members, an abstract, supporting data or media.
In addition to the electronic theses found in the ASU Digital Repository, ASU Theses and Dissertations can be found in the ASU Library Catalog.
Dissertations and Theses granted by Arizona State University are archived and made available through a joint effort of the ASU Graduate College and the ASU Libraries. For more information or questions about this collection contact or visit the Digital Repository ETD Library Guide or contact the ASU Graduate College at gradformat@asu.edu.
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- Creators: Shock, Everett
Hydrothermal reactions of organic compounds in the presence of minerals: a study of carboxylic acids
Description
Carboxylic acids are an abundant and reactive species present throughout our solar system. The reactions of carboxylic acids can shape the organic abundances within oil field brines, carbonaceous chondrites, and different ranks of coal.
I have performed hydrothermal experiments with model aromatic carboxylic acids in the presences of different oxide minerals to investigate the reactions available to carboxylic acids in the presence of mineral surfaces. By performing experiments containing one organic compound and one mineral surface, I can begin to unravel the different reactions that can occur in the presence of different minerals.
I performed experiments with phenylacetic acid (PAA), hydrocinnamic acid (HCA) and benzoic acid (BA) in the presence of spinel (MgAl2O4), magnetite (Fe3O4), hematite (Fe2O3), and corundum (Al2O3). The focus of this work was metal oxide minerals, with and without transition metal atoms, and with different crystal structures. I found that all four oxide minerals facilitated ketonic decarboxylation reactions of carboxylic acids to form ketone structures. The two minerals containing transition metals (magnetite and hematite) also opened a reaction path involving electrochemical oxidation of one carboxylic acid, PAA, to the shorter chain version of a second carboxylic acid, BA, in experiments starting with PAA. Fundamental studies like these can help to shape our knowledge of the breadth of organic reactions that are possible in geologic systems and the mechanisms of those reactions.
I have performed hydrothermal experiments with model aromatic carboxylic acids in the presences of different oxide minerals to investigate the reactions available to carboxylic acids in the presence of mineral surfaces. By performing experiments containing one organic compound and one mineral surface, I can begin to unravel the different reactions that can occur in the presence of different minerals.
I performed experiments with phenylacetic acid (PAA), hydrocinnamic acid (HCA) and benzoic acid (BA) in the presence of spinel (MgAl2O4), magnetite (Fe3O4), hematite (Fe2O3), and corundum (Al2O3). The focus of this work was metal oxide minerals, with and without transition metal atoms, and with different crystal structures. I found that all four oxide minerals facilitated ketonic decarboxylation reactions of carboxylic acids to form ketone structures. The two minerals containing transition metals (magnetite and hematite) also opened a reaction path involving electrochemical oxidation of one carboxylic acid, PAA, to the shorter chain version of a second carboxylic acid, BA, in experiments starting with PAA. Fundamental studies like these can help to shape our knowledge of the breadth of organic reactions that are possible in geologic systems and the mechanisms of those reactions.
ContributorsJohnson, Kristin Nicole (Author) / Shock, Everett (Thesis advisor) / Hartnett, Hilairy (Committee member) / Gould, Ian (Committee member) / Arizona State University (Publisher)
Created2017
Description
Organic compounds are influenced by hydrothermal conditions in both marine and terrestrial environments. Sedimentary organic reservoirs make up the largest share of organic carbon in the carbon cycle, leading to petroleum generation and to chemoautotrophic microbial communities. There have been numerous studies on the reactivity of organic compounds in water at elevated temperatures, but these studies rarely explore the consequences of inorganic solutes in hydrothermal fluids. The experiments in this thesis explore new reaction pathways of organic compounds mediated by aqueous and solid phase metals, mainly Earth-abundant copper. These experiments show that copper species have the potential to oxidize benzene and toluene, which are typically viewed as unreactive. These pathways add to the growing list of known organic transformations that are possible in natural hydrothermal systems. In addition to the characterization of reactions in natural systems, there has been recent interest in using hydrothermal conditions to facilitate organic transformations that would be useful in an applied, industrial or synthetic setting. This thesis identifies two sets of conditions that may serve as alternatives to commonplace industrial processes. The first process is the oxidation of benzene with copper to form phenol and chlorobenzene. The second is the copper mediated dehalogenation of aryl halides. Both of these processes apply the concepts of geomimicry by carrying out organic reactions under Earth-like conditions. Only water and copper are needed to implement these processes and there is no need for exotic catalysts or toxic reagents.
ContributorsLoescher, Grant (Author) / Shock, Everett (Thesis advisor) / Hartnett, Hilairy (Committee member) / Gould, Ian (Committee member) / Arizona State University (Publisher)
Created2020