Dissertation
Molecular properties and predictive NMR spectroscopy through ab-initio ensemble analysis and network theory
Doctor of Philosophy (PhD), Washington State University
01/2020
Handle:
https://hdl.handle.net/2376/111671
Abstract
Electrolyte solutions are of importance in a wide range of chemical, biological and industrial applications. A relevant example derives from the underlying chemistry of the bauxite ore processing (Bayer process), and the reprocessing activities of High Level Waste (HLW) at Hanford Site, mandated by complex dissolution/precipitation dynamics of highly alkaline sodium-aluminate electrolyte solutions. These aluminum-containing systems show a complex speciation picture and intricate behavior. As such, have attracted considerable theoretical and experimental efforts over the years. However, there is still no generally agreed on complete structural model of these electrolyte solutions.
This thesis focuses on the exploration of industrially relevant Al(III)-containing electrolyte solutions in alkaline media at the molecular level. We employ a computational approach that combines 1) ab-initio ensemble analysis, 2) network theory tools and 3) predictive NMR spectroscopy to gain new information from this system. Concurrently, new computational capacities, adapted from graph-theory concepts and sub-ensemble analysis, are developed and applied to the study of chemical solutions of interest.
The studies include 1) exploration of the hydration structure and dynamics of aluminate at the dilute limit and in the presence of alkali-metal cations in ion-pairing conditions which are of utmost importance in Hanford waste chemistry due to the presence of high quantities of Na+ coexisting with the Al(III) caustic phases, 2) investigation of capabilities of the network-based algorithm of PageRank to study chemical transformations with a focus on structural and association changes in solution, 3) analysis of Al3+ speciation through 27Al NMR shielding computations of plausible stable species in alkaline media, and lastly 4) the advancement of NMR methodological aspects of absolute shielding computations when error cancellations cannot be relied upon.
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Details
- Title
- Molecular properties and predictive NMR spectroscopy through ab-initio ensemble analysis and network theory
- Creators
- Ernesto Martinez Baez
- Contributors
- Aurora E Clark (Advisor)Kirk Peterson (Committee Member)Jean-Sabin McEwen (Committee Member)Gregory Schenter (Committee Member)Christopher Mundy (Committee Member)
- Awarding Institution
- Washington State University
- Academic Unit
- Chemistry, Department of
- Theses and Dissertations
- Doctor of Philosophy (PhD), Washington State University
- Number of pages
- 190
- Identifiers
- 99900581809401842
- Language
- English
- Resource Type
- Dissertation