AuthorHubler, David K.
Keywordsdensity functional theory
AdvisorBaygents, James C.
MetadataShow full item record
PublisherThe University of Arizona.
RightsCopyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.
AbstractSeveral electrochemical processes are modeled at process levels and atomic scales. Processes are presented for acid generation and ion exchange media regeneration, along with corresponding process models. Transport and reaction processes in individual ion exchange beads are also modeled. Acids of mild strength (pH = ~1-2) are generated from electrolyte solutions and their strength is effectively modeled as a function of time. The regeneration of ion exchange media is also modeled, to close agreement with measurements, and the process model is reconciled with a model for solute flux from an individual ion exchange bead. Together, the models show that the "gentle" regeneration process is controlled by the plating rate. Processes interior to the particle are controlled by diffusion, but all processes are faster than the characteristic time for plating. In a separate process, an electrochemical method is used to produce hypochlorite for disinfection. The process generates perchlorate as a toxic byproduct. Density function theory is used to construct an atomic-scale model of the mechanism for producing perchlorate, as well as the aging of the boron-doped diamond anode used in the process. The mechanism shows that the boron-doped diamond surface plays an important role in chemisorbing and stabilizing radicals of oxychlorine anions, allowing the radicals to live long enough to react and form higher ions like perchlorate. Wear mechanisms that occur on the anode are shown to oxidize and etch the surface, changing its chemical functionality over time. As the surface ages, the overpotential for water oxidation is decreased, decreasing the efficiency of the electrode.
Degree ProgramGraduate College