In the 2018 Nuclear Posture Review, it has been emphasized that the continued production of nuclear materials is and will continue to be
an essential part of American interest and policy. Necessarily, the cleanup and environmental management of excess nuclear waste, especially
from the Cold War era, also continues to be an ongoing effort. For example, just the disposition of legacy plutonium, amounting to 34 MT, is not
scheduled to be complete for several decades. The electrochemistry of lanthanide and actinide ligand complexes has been studied to various
degrees. In some cases, this area has been very understudied. Most of the known coordination complexes are unstudied. Plutonium as an element
perhaps presents some of the most interesting redox phenomena, exhibiting up to four oxidation states simultaneously in solution. Later
actinides berkelium and californium have very scarce published literature, especially non-aqueous based electrochemistry. Other physical data
such as log β and diffusion coefficients are also hard to find for many actinides. The beginning chapters focus on a well-studied ligand,
2,6-pyridinedicarboxylic acid (H2DPA) that has been well-characterized in solid-state methods for the lanthanides and actinides. This ligand has
almost exclusively been studied under aqueous conditions, yet for reductive efforts with elements such as Sm, developing a non-aqueous approach
was preferred. Detailed solubility investigations are provided, as well as detailed studies with cerium and plutonium, and finally studies with
europium and samarium. The next set of chapters deals with later actinide investigations. For reductive electrochemistry with californium,
detailed studies with cryptand were developed with the lanthanides. A preferred method was developed that was ultimately used to obtain novel
data for californium. In the case of Bk, a pyridyl nitroxide ligand (pyNO) was used to collect the first non-aqueous cyclic voltammogram for
this element. Lastly, the final chapter covers a few others systems that were given some efforts. Many of these systems have very interesting
electrochemistry, but they were beyond the scope of just one dissertation to complete. These include Schiff bases and DOPO chemistry. The Schiff
base data adds insightful data along with the tetravalent chemistry studied in earlier chapters, while the DOPO chemistry covers non-innocent
redox phenomena affected by Pu. / A Dissertation submitted to the Department of Chemistry and Biochemistry in partial fulfillment of the
requirements for the degree of Doctor of Philosophy. / Fall Semester 2018. / September 27, 2018. / Actinides, Berkelium, Californium, Cyclic Voltammetry, Electrochemistry, Lanthanides / Includes bibliographical references. / Thomas E. Albrecht-Schmitt, Professor Directing Dissertation; Todd Adams, University Representative;
Yan-Yan Hu, Committee Member; Michael Shatruk, Committee Member.
| Identifer | oai:union.ndltd.org:fsu.edu/oai:fsu.digital.flvc.org:fsu_661162 |
| Contributors | Marsh, Matthew L. (author), Albrecht-Schmitt, Thomas E. (professor directing dissertation), Adams, Todd (university representative), Hu, Yan-yan (committee member), Shatruk, Mykhailo (committee member), Florida State University (degree granting institution), College of Arts and Sciences (degree granting college), Department of Chemistry and Biochemistry (degree granting departmentdgg) |
| Publisher | Florida State University |
| Source Sets | Florida State University |
| Language | English, English |
| Detected Language | English |
| Type | Text, text, doctoral thesis |
| Format | 1 online resource (175 pages), computer, application/pdf |
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