Thesis (M.S. in Chemistry)--University of California, Berkeley, June 1960. / Includes bibliographical references (leaves 45-46).

This is a study involving some of the chemistry of osmium tetroxide in perchloric acid solution. The research was originally instigated from a seminar report on the ruthenium III thiocyanate complex ion which was studied in perchloric acid solution. The seminar report given by Craig Townsend discussed how a spectrophotometric study by Yaffe and Voight (1951) was made of the ruthenium III thiocyanate complex ion, Similar possibilities were recognized as being possible in attacking the problem of an osmium thiocyanate complex or complexed. Some of the chemistry involved in the study of the ruthenium III thiocyanate complex will be discussed later. It will now suffice to say that the complex was studied by reacting ruthenium IV perchlorate and sodium thiocyanate to produce the complex ion. Townsend (1953), following the general procedure of Yaffe and Voight, took osmium tetroxide and sodium thiocyanate in a perchloric acid solution and reacted them to produce a rose colored osmium thiocyanate complex ion. He then determined a general formula and a value for the dissociation constant for the complex. Many problems were encountered in the Townsend study; and, therefore, there was reason for further study along these same lines. Some of the general characteristics of osmium and its related elements will be noted first.

No description available.

M.S.

No description available.

Uranium-zirconium alloy nuclear fuels have many advantages as compared with ceramic fuels, especially for fast reactor systems. However, metallic fuels aren’t currently used in commercial power production due in part to issues with fuel swelling during irradiation. A major contributor to this expansion issue, the formation of fission gasses into bubbles, is examined here. Methods to evaluate evolution of fission gas bubbles within a U-Zr alloy are discussed and refined. Specifically, transmission electron microscopy (TEM) for viewing bubbles within the interior of the alloy is investigated. One constraint on the use of the TEM is the lack of literature pertaining to what thinning techniques are successful for U-10Zr alloy. Both initial and final thinning techniques were investigated. After thinning was complete, the specimens were viewed via TEM to determine their suitability. In addition, samples of U-Zr alloy were irradiated with gas atoms in an accelerator to simulate bubble initiation and formation and viewed via TEM. Only preliminary investigations were completed. Evaluated electrolyte solutions included one part phosphoric acid to two parts sulfuric acid and two parts water (A), one part phosphoric acid to one part ethanol and one part glycerol (B), one part hydrochloric acid to one part water (C), two parts methanol to 13 parts phosphoric acid (D), and one part perchloric acid to nine parts acetic acid (G). Positive responses were received from the solutions A, C, and G which generated electron transparent areas with few to no process induced artifacts. TEM trials with each electrolyte were performed on un-irradiated U-10Zr alloy. These trials indicated that the polishing methods would work but are not yet optimal. In addition, U-10Zr alloy was irradiated and viewed in the TEM where those polished with electrolyte A consistently included the presence of large circular features that could indicate bubbles or voids. The foundation was laid for further study to be done on this topic through the use of electropolishing solutions as final thinning techniques. Additional work that is recommended includes: electropolishing parameter refinement; implantation of heavier gas atoms or at elevated temperatures; annealing of the implanted alloy; and computer modeling of resulting first principles phenomena.

The CANDU Supercritical Water-Cooled Reactor’s extreme operating conditions and single-loop design have fuelled a need for better understanding of hydrothermal chemistry. This thesis reports the thermal stability and decomposition kinetics of perchloric acid in quartz and Pyrex® cells. HClO4 is an appropriate internal standard for Raman measurements of nickel(II) chloro complexes in quartz cells up to 200 ºC Raman spectroscopy. This thesis also reports the first Raman spectra for Ni2+, NiCl+ and NiCl2 from 8 to 120 ºC. Due to very weak bands and overlap of the contributing species, a thermodynamic speciation model, principle component analysis, and quantum mechanical predictions of the nickel(II) chloro Raman spectra were required to assign peaks. The assignment was confirmed by calculating temperature independent scattering coefficients from the spectra. This is the first study to obtain a spectrum for NiCl2 below 100 ºC. / University of Guelph, Atomic Energy of Canada Limited (AECL), Bruce Power, University Network of Excellence in Nuclear Engineering (UNENE), National Sciences and Engineering Research Council of Canada (NSERC), Natural Resources Canada, Ontario Power Generation (OPG), Canada Foundation for Innovation

Chronic, noncommunicable diseases such as chronic fatigue syndrome (also known as myalgic encephalomyelitis) are rapidly becoming a worldwide epidemic that profoundly affects public health and productivity. Chronic fatigue syndrome (CFS) is characterised by severe and debilitating fatigue and although its etiology is still unknown, recent studies have found considerable evidence that mitochondrial dysfunction and oxidative stress might be responsible for the underlying energy deficit in these patients. Adenine and pyridine nucleotides could be used as potential biomarkers for energy related disorders such as chronic fatigue syndrome because of their various functions in the energy and redox pathways. The first part of this study focussed on developing a liquid chromatography electrosprayionisation tandem mass spectrometry (LC-ESI-MS/MS) method for the quantification of these nucleotides in blood samples. Due to the instability of nucleotides in biological matrices it was also necessary to find a suitable extraction method that would be able to stop enzymatic activity via protein precipitation. Out of the four extraction methods investigated during this study, deproteinisation of whole blood samples with perchloric acid produced the highest nucleotide abundances. Although nucleotide standards were found to be stable in perchloric acid, nucleotide levels in blood samples were not stabilised by addition of perchloric acid. The second part of this study consisted of measuring the nucleotide levels in blood samples of controls and possible CFS patients in order to test the proof of concept of the new LCESI- MS/MS method. Despite changes in the nucleotide levels due to perchloric acid and problems with nucleotide instability, it was still possible to distinguish between the two groups based on the results obtained with the new LC-ESI-MS/MS method. The newly developed LC-ESI-MS/MS method proved to be reliable and adequate for nucleotide quantification in whole blood samples, thus the aim of this study was achieved. / MSc (Biochemistry), North-West University, Potchefstroom Campus, 2014

Chronic, noncommunicable diseases such as chronic fatigue syndrome (also known as myalgic encephalomyelitis) are rapidly becoming a worldwide epidemic that profoundly affects public health and productivity. Chronic fatigue syndrome (CFS) is characterised by severe and debilitating fatigue and although its etiology is still unknown, recent studies have found considerable evidence that mitochondrial dysfunction and oxidative stress might be responsible for the underlying energy deficit in these patients. Adenine and pyridine nucleotides could be used as potential biomarkers for energy related disorders such as chronic fatigue syndrome because of their various functions in the energy and redox pathways. The first part of this study focussed on developing a liquid chromatography electrosprayionisation tandem mass spectrometry (LC-ESI-MS/MS) method for the quantification of these nucleotides in blood samples. Due to the instability of nucleotides in biological matrices it was also necessary to find a suitable extraction method that would be able to stop enzymatic activity via protein precipitation. Out of the four extraction methods investigated during this study, deproteinisation of whole blood samples with perchloric acid produced the highest nucleotide abundances. Although nucleotide standards were found to be stable in perchloric acid, nucleotide levels in blood samples were not stabilised by addition of perchloric acid. The second part of this study consisted of measuring the nucleotide levels in blood samples of controls and possible CFS patients in order to test the proof of concept of the new LCESI- MS/MS method. Despite changes in the nucleotide levels due to perchloric acid and problems with nucleotide instability, it was still possible to distinguish between the two groups based on the results obtained with the new LC-ESI-MS/MS method. The newly developed LC-ESI-MS/MS method proved to be reliable and adequate for nucleotide quantification in whole blood samples, thus the aim of this study was achieved. / MSc (Biochemistry), North-West University, Potchefstroom Campus, 2014