Master of Science / Department of Animal Sciences and Industry / Teresa L. Douthit / Supplementation of lipids in the form of triglycerides is a safe method for increasing energy density in equine diets; however the effects of calcium salts of fatty acids (CSFA) on nutrient digestibilities in the horse are unknown. Eight cecally cannulated Quarter Horses were utilized in a crossover design in which horses consumed 1.5% BW smooth bromegrass hay and 0.5% BW concentrate supplemented with 4.1% soybean oil (SB) or 4.9% Enertia s/f® (E), a proprietary CSFA, for 28 d. Feces were collected for determination of apparent total tract digestibility of nutrients, and cecal digesta was evaluated for pH and concentrations of VFA and LCFA. Serum was collected following a 16-h fast and analyzed for triglycerides and cholesterol. Apparent total tract digestibilities of DM, NDF, ADF, CP, ether extract, and GE were unaffected by lipid source (P > 0.10). Serum triglycerides tended to be greater in horses consuming E compared to SB (P = 0.10); but, serum cholesterol concentrations were not different (P = 0.45). Cecal pH was unaffected by lipid source. Cecal concentration of total VFA tended to be greater in horses consuming SB compared to E at 2-h post feeding (P = 0.07). Cecal propionate concentrations were greater at 2-h post feeding for horses fed SB compared to horses fed E (P = 0.03). A treatment × time interaction was detected for total cecal LCFA concentration in which total cecal LCFA were greater in horses consuming E compared to SB at 2-h following consumption of a meal but became more similar as time progressed (P < 0.01). Secondly, an in vitro study was conducted to determine the effect of Co chloride on fermentation parameters using an equine cecal fluid inoculum in a 2 × 5 factorial arrangement of treatments. Alfalfa or smooth bromegrass hay (5 g DM) were utilized as substrates and were supplemented with 0.0, 0.5, 5.0, 25.0, or 50.0 mg Co/kg substrate DM. Cultures containing alfalfa had greater IVDMD compared to those with smooth bromegrass hay (P < 0.01). There was a forage × Co interaction in which gas production increased with time and was greater in cultures containing alfalfa (P < 0.01). Production of acetate, propionate, butyrate, isobutyrate, isovalerate, and total VFA, as well as acetate:propionate, were increased in cultures containing alfalfa compared to those containing brome hay (P < 0.05).

M.Sc. / The metallurgical industrial losses of base metals with waste solutions are an environmental threat to water sources, hence these metal ions must be removed prior to discharge into receiving bodies. In this study, Southern African clinoptilolite’s capability as an ion-exchanger with respect to Cu2+ and Co2+ was investigated in order to consider its application in metal cation removal from aqueous solutions. The clinoptilolite was characterised with X-ray powder diffraction (XRD), X-ray fluorescence (XRF), FTIR, thermogravimetric analyser (TGA) and SEM-EDS. The clinoptilolite was found to be a thermally stable alumino-silicate with calcite, dolomite and quartz as the main minerals. Investigations of Co2+ and Cu2+ uptake were first performed on non-mixed solutions of these cations. It was found that Cu2+ was removed faster than Co2+ with removal efficiencies of 79% and 63% respectively. The column method was used in the cation-exchange processes with synthetic solutions of 0.0020 M, 0.0698 M and 0.2000 M of Co2+ and Cu2+ concentrations which were measured using atomic absorption spectroscopy (AAS). The effects of Co2+ and Cu2+ ions on one another’s removal efficiency were investigated on Co/Cu mixed synthetic solutions by varying their concentration ratios in solution. The Cu2+ was generally found to be removed at lower rates than the Co2+. Investigations on added impurities in the form of Si4+ and Fe2+ in the mixed Co/Cu synthetic solutions were carried out to determine their effect on the removal efficiencies of the targeted metals. It was found that both Si4+ and Fe2+ greatly reduced the removal efficiency of Cu2+, especially with increased amounts of Si4+ in the Co/Cu solution.

M.Sc. (Chemistry) / Cobalt is mainly associated with copper, both in the primary ores and in the oxidation zone. In Southern Africa cobalt metal is produced as a by-product of the extraction of copper, nickel and platinum group metals. The hydrometallurgical route is commonly used, since cobalt bearing materials are acid leached prior to the clarification and impurity removal process preceding the electrowinning of the value. In order to understand the dissolution behaviour of cobalt and copper bearing minerals from Co-Cu oxide ores, the relationship between and the impact of physical, chemical and mineralogical properties of the materials and the dissolution behaviour of cobalt and copper bearing minerals contained in the feed materials was studied. Four Co-Cu oxide ore samples namely; high cobalt ore (HCo), high copper ore (HCu), low cobalt ore 1 (LCo1) and low cobalt ore 2 (LCo2) were characterised in terms of elemental composition, cobalt and copper species, functional groups, mineral phases, mineral abundances, mineral/ore grains size distribution, particle specific surface area, particle ore density and porosity, in order to elucidate the impact of these properties on the dissolution rate and percentage recovery of cobalt and copper in the acid generated leachate...

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The decomposition of formic acid proceeds via two principal reaction pathways: dehydration and dehydrogenation. Mechanisms and reaction ratios depend on the nature of the catalysts used. This work provides mechanistic insight into the decomposition of formic acid on Co(0001) and a highly stepped cobalt surface. The catalytic systems were studied in ultra-high vacuum by XPS and temperature programmed desorption. On both surfaces, an overall reaction (1) was observed: 2 HCOOH→H_2 O+CO+H_2+CO_2 (1) The surfaces had differing reaction intermediates, reaction temperatures, and activation energies. On Co(0001), formate, carbon, and hydroxyl are intermediates and the reaction has an activation energy of 44.3 ± 0.6 kJ/mol, pre-exponential factor of 0.7 ± 0.05 mbar/s. On highly stepped cobalt, formate and formyl are intermediates and the reaction has an activation energy of 147.2 ± 2.0 kJ/mol and pre-exponential factor of 1011.3 ± 0.2 mbar/s. Desorption energies of observed species and mechanisms of observed reactions are reported. A detailed description and proof of concept of a PM-IRRAS reactor designed for this thesis is also presented.

Fluorinated organic compounds play important roles in our society, as these products range from life-saving pharmaceuticals and agrochemicals, to fluoropolymers with extremely high thermal and chemical stability. Although elemental fluorine (F2) is the most reactive element, some fluoro-organic compounds are chemically inert. As such, controlled reactivity of fluorine or highly-fluorinated organic fragments is a considerable, yet important challenge for synthetic chemists. Fluoro-organometallic chemistry has been studied for decades, as researchers attempt to maximize the potential of metal mediated/catalyzed processes for the synthesis of fluorinated organic molecules. Within this framework, metal fluorocarbene complexes are particularly interesting because of their highly tunable reactivity, and are proposed for use in important metathesis/polymerization reactions of perfluorinated alkenes. While considerable work is still needed to make these proposed reactions a reality, this thesis outlines contributions from our research group. We showed that cobalt fluorocarbene complexes CpCo(=CFRF)(PPh2Me) (RF = F, CF3) undergo [2+2] cycloaddition reactions with tetrafluoroethylene (TFE) and phenylacetylene to form perfluorometallacyclobutane and partially fluorinated metallacyclobutene products, respectively. For both reactions, computational studies reveal a stepwise ring-closing mechanism, which proceeds through a singlet 1,4-diradical intermediate. Next, the formation of CpCo(=CF2)(L) complexes is achieved via the direct addition of difluorocarbene, generated in situ, to a cobalt(I) precursor. Subsequent addition of CF2 to cobalt fluorocarbene complexes results in [2+1] cycloaddition and formation of perfluorinated alkene complexes. The [2+1] addition is highly favored as the cobalt fluorocarbenes readily react with electrophilic CF2. A series of experiments provide evidence for the stepwise nature of fluoroalkene complex formation. From Co(I) fluorocarbene complexes, the focus shifts to preparing metal fluorocarbenes with electrophilic-type reactivity. The synthesis of bis(perfluoroalkyl) complexes serve as precursors for preparation of perfluoroalkyl cobalt(III) fluorocarbenes, which undergo migratory insertion reactions of the fluorocarbene into the perfluoroalkyl ligand. Using a similar synthetic approach, nickel(II) and palladium(II) difluorocarbene complexes are prepared from their corresponding trifluoromethyl precursors. The synthesis, characterization and reactivity of cobalt(III) fluoride complexes is also described, including the catalytic fluorination of acyl chlorides, demonstrating the first example of a cobalt(III) catalyzed fluorination reaction. The effects of the various ancillary ligands on these cobalt catalysts are investigated using high-throughput experimentation technology, and the scope of the reaction is expanded to include the synthesis of a variety of acyl fluoride compounds. Finally, the results and learnings from this work will be summarized and highlighted. The future directions and novel research which could result from the continuation of these projects is discussed, with an emphasis placed on the areas believed to have the highest potential impact.

Bibliography: pages 68-70. / An investigation involving the vibratory cavitation erosion of WC-Co alloys was undertaken in order to determine the mechanisms of material removal. Nineteen grades of WC-Co alloys were studied. These alloys had been previously characterised according to microstructural and mechanical properties. Further characterisation by way of Young's modulus and density of the materials was undertaken. An investigation of the i nfluence of various parameters on cavitation erosion established a binder content dependence on erosion. For two grain sizes, erosion was found to increase to a maximum at 12 vo1-% binder content (1.8 μm grain size) and 23 vol-% binder (2.8 μm grain size). The main mode of material removal was found to be cobalt removal followed by WC grain pull-out. In high binder content alloys, cobalt removal was predominant with little loss of WC grains. X-ray diffraction showed that the allotropic phase transformation of the binder under cavitational attack was beneficial to the erosion resistance of these alloys. The erosion of low binder content alloys was controlled by the contiguity of the WC skeleton. Maximum erosion occurred at binder contents which corresponded to the combination of a fragile WC skeleton and a small volume of available cobalt for strain induced transformation.

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Soybean (Glycine max L. Merrill) is a new cash crop for north central and northwestern North Dakota producers. Soils and climate in these new soybean areas differ from those regions where the current fertilizer recommendations were based. Northcentral and northwestern North Dakota is more undulating, drier, cooler, and has differencing soils than eastern North Dakota and Minnesota. A three-year study to evaluate soybean best management practices was conducted during the 2016 to 2018 growing seasons. Each year, the study consisted of two sites and 12 treatments. By design, one site was on acidic (pH < 6) soil while the other was on alkaline (pH > 7.3) soil. Both site treatments were: untreated check, inoculated with rhizobia (B. japonicum L.), broadcast urea (55 kg ha-1), broadcast MAP (monoammonium phosphate, 11-52-0) (110 kg ha-1), in-furrow 10-34-0 (28 L ha-1), in-furrow 6-24-6 (28 L ha-1), foliar 3-18-18 (28 L ha-1) at V5 and R2 growth stages, and foliar 3-18-18 (28 L ha-1) with sulfate (1.1 kg ha-1) at V5 and R2. The acidic sites alone included two treatments of sugar beet (Beta vulgaris L.) waste lime (4.4 Mg ha-1 and 8.8 Mg ha-1). The alkaline sites alone received treatments of iron ortho-ortho-EDDHA (1.8% Fe) (7.1 L ha-1), and sodium (naked- without Fe) ortho-ortho-EDDHA (7.1 L ha-1). Treatments did not impact soybean yield, protein content or oil content at the 95% significance level. Sugar beet waste lime surface applied at planting at rates of 4.4 Mg ha-1 and 8.8 Mg ha-1 increased soil pH to a depth of 10 cm over the course of the growing season. / North Dakota Soybean Council