The purpose of this thesis was two fold: (i) The synthesis and characterization of SF5 containing dienes. (ii) The characterization of hydro/fluorocarbon compounds containing SF5/S02F groups via their 13C NMR spectra. A new SF5CH2CHBrCH2CF=CF2 was prepared and characterized as a precursor to new dielectric polymers. This new adduct was made from the reaction of pentafluorothio bromide with l,l,2-trifluoro-1,4-pentadiene. A SF5-diene was prepared from the reaction of pentafluorothio chloride with acetylene. This reaction involves a radical addition mechanism. The SF5 group is bonded to the carbon atom carrying the most hydrogens. SF5 - dienes are capable of undergoing different reactions, such as polymerization. Fluorocarbon sulfonyl fluorides (RS02F), which have been synthesized in our lab, were characterized by their 13C NMR spectra. The 13C NMR data of these sulfonyl fluorides show chemical shift values for the methyl and methylene groups next to a fluoroalkyl sulfonyl fluoride group in the 52.8-65.7 ppm range. The spectra showed that the inductive effect of electronegative substituents has a major influence on the 1Jc-F and 1Jc-H coupling. Infrared, 1H, 19F and 13C nuclear magnetic resonance and mass spectra are presented to support the assigned structure for the new compounds, SF5CH=CHCH=CHC1 and SF5CH2CHBrCH2CF=CF2.

Abstract is not available

Tetrahydrofolate-mediated one-carbon metabolism is required for the biosynthesis of many central metabolites, including some amino acids, nucleobases, and nucleotides, and hence dysfunction of one-carbon metabolism is associated with many human diseases and disorders. The mitochondrial glycine decarboxylase complex (GDC) is an important component of one-carbon metabolism, generating 5,10-methylene-tetrahydrofolate (5,10-CH2-H??4folate) from glycine. Previous work has shown that the genes encoding the unique sub-units of the Saccharomyces cerevisiae GDC (GCV1, GCV2 and GCV3) are regulated in response to changes in the levels of cytosolic 5,10-CH2-H??4folate (Piper et al., 2000). Given the centrality of 5,10-CH2-H??4folate to many aspects of metabolism, it was hypothesised that other genes may be regulated by the same mechanism. Using microarray analysis of S. cerevisiae under a number of conditions that affect 5,10-CH2-H??4folate levels, the ??one-carbon regulon??, a group of genes that were co-regulated with the GCV genes was identified. The one-carbon regulon corresponds closely to genes whose promoters are bound by the purine biosynthesis regulator Bas1p, but not all one-carbon regulon members are significantly purine regulated. Genetic approaches demonstrated that the one-carbon unit response and the purine response are distinct, though both depend on the presence of Bas1p. This demonstrated that the close metabolic connections of one-carbon and purine metabolism are reflected in over-lapping, but separable regulatory mechanisms. The identity of the sensor of one-carbon unit depletion remains unknown, but in the course of investigation of the candidate regulator Caf17p, it was demonstrated that Caf17p is in fact involved in Fe/S cluster protein maturation. Examination of the effects of Caf17p depletion revealed that Caf17p is required for the function and maturation of the related mitochondrial Fe/S proteins aconitase and homoaconitase, as well as the function of, but not de novo iron incorporation into, the mitochondrial radical-SAM Fe/S protein biotin synthase. Because other Fe/S proteins were unaffected, Caf17p appears to be a specialised Fe/S maturation factor. The presence of a putative H4folate binding site indicates that Caf17p may constitute a metabolic link between one-carbon and iron metabolism.

A systematic study of highly branched isoprenoids (HBI) was carried out in suspended particulate material (SPM) and Washington coastal sediments to determine their origin and fate. SPM collected at 10 m depth was filtered through Nitex membranes. C₂₅ HBI were found only in the 1.2-40 μm range over the shelf. The particle size fractionation of SPM shows different enrichment for HEH, a common hydrocarbon in phytoplankton, and the sum of C₂₅ HBI in the finer fractions suggesting these hydrocarbons do not share a common source. The distribution of C₂₅ and C₃₀ HBI correlates with the chlorophyll maxima suggesting an upper-water microbial source associated with phytoplankton biomass. It has been hypothesized that sulfur addition into specific biomarkers occurs during the early stages of diagenesis. Incorporation of the HBI into a refractory geomacromolecule via a sulfur linkage or formation of HBI-thiophenes are not evident in the sedimentary lipids. HBI show a rapid decrease in concentration with depth in both midshelf and slope sediments suggesting that biodegradation is the major pathway for their disappearance in Washington coastal sediments. Sediment cores from a midshelf and slope locations show the existence of suboxic/anaerobic conditions within the first 5 cm in the sediments. Elemental sulfur distribution in the midshelf appears to be controlled by bioturbation. On the slope, its profile indicates a quasi steady state regime. Phytane and phytenes (∑Phy) are the major products of Raney nickel desulfurization in both midshelf and slope sediments. Spinach and a strain of Emiliana huxleyi treated with Raney nickel showed strikingly similar patterns to the desulfurization products of sedimentary lipids. The amount of ∑Phy in the slope decreases abruptly by a factor of 6 in the top 2 cm and gradually increases with depth. These results are interpreted as phytyl coming from two sources: (1) chlorophyll-a and (2) S-bound to geomacromolecules. Partial released of phytyl moieties from chlorophyll-a warrants a reevaluation of Raney nickel as a selective desulfurizing agent before its application for paleoenvironmental reconstruction. Reducing micro-environments appear to exist within the bioturbated zone in shelf sediments. However, there is no clear evidence for phytyl moieties S-linked to macromolecules within the mixed layer. Results obtained during this study indicate that sulfur incorporation to biomarkers, although present, does not represent a significant mechanism for the preservation of organic carbon in normal marine sediments. / Graduation date: 1994

The utilisation of alternate sources of energy has reached critical levels due to the constantly growing demand for energy and the diminishing of fossil fuels. The production of hydrogen through the Hybrid Sulphur process is a possible alternative that may contribute towards alleviating the pressure on the world's energy resources. The two-step thermochemical cycle for decomposing water into hydrogen and oxygen offers the potential to obtain acceptable thermal efficiencies, while still using common and inexpensive chemicals. The process mainly makes use of two unit process operations: an electrolyser and a chemical decomposition reactor. This research project focuses on the concept design of the decomposition reactor operated adiabatically as a multi-stage reactor system with inter-stage heating, in order to simplify the reactor design. This approach allows for the independent evaluation of the reaction kinetics and the heat transfer mechanism. / Thesis (M.Ing. (Nuclear Engineering))--North-West University, Potchefstroom Campus, 2009.

Elemental sulphur (S0) is produced from processing bitumen from the oil sands region, Alberta. Long term storage of this S0 is under consideration. The objective of the current study was to determine the controls on water migration in variably saturated S0 blocks. Based on visual observations of S0 blocks, they were characterized as a hydrophobic fractured porous media. Thus, measurements of the hydraulic characteristics, including porosity (n) and hydraulic conductivity (K) of the matrix and the fractured media, were undertaken. These data were used to create characteristic relationships of unsaturated K (Kunsat) and volumetric moisture content (è) change with change in positive injection pressure (Ø).<p>Analyses showed that the mean total matrix n (nm) was 0.094 ± 0.035 (n = 280), the mean n available for water migration (na) was 0.065 ± 0.044 (n = 8) and the mean (geometric) K for the matrix was 2.0 x 10-6 ± 2.1 x 10-6 ms-1. In the case of vertical fractures, the aperture frequencies were measured to be 2.5, 10.0 and 21.0 m-1 for fractures with apertures > 1.4, 1.4 to 0.6 and < 0.6 mm respectively while the frequency of horizontal fractures, were measured to be 1.7 and 3.7 m-1 for with apertures > 1.4, and < 1.4 mm respectively. The fracture n (nf) was determined to be 0.0135. è Ø relationships were determined for both the fractured and non fractured media. From these plots, water entry values of 9 mm and 1 m were determined for the fracture pore space and the matrix pore space, respectively.<p>Simulations of packer tests resulted in a bulk saturated K (Kb) values ranging from 8.5 x 10-5 to 2 x 10-4 ms-1 above 9 m depth and 3 x 10-6 to 1.5 x 10-5 ms-1 below 9 m depth. Coupled Kunsat Ø and è Ø relationships were used to conceptually describe water migration in S0 blocks under different precipitation and mounding conditions. These plots also showed that the Kb is dominated by the fractures.

Elemental sulphur (S0) is produced from processing bitumen from the oil sands region, Alberta. Long term storage of this S0 is under consideration. The objective of the current study was to determine the controls on water migration in variably saturated S0 blocks. Based on visual observations of S0 blocks, they were characterized as a hydrophobic fractured porous media. Thus, measurements of the hydraulic characteristics, including porosity (n) and hydraulic conductivity (K) of the matrix and the fractured media, were undertaken. These data were used to create characteristic relationships of unsaturated K (Kunsat) and volumetric moisture content (è) change with change in positive injection pressure (Ø).<p>Analyses showed that the mean total matrix n (nm) was 0.094 ± 0.035 (n = 280), the mean n available for water migration (na) was 0.065 ± 0.044 (n = 8) and the mean (geometric) K for the matrix was 2.0 x 10-6 ± 2.1 x 10-6 ms-1. In the case of vertical fractures, the aperture frequencies were measured to be 2.5, 10.0 and 21.0 m-1 for fractures with apertures > 1.4, 1.4 to 0.6 and < 0.6 mm respectively while the frequency of horizontal fractures, were measured to be 1.7 and 3.7 m-1 for with apertures > 1.4, and < 1.4 mm respectively. The fracture n (nf) was determined to be 0.0135. è Ø relationships were determined for both the fractured and non fractured media. From these plots, water entry values of 9 mm and 1 m were determined for the fracture pore space and the matrix pore space, respectively.<p>Simulations of packer tests resulted in a bulk saturated K (Kb) values ranging from 8.5 x 10-5 to 2 x 10-4 ms-1 above 9 m depth and 3 x 10-6 to 1.5 x 10-5 ms-1 below 9 m depth. Coupled Kunsat Ø and è Ø relationships were used to conceptually describe water migration in S0 blocks under different precipitation and mounding conditions. These plots also showed that the Kb is dominated by the fractures.

No description available.

In this thesis, the morphological changes of the anode surface in lithium sulphur cell, during early cycling, were simulated using symmetrical lithium electrode cells with dissolved polysulphides (PS) in the electrolyte. Electron microscopy (SEM) was used as the principal investigation technique to study and record the morphological changes. The resulting images from the SEM were analysed and discussed. The initial surface structure of the lithium anode largely influenced the ensuing morphological changes taking place through lithium dissolution (pits) and lithium deposition (dendrites) during discharge and charge respectively. The rate of lithium dissolution and deposition was found to be linearly proportional to the current density applied to the cell and the effect of cycling on the anode was proportional to the total charge of the cell in general in agreement with the expected reaction. The effect of self-discharge on the anode was also studied using photoelectron spectroscopy (XPS) in tandem with SEM. The results indicated that self-discharge, occurring in the form of corrosion of the anode SEI by PS reduction, was influenced by the altered morphology of the cell after cycling. The findings presented in this project can be understood as a preliminary description for the morphological changes in the anode and their influence in the performance of lithium sulphur battery, which can be further investigated by more advanced methods. / <p>Joint collaboration project between Scania CV AB and Uppsala University.</p>

In order to reduce the amount of pollution that is generated by burning fossil fuels alternative energy sources should be explored. Hydrogen has been identified as the most promising replacement for fossil fuels and can be produced by using the Hybrid Sulphur (HyS) cycle. Currently the SO2/O2 separation step in the HyS process has a large amount of knock out drums. The aim of this study was to investigate new technology to separate the SO2 and O2. The technology that was identified and investigated was to separate the SO2 and O2 by absorbing the SO2 into an ionic liquid. In this study the maximum absorption, absorption rate and desorption rate of SO2 from the ionic liquid [BMIm][MeSO4] with purities of 95% and 98% was investigated. These ionic liquid properties were investigated for pure O2 at pressures ranging from 1.5 to 9 bar(a) and for pure SO2 at pressures from 1.5 to 3 bar(a) at ambient temperature. Experiments were also carried out where the composition of the feed-stream to the ionic liquid was varied with compositions of 0, 25, 50, 75 and 100 mol% SO2 with O2 as the balance. For each of these compositions the temperature of the ionic liquid was changed from 30oC to 60oC, in increments of 10oC. The absorption rate of SO2 in the ionic liquid increased when the mole percentage SO2 in the feed stream was increased. When the temperature of the ionic liquid was decreased the maximum amount of SO2 that the ionic liquid absorbed increased dramatically. However, the absorption rate was not influenced by a change in the absorption temperature. The experimental results for the maximum SO2 absorption were modelled with the Langmuir absorption model. The model fitted the data well, with an average standard deviation of 17.07% over all the experiments. In order to determine if the absorption reaction was endothermic or exothermic the Clausius-Clapeyron equation was used to calculate the heat of desorption for the desorption step. The heat of desorption data indicated that the desorption of SO2 from this ionic liquid was an endothermic reaction because the heat of desorption values was positive. Therefore the absorption reaction was exothermic. From the pressure-change experiments the results showed that the mole percentage of O2 gas that was absorbed into the ionic liquid was independent of the pressure of the O2 feed.On the other hand, there was a clear correlation between the mole percentage SO2 that was absorbed into the ionic liquid and the feed pressure of the SO2. When the feed pressure of the SO2 was increased the amount of SO2 absorbed also increased, this trend was explained with Fick’s law. In the study the effect of the ionic liquid purity on the SO2 absorption capacity was investigated. The experimental results for the pressure experiments showed that the 95% and 98% pure ionic liquid absorbed about the same amount of SO2. During the temperature experiments the 95% pure ionic liquid absorbed more SO2 than the 98% pure ionic liquid for all but two of the experiments. However the 95% pure ionic liquid also absorbed small amounts of O2 at 30 and 40oC which indicated that the 95% pure ionic liquid had a lower selectivity than the 98% pure ionic liquid. Therefore, the 95% pure ionic liquid had better SO2 absorption capabilities than the 98% pure ionic liquid. These result showed that the 98% pure ionic liquid did not absorb more SO2 than the 95% pure ionic liquid, but it did, however, show that the 98% pure ionic liquid had a better selectivity towards the SO2. Hence, it can be concluded that even with the O2 that is absorbed it would be economically more advantageous to use the less expensive 95% pure ionic liquid rather than the expensive 98% pure ionic liquid, because the O2 would not influence the performance of the process negatively in such low quantities. / Thesis (MIng (Chemical Engineering))--North-West University, Potchefstroom Campus, 2013