Thesis (M.Sc.(Chemistry))--University of Pretoria, 2003. / Summaries in Afrikaans and English. Includes bibliographical references.

Thesis (Ph. D.)--University of Pennsylvania, 1927. / 'Literature": p. 29.

Thesis (Ph. D.)--University of Pennsylvania, 1942. / Reproduced from type-written copy. Bibliography: p. 44.

Thesis (Ph. D.)--State University of New York at Binghamton, Department of Chemistry, 2005. / Includes bibliographical references.

Ph.D. (Chemistry) / Materials that are to be used as reference samples are frequently analysed using costly and sophisticated instrumentation, itself calibrated with similar certified standards. Analytical programmes using such instrumentation are only as accurate as the initial calibrations, and their poor results have led to the adoption by the United States National Bureau of Standards of definitive methods of analysis for the determination cf trace elements ...

M.Sc. (Geology) / This study involves the quantitative analysis of fluorspar-containing slurries by two X-ray diffraction methods, whereby these two methods of on-stream analysis are compared. The first method involves a single counter with a diffracted beam monochromator, and the second method involves a fixed geometry with an incident beam monochromator. The second method is a cheaper and more robust apparatus, which can withstand the harsh environment of the flotation plants. A new algorithm was developed for a more accurate calibration method. Programmes for calibration, recalibration and measuring of unknown samples were developed. The measuring apparatus was interfaced with a microcomputer for computerised operation of the system. Results from both methods were comparable, with more accurate results obtained for the feed and tailings than for the concentrate samples. The single detector apparatus can thus be replaced by the fixed geometry model, which is less expensive and more robust.

A study of the role of different oxidants with silicon as the fuel in simple binary pyrotechnic compositions is reported. Several oxidants were examined, but only three (Sb₂0₃, Fe₂0₃ and Sn0₂) satisfied the restrictions that the combustion temperatures should be below the melting point of platinum/rhodium thermocouples (1760°C), that burning rates should not exceed the response of the thermocouples, and that burning should occur without significant mass-transport. A fourth oxidant, KN0₃, was selected on account of its low melting point and general importance as a pyrotechnic oxidant. The oxidation of silicon in the presence of either Sb₂0₃ or KN0₃ could be identified from thermal analysis curves. No thermal events were noted when Si/Sn0₂ and SiFe₂0₃ compositions were heated under similar conditions. The oxidation of Si powder in oxygen was also studied. All four binary systems sustained burning over a reasonably wide range of compositions. The range of burning rates measured (2 to 35 mm s⁻¹) depended on the oxidant used. Fe₂0₃ and Sb₂0₃ gave slow burning mixtures compared to Sn0₂ and to KN0₃ compositions with a high Si content. Burning rates generally increased with increasing specific surface area of silicon, but decreased in the presence of inert diluents and moisture. The burning rates of the Si/Fe₂0₃ and Si/Sn0₂ systems increased with increasing compaction of the samples. Kinetic parameters derived from the temperature proftles recorded during combustion were generally low (6 to 37 kJ mol⁻¹). This is in keeping with proposals that burning is diffusion controlled. The values of kinetic parameters derived from thermal analysis curves were considerably greater ( > 250 kJ mol⁻¹). Two other fuels, FeSi₇ and CaSi₂, gave similar thermal analysis curves when used instead of silicon. There were considerable differences in the burning rates for binary mixtures of these fuels compared to silicon. Ternary systems with two fuels or two oxidants showed that only limited interaction occurs during thermal analysis. The use of a second fuel or oxidant did, however, modify the burning behaviour considerably. Other techniques used in this study to probe the details of the reaction processes included bomb calorimetry, measurement of thermal conductivities, infrared spectroscopy, X-ray diffraction and scanning electron micoscropy.

From Summary: The structural elucidation of condensed tannins, which are considered to consist of C₁₅-flavan units, presents certain difficulties. These tannins occur in extremely complex mixtures, and their isolation is complicated by their susceptibility to oxidative denaturation. Limitations in the formation of significant degradation products add to these problems. Since condensed tannins of black wattle bark yield anthocyanidins on treatment with mineral acids, they are considered to be proanthocyanidin in character. For this reason the initial approach to the investigation of the structures of condensed tannins was by way of the synthesis of novel 7-hydroxyflavan-3,4-diols having a low degree of hydroxyl substitution. Submission of these to modern physical techniques such as nuclear magnetic resonance (n.m.r.) spectroscopy would yield valuable data regarding the chemical shifts and coupling constants of heterocyclic and benzenoid protons which may be used for subsequent work on more highly hydroxylated diols, biflavanols and finally the condensed tannins themselves.

Marrubiin and the other two diterpenoids, compounds X and Y, which had previously been isolated from Leonotus leonurus have been reinvestigated. Although the structure for marrubiin is well known its stereochemistry has been the subject of protracted discussion and is by no means secure except at C₅ and C₁₀ . N.M.R. spectral evidence showed that the lactone ring was cis-fused and β-orientated. Dehydration experiments carried out by previous workers were repeated, in order to resolve the residual uncertainty regarding the stereochemistry at C₉, an attempt was made to prepare iodoacetyl marrubic acid for X-ray crystallographic studies. Compound Y, C₂₀H₂₈0₃, a triply-unsaturated compound was shown by spectral studies to contain a furan ring and an α,β- unsaturated keto-group. It possesses a hydroxyl group incapable of acetylation, but readily removed by alkali and dehydrating agents to yield a tetraunsaturated compound, anhydro~Y; the hydroxyl is thus tertiary, Isolation of 1:2:5-trimethylnaphthalene on dehydrogenation indicated a relationship with the labdane diterpene group and supported the C₂₀ formula, The position of the α,β-unsaturated keto-group was resolved by interpretation of the ultraviolet spectra of degradation products and also by isolation of 1:2:3:5- trimethylnaphthalene on dehydrogenation of a suitable grignard product, The presence of a β-substituted furan was further indicated by colour reactions and confirmed by mass and n.m.r. spectra. The skeleton of compound Y is correlated with marrubiin via "iso-ambreinolide " and its stereochemistry is discussed. Further stereochemical assignments are postulated from the study of the n.m.r. spectra. Compound X, C₂₀H₂₈0₅, was shown by spectral and chemical evidence to be a diterpenoid dilactone containing an ether bridge between C₉ and C₁₃ Isolation of 1:2:5 trimethylnaphthal ene on dehydrogenation showed it to be closely related to marrubiin, This was supported by n.m.r. spectral results. A structure for compound X is proposed and the stereochemistry discussed. The aerial portions of Leonotis leonitis were also extracted and shown to contain a new compound, compound R. Preliminary investigation showed that it was a dilactone containing a furan ring, The n.m.r. spectrum of the compound is discussed.

Barium peroxide was selected as oxidant in a fundamental physico-chemical study of binary pyrotechnic systems on account of its apparently simple decomposition stoichiometry. With this selection, the choice of fuel was governed by the requirements of a self-sustaining reaction at combustion temperatures below the melting point of the platinum/rhodium thermocouples (∼1760°C) used for recording temperature-time profiles during burning, and at burning rates not exceeding the response of the sensors used to monitor combustion. Both manganese and molybdenum metal powders satisfied the above requirements. Strontium peroxide was also available as an oxidant and so the combustion of binary metal/oxidant systems using both fuels and both BaO₂ and SrO₂ oxidants was investigated. The Mn/BaO₂, MoBaO₂ and Mn/SrO₂ systems burnt over a wide range of compositions, but the range of ignitable compositions for the Mo/SrO₂ system was very limited. The linear burning rates, for all these systems, ranged from 2 to 12 mm s⁻¹ and burning rates were increased by the use of smaller particle-sizes of fuel and greater loading pressures. Inert additives generally decreased the burning rate. Temperature-time profiles were recorded for all the compositions which sustained combustion. Kinetic parameters were estimated from the shapes of these profiles using procedures developed by Hill et al and Boddington and Laye. Activation energies derived from the profiles were low (3 to 40 kJ mol⁻¹) and support suggestions that reactions at high temperatures are controlled by diffusion processes. Thermal analysis was used to identify the processes occurring in the four systems. The main exothermic events were observed to correspond approximately with the onset of oxidant decomposition. A pre-ignition reaction was tentatively identified in the Mn/BaO₂ system. Oxidation of the metal fuels was generally incomplete, probably because of the formation of protective layers of product. Activation energies, derived from thermal analysis results, were in the range of from 70 to 720 kJ mol⁻¹. Ternary systems containing either mixed fuels or mixed oxidants were also examined. No interactions hetween the fuels or between the oxidants were observed. Other techniques used included bomb calorimetry, measurement of thermal conductivity, X-ray powder diffraction, infrared spectroscopy and scanning electron microscopy.