I have chosen the title for this thesis, "Reactions in the Solid State", for two reasons: Firstly, it is broad enough to cover all of my areas of research, which have been: • Effects of irradiation on solids (PhD topic) • Silver refining (while at the Chamber of Mines) • Kinetics of decomposition of solids (with Dr A.K. Galwey and various others) • Techniques of thermal analysis • Pyrotechnic delay systems (with support from AECI Explosives) • Thermal and photostability of drugs (with Prof B.D. Glass) and, secondly, it was the title of the very successful book co-authored by Drs Andrew Galwey, David Dollimore and me. A large part of my research has been involved in the writing and editing of books, so these are covered in a separate commentary, while commentary on the more than 100 papers to which I have contributed forms the main part of this compilation. It is hoped that the electronic format will enable ready access of to all aspects of my research, including electronic versions of the original papers. The reader will need a copy of Adobe Acrobat Reader to access these.

Please read the abstract in the section 00front of this document / Dissertation (MSc (Applied Chemistry))--University of Pretoria, 2006. / Chemistry / unrestricted

Two labdane diterpenoids 8-hydroxymarrubiin and leonitin were isolated from Leonotis dysophylla (Benth.) and Leonotis leonitis respectively. Spectral studies of 8-hydroxymarrubiin, C₂₀H₂₈ O₅ʻ showed the presence of a β -substituted furan, a Ϫ-lactone, three tertiary methyl groups and tertiary hydroxyl group (s). The NMR spectrum of 8-hydroxymarrubiin and marrubiin C₂₀H₂₈O₄ʻ were almost identical with the exception of the C₁₇- methyl group which appeared as a singlet in 8-hydroxymarrubiin and as a doublet in marrubiin. The extra oxygen atom was therefore assumed to be present as a hydroxyl group substituted in the C₈₋ position. This was further confirmed by the formation of an epoxide and a Ϫό-dilactone. Leonitin, C₂₀H₂₈O₇ʻ was shown by spectral and chemical evidence to be a diterpenoid dilactone possessing an ester function and an ether linkage. Comparison of the NMR spectra of compound X and leonitin suggested that the acetoxy function occurs in the C₂₀- position. This was further supported by the formation of a 'Ϫό -dilactone. The absence of a β -furan moiety was apparent from chemical and spectral evidence, A structure for leonitin is proposed and aspects of its stereochemistry discussed.

The important facts developed by the investigation are: Group III can be subdivided into two divisions without much injury to the delicacy of the individual tests. [See document for Scheme of Analysis For Group III] [See document for Diagramatic Scheme of Group III] The successful division of this group has eliminated the possibility of certain metals oxidizing during their initial precipitation and washing.* That the present of chromium precipitates an additional eleven per cent of zinc, but does not appreciably effect manganese. That different concentrations of ammonium hydroxide and ammonium chloride will precipitate varying amounts of zinc and manganese. The writer feels quite sure that his method requires less time and is less expensive than other methods.* / M.S.

A full IH, l3C and 31P NMR assignments of phosphoric triamides 1-oxo-2,8-diphenyl-2,5,8-triaza-l-phosphabicyclo [3.3.0]octane (1), l-oxo-lO-phenyl-4,7,lO-triaza-2.3-benzo-l-phoshabicyclo [5.3.0]decane (2) and 1-oxo-4,7,lO-triaza-2,3,11,12-dibenzo-l-phosphabicyclo[5.5.0]dodecane (3) which have been recently synthesised was accomplished. The solution state NMR analysis of these compounds showed a number of interesting spin systems upon moving from 1→2→3, spanning from ABC to ABCDX spin systems where X is phosphorus nucleus. The three systems showed a high degree of rigidity in solution state, which made it possible to compare dihedral/torsion angles determined from solution state NMR with those of X-ray diffraction data. Both X-ray diffraction and NMR analysis supported the molecular conformations. A significant solvent effect was observed for solutions of compounds 1, 2 and 3 in benzene-d6 compared to solutions in chloroform-d1 and acetone. Benzene-d6 showed a generally upfield chemical shift of methylene protons in particular, and this is assumed to be due to different solvent-substrate interactions and to the magnetic anisotropic effect of the solvent. / Dissertation (MSc (Chemistry))--University of Pretoria, 2007. / Chemistry / unrestricted

Thesis (MSc)--Stellenbosch University, 2000. / ENGLISH ABSTRACT: This study was initialized to introduce capillary electrophoresis (CE) as a useful technique in the analysis of fluid inclusions in quartz. lts advantages are low detection limits for the dissolved ionic content of the fluid, the small amount of sample (1 g or less) for a detailed qualitative and quantitative analysis, and the short time required to obtain results (one run for either cations or anions take approximately 10 minutes). The study area from which quartz veins were selected is situated within the Neoproterozoic Saldania belt. Syn- and post-tectonic S-, 1- and A-type granitoids from the Cape Granite Suite intruded the metamorphosed Malmesbury greywacke and pelites between 550 and 510 Ma. Additional periods of tectonism and metamorphism occurred during Cape Supergroup sedimentation (480 - 400 Ma) as well as Karoo sedimentation and the simultaneous Cape Orogeny (280 -215 Ma). The quartz-biotite±chlorite vems are hosted by Cape Granite as well as Malmesbury sediments. These barren quartz veins are part of two vein sets, one dipping at an angle between 15 and 500 to the S to SE and striking W, similar to Sn-mineralized quartz veins in the SW-cape, while the other is near-vertical and striking W to NW. Except for their orientation, no differences regarding associated minerals, inclusion characteristics or fluid chemistry indicated a difference in origin. Four fluid phases within a temperature range of 160 - 390 °C were identified as being largely late-magmatic and released from the underlying Cape Granite plutons, namely an early 370- 390 °C population, followed by the 310 - 360, 230 - 300 and lastly the 160 - 200 °C populations. Initiation of this fluid system occurred from at least SlOMa, after final granite intrusion, but the age of the final stage is unknown. Renewed fluid circulation occurred during a later period of metamorphism, possibly during the Cape Orogeny. These fluids had temperatures between 240 and 360°C and are of sedimentary origin, most likely released from the Malmesbury metamorphites. The technique of capillary electrophoresis has been evaluated for its application to bulk fluid inclusion analysis, and the crush-leach fluid extraction procedure of Bottrell, et al., (1988) optimized for CE analysis. Contamination factors were identified and minimized or eliminated, where possible. Bulk fluid inclusion chemistry obtained by CE was therefore proved to provide valuable information regarding the various fluid generations as long as inclusion populations are investigated individually to explain and correlate bulk data. / AFRIKAANSE OPSOMMING: Die doel van die studie was om te toon dat die tegniek van kapillêre elektroforese bruikbaar is in die analiese van vloeistofmsluitsels in kwarts. Die voordele van hierdie tegniek is lae deteksie limiete vir die opgeloste ioon inhoud van die vloeistof, die klein monstergrootte (< 1g) wat nodig is vir 'n omvattende kwalitatiewe en kwantitatiewe analise, en die kort tydsduur waarin resultate verkry word ('n katioon of anioon analise vir een monster duur lO minute). Die studie gebied waar kwarts are gemonster is, is binne die Neoproterosoïese Saldania Gordel geleë. Sin- en laat-tektoniese S-, I- en A-tipe graniete van die Kaapse Graniet Suite het die gemetamorfiseerde Malmesbury grouwakke en peliete tussen 550 en 510 Ma binnegedring. Latere periodes van tektonisme en metamorfose het tydens deponering van die Kaap Supergroep (480 - 400 Ma), en die gelyktydige episodes van Karoo sedimentasie en Kaapse Orogenese (280 - 215 Ma) plaasgevind. Die gasheer gesteentes vir die kwarts-biotiet±chloriet are is Kaapse Graniet sowel as Malmesbury sedimente. Hierdie ongemineraliseerde are is deel van twee aarstelsels, nl. een met 'n duik hoek tussen 15 en 50° S tot SO en 'n westelike strekking, soortgelyk aan die Sn- ,.gemineraliseerde are in die SW-Kaap, terwyl die ander stel are feitlik vertikaal is en W tot NW strek. Behalwe vir die verskil in oriëntasie was daar geen aanduiding, wat betref 'n verskil in geassosieerde minerale, vloeistofinsluitsel kenmerke of vloeistof chemie, dat hierdie twee aarstelsels van verskillende oorsprong is nie. Vier vloeistof fases binne 'n temperatuur gebied van 160 - 390 °C en 'n vloeistof saliniteit van 0 - 5.7 gewig % NaC1 ekw. is geïdentifiseer, met 'n laat-magmatiese assosiasie en vrygestel deur die onderliggende Kaapse Graniete. Dit behels 'n vroeë 370 - 390 °C populasie, gevolg deur die 310 - 360, 230 - 300 en laastens die 160 - 200 °C populasies. Inisiasie van hierdie sisteem kon moontlik rondom 510 Ma gelede plaasgevind het, maar die ouderdom van die finale fase is onbekend. Hernude vloeistof sirkulasie het tydens 'n later stadium van metamorfose onstaan, moontlik tydens die Kaapse Orogenese. Hierdie vloeistowwe het temperature tussen 240 en 360 °C en is van sedimentêre oorsprong waar dit moontlik deur metamorfose van die reeds gemetamorfiseerde Malmesbury gesteentes vrygestel is. Die tegniek van kapillêre elektroforese is vir die toepassing daarvan in die analise van vloeistof insluitsels in kwarts geëvalueer, terwyl die vloeistof vrystellingsmetode van Bottrell en Yardley (1988) vir hierdie tegniek geoptimaliseer is. Kontaminasie faktore is geïdentifiseer en verminder of uitgeskakel waar moontlik. Daar is getoon dat die vloeistof chemie, wat verteenwoordigend is van al die insluitsel populasies in 'n monster, wel bruikbaar is t.o.v. afsonderlike vloeistof generasies, solank elke populasie individueel bestudeer is om die omvattende chemiese data te verduidelik en met 'n enkele populasie te korrelleer.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Master / Master of Science

PCBs are persistent organic pollutants that have intentionally and unintentionally (through contamination) been added to mineral insulating oil to improve its insulating and cooling properties within electrical equipment. The Stockholm Convention on Persistent Organic Pollutants (2001) orders the eradication of PCBs from use by 2025. Sodium based dechlorination is a PCB destruction process that is non-thermal, relatively cost effective and allows for the recovery of a reusable end product. A comparative benefits study, contained in chapter 2 of this dissertation, describes the increased financial and environmental impact associated with incinerating large volumes of PCB contaminated mineral oil. The results of the comparative analysis indicate a cost ratio of 1: 2.5, in favour of sodium dechlorination. In addition to the financial benefit, the sodium based PCB dechlorination process is versatile and can be either batched or skid mounted and is typically combined with an oil regeneration step, allowing for transformers to be treated onsite and whilst energised. Eskom is currently considering obtaining the mobile dechlorination unit for the purpose of conducting dechlorination and regeneration on its PCB contaminated transformers while energised. Mineral insulating oil is considered a strategic asset within most industries. Eskom uses mainly uninhibited mineral oil in its older transformers and the effects of PCB dechlorination on the natural inhibitor content of the oil is uncertain. The objective of this study was to investigate the effects of sodium dechlorination on the oxidation stability and thereby indirectly the natural inhibitor content of uninhibited naphthenic based mineral oil. The study involved the dechlorination, regeneration and subsequent chemical analyses of PCB contaminated oils in the PCB ranges <50ppm, 50 to 500 ppm and >500 ppm as stipulated by the Stockholm Convention on Persistent Organic Pollutants (2001). The study confirmed the reduction in oxidation stability and thereby the natural inhibitor content of the mineral oil after sodium dechlorination. Based on the results obtain a preliminary algorithm was established to predict the reduction in oxidation stability after sodium dechlorination, as a function of the PCB concentration prior to dechlorination. This will provide an indirect indication of the rate of natural inhibitor depletion of the oil, based on its exposure to the sodium dechlorination reagents and process conditions. / Thesis (M.Sc.Eng.)-University of KwaZulu-Natal, Durban, 2010.

Thesis (Ph. D.)--Florida State University, 2004. / Advisor: Dr. John G. Dorsey, Florida State University, College of Arts and Sciences, Dept. of Chemistry and Biochemistry. Title and description from dissertation home page (viewed June 16, 2004). Includes bibliographical references.