Hydromagnesite, the most stable of the basic magnesium carbonates, can be obtained by mining or by synthesis. Existing synthetic procedures have certain drawbacks which include, undesirable environmental effluents or high pressure and/or temperature requirements. Due to the lack of information in the literature, the aim of this study was to develop a cost effective procedure for the synthesis of basic magnesium carbonate from Mg(OH)2, not hampered by the above mentioned drawbacks. Following an extensive investigation into various parameters that influenced the final product, a simple procedure, based on sparging CO2 through a slurry of magnesium hydroxide in water until the pH reached 7.5-8.5, was developed. The solid portion of the slurry is dried at 80 or 120°C to deliver an unidentified basic magnesium carbonate and hydromagnesite respectively. The products were characterised by XRD, TG-DTA, surface area determination, SEM and FT-IR. The rehydration characteristics of the products were also investigated. By combining the information obtained by each technique, valuable information could be obtained. The synthesised products were evaluated for flame retardant application, due to the demand of mineral flame retardants which could compete with Mg(OH)2 and AI(OH)3. Compared to the traditionally used halogenated flame retardants, the mineral flame retardants deliver non-toxic, non-corrosive decomposition products and contributes in suppressing the emission of smoke in a fire. Results indicated that the basic magnesium carbonates compared favourably to Mg(OH)2 and AI(OH)3 and presented several advantages in terms of flame retardant applications. Further tests will be necessary to accurately assess the flame retardant effect of the basic magnesium carbonates. The possibilities however seem promising. / Thesis (PhD (Chemistry))--University of Pretoria, 2006. / Chemistry / unrestricted

The calcination of calcium carbonate in a cement or a lime kiln uses approximately two to four times the theoretical quantity of energy predicted from thermodynamic calculation depending upon the type of the kiln used (1.4 x 10^6 Btu/ton theoretical to 6 x 10^6 Btu/ton actual). The objective of this research was to attempt to reduce the energy required for the calcination by 1. decreasing the calcination temperature of calcium carbonate, and/or 2. increasing the rate of calcination at a specific temperature. Assuming a catalytic enhancement of 20 percent in the industrial applications, an energy savings of 300 million dollars annually in the United States could be reached in the cement and lime industries. Three classes of compounds to date have shown a positive catalytic effect on the calcination of calcium carbonate. These include alkali halides, phospho- and silico-molybdate complexes, and the fused carbonates system.

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Depuis les années 70, la synthèse de carbonates organiques a rencontré un grand intérêt dans diverses applications de l’industrie chimique. Parmi ces composés, le carbonate de diméthyle, qui est à la base de la fabrication de certains polycarbonates, est particulièrement intéressant. C’est un excellent solvant, et plus récemment, il s’est révélé être un additif potentiel pour les essences grâce à son contenu élevé en oxygène. Encore aujourd’hui, au niveau industriel, la synthèse de carbonate de diméthyle est basée sur l’utilisation de réactifs dangereux tels que le phosgène ou le monoxyde de carbone. Pour s’aligner sur les demandes de la chimie verte, une recherche assidue a été développée afin de trouver une voie de synthèse plus propre mais efficace qui pourrait être appliquée au niveau industriel. Parmi celles-ci, la voie la plus appropriée est la réaction directe du CO2 et du méthanol en présence d’un catalyseur capable d’activer le dioxyde de carbone. Dans ce travail, l’activité des complexes de type métallophthalocyanines a été testée en conditions atmosphériques et sous haute pression et haute température. Les méthodes de spectroscopie infrarouge, UV-visible etRMN ont été mise en oeuvre pour caractériser les intermédiaires réactionnels formés. Les travaux ont démontré que ces complexes métalliques possèdent une capacité d’activation du CO2 et du méthanol pour former le carbonate de diméthyle, tout en ayant une activité catalytique encore trop faible pour envisager de développer un procédé industriel. Ce type de complexes a cependant montré une activité satisfaisante pour la synthèse de carbonate de propylène à partir de CO2 et d’oxyde de propylène. / Since the 1970’s, the synthesis of organic carbonates has been of a strong interest in applications in the chemical industry as an intermediate in the synthesis of polycarbonates, as a solvent and more recently as a possible additive in gasoline due to its high oxygen content. Until now, industrial dimethyl carbonate synthesis has been based on the use of harmful reagents such as phosgene and carbon monoxide. To bring it into line with the requirements of green chemistry, research has been carried out to find a cleaner way of synthesis that could be also applied at an industrial scale. It was found that one of the most suitable chemical routes is the use of carbon dioxide and methanol in the presence of a catalyst that is able to activate the CO2 molecule. In this work, the activity of metallophthalocyanine complexes was tested under atmospheric, as well as high pressure and high temperature conditions. Infrared, UV-visible and RMN spectroscopy has been used to attempt to identify the reaction intermediates. In this work metallophthalocyanine complexes have been shown to activate methanol and CO2 molecules by forming dimethyl carbonate. However, the yields are too low to develop a chemical process at the industrial scale. Nevertheless, this type of complex has shown to be active in the synthesis of propylene carbonate from carbon dioxide and propylene oxide.

A dissertation submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Master of Science in Chemistry. University of the Witwatersrand, Johannesburg. May 2016 / In this research project, the morphogenesis and polymorphism of calcium carbonate (CaCO3) and its subsequent use as a template in the fabrication of hollow carbon spheres (HCS) is reported. A series of ratios (i.e. 5:0, 5:1, 5:2, 5:3, 5:4, 5:5, and 0:5) of binary solvent mixtures consisting of polar aprotic (dimethylformamide and dimethyl sulfoxide) and polar protic (methanol, ethanol, isopropanol, and 2-butanol) solvents, with 10% PEG200 as a crystal modifier, were used to influence the morphogenesis and polymorphism of precipitated CaCO3 (PCC). The PCC products were characterised using scanning electron microscopy (SEM), powder X-ray diffraction (PXRD), and laser Raman spectroscopy. An increase in the ratio of the polar protic solvent (methanol, ethanol, isopropanol, and 2-butanol) relative to the polar aprotic solvent (DMF & DMSO) within the binary solvent mixture favored the formation of vaterite particles of different morphologies, while an increase in the ratio of polar aprotic solvent (DMF & DMSO) within the binary solvent mixture favored the precipitation of rhombohedral calcite crystals. Time-resolved ex situ PXRD and SEM measurements revealed that the nucleation and phase transformation of the CaCO3 under polar protic and aprotic solvents followed the dissolution-reprecipitation mechanism. The major phase transformation occurred within 3 hours after mixing the precursor solutions. The effect of poly (4-styrenesulfonic acid) (PSSA) as an additive in the crystallisation of CaCO3 at different temperatures (i.e. 30, 40, 75, and 100 °C) and different crystallisation times (3, 6, 12, and 24 hrs) was investigated. The as-synthesised CaCO3 products were subjected to: SEM, laser Raman spectroscopy, PXRD, thermogravimetric analysis (TGA), and transmission electron microscopy (TEM). The crystallisation of CaCO3 in the presence of PSSA resulted in the self-assembly of vaterite particles into spherical bulk crystals. Varying the crystallisation temperature led to different particle attachment (CPA) pathways, which in turn resulted in bulk crystal morphologies that varied. Changes in the crystallisation temperature were found to not have changed the polymorphism of the precipitated CaCO3 due to the kinetic stabilisation effects of PSSA, instead hollow vaterite spheres formed at 75 and 100 °C. The possibility to synthesise HCS using CaCO3 as a template under chemical vapour deposition (CVD) at different temperatures (i.e. 600, 700 and 800 °C) was, for the first time, demonstrated. The evolution of CO2(g) from the decomposition of the template during CVD resulted in the formation of a rough surface topography on the carbon shell of the HCS. This surface roughness increased with the increase in the reaction temperature due to the increased rate of CaCO3 decomposition. The structural integrity of the spherical template was not affected by the CO2(g) evolution during carbonisation at all the reaction temperatures. The as-synthesised HCS at 600, 700, and 800 °C gave specific BET surface areas of: 193, 55, and 51 m2/g, respectively. / MT2016

The aims of this study are to extend the established high-resolution sequence stratigraphic framework of the Madison Formation of Wyoming and southern central Montana to the correlative and genetically-related Mississippian carbonate ramp, ramp margin, and basin strata of the central Montana trough and Antler foreland basin in order to examine and discriminate the controls on depositional processes and the resulting stratigraphic architecture through space and time in tectonically-active settings. An outcrop-based, high-resolution sequence stratigraphic study of two ramp-to-basin transects, one in central Montana and the other in southwestern Montana and east-central Idaho, is conducted in order to examine these deposits across two coeval margins with differing subsidence, hydrodynamic, and physiographic configurations and histories. Independent measurements of system response to global and local forcings allows disentanglement of primary controls on deposition and allows us to gain understanding of the roles and interplay of these controls, in particular eustasy and tectonics, on the system's architectural development. Conversely, insight into the geodynamic evolution of western North America, glacioeustatic changes, and variations in global climate and oceanographic systems during the greenhouse-to-icehouse transition is gained. A series of high-resolution sequence stratigraphic cross-sections and time-slices are produced incorporating outcrop measured sections and measured sections previously collected by members of the Comparative Sedimentology Laboratory in a series of transects across the Madison ramp system. A new chronostratigraphic framework for Madison carbonates is developed by using Lower Carboniferous delta C-13 isotope excursions as isochronous tie points between ramp-top, margin, and basinal sections. These delta C-13 excursion events have been documented to be time-invariant globally due to global changes in ocean chemistry. The results of the study include resolution and discrimination of sequential foreland basin subsidence, carbonate sediment production and progradation, subsidence and uplift of foreland basin structures along a carbonate shelf edge, diachronous subsidence of discrete depocenters, and eustasy.