List of Titles

Investigation of the synthesis and characterisation of spiro orthocarbonates and heterocyclic orthocarbonates

Authors: Cuthbertson, Jarryd Pierre
Date: 2024-04
Subjects: Chemistry, Analytic , Analytical chemistry , Chemistry
Language: English
Type: Master's theses , text
Identifier: http://hdl.handle.net/10948/63678 , vital:73578
Description: A series of mostly asymmetrical spiro orthocarbonates and heterospirocyclic derivatives of orthocarbonic acid was synthesized from 2,2-dichlorobenzodioxole and a number of difunctional reagents. A systematic study of the size of the chelate rings formed around the spirocentric carbon atom was conducted by selecting representative samples of aliphatic and aromatic diols. The feasibility and scope of potential starting materials used was expanded by reacting DCBD successfully with thiols. Molecular structures of these compounds were confirmed using diffraction studies on single crystals. All compounds were analyzed using multinuclear NMR. DFT calculations performed on the compounds allowed for the development of equations that can accurately predict 13C chemical shifts of SOCs. Furthermore, the experimental NMR spectroscopy gave rise to an increment shift system for the 13C NMR shifts allowing for further assignment of carbon atom positions in compounds with multiple possible bonding patterns. , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
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Date Issued: 2024-04

The on-demand continuous flow generation, separation, and utilization of monosilane gas, a feedstock for solar-grade silicon

- Mathe, Francis Matota

Authors: Mathe, Francis Matota
Date: 2024-04
Subjects: Chemistry, Organic , Chemistry , Silicon -- Synthesis
Language: English
Type: Doctoral theses , text
Identifier: http://hdl.handle.net/10948/64179 , vital:73660
Description: This research is dedicated to the development of a continuous flow process for the production and utilization of monosilane gas. The utilization of continuous flow techniques was instrumental in addressing the challenges and conditions associated with the handling of monosilane gas. Furthermore, the integration of Process Analytical Technologies (PAT) facilitated in-process monitoring and analysis. Chapter one of this research provides an extensive background and literature review encompassing the purification methods of silicon, the latest advancements in the direct synthesis of alkoxysilanes, current synthesis methods for monosilane, the various applications of monosilane, as well as the utilization of continuous flow technology and process analytical technologies. In chapter two, a detailed account of the experimental procedures employed in this research is presented. Chapter three delves into the results derived from each section of the research. The first section discusses an attempt to upscale the continuous flow synthesis of triethoxysilane, based on previous group research. Process Analytical Technologies (PAT), specifically thermocouples, were utilized in this endeavor. The study revealed temperature inconsistencies along the packed bed reactor, which had a notable impact on the reaction capabilities. The subsequent section explores the continuous flow synthesis of monosilane from triethoxysilane. A Design of Experiment (DoE) approach was employed to identify the optimal reaction conditions and compare the effectiveness of two catalysts. The study determined that Amberlyst-A26 emerged as the superior catalyst, offering stability and reasonable conversions over a 24-hour period. In a residence time of 6 minutes and at a temperature of 55 °C, the maximum triethoxysilane conversion of 100% was achieved. PAT, particularly inline FT-IR, was instrumental in monitoring catalyst activity, while continuous flow gas separation techniques facilitated the separation of monosilane. The research also demonstrated further applications of continuous flow techniques in the synthesis of monosilane from tetraethoxysilane and magnesium silicide. The former aimed to , Thesis (PhD) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2024
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Date Issued: 2024-04

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Photocatalytic reduction of CO2 by cobalt doped TiO2 and ZnO micro/nanostructured materials

- Mgolombane, Mvano

Authors: Mgolombane, Mvano
Date: 2020
Subjects: Nanostructures , Catalysis , Nanotechnology , Chemistry
Language: English
Type: Thesis , Masters , MSc
Identifier: http://hdl.handle.net/10948/49171 , vital:41607
Description: Large emissions of carbon dioxide (CO2) in the atmosphere have caused many harmful effects on humans and the environment. Carbon dioxide is a good source C and is used in a number of applications such as synthesis of fossil fuels. Redox reaction of CO2 and H2O with photocatalysts such as TiO2 and ZnO to produce solar fuels is a promising approach in reducing the environmental impacts of greenhouse gasses. This dissertation describes an in-depth synthesis of four photochemical catalysts and their photocatalytic conversion of CO2 to methanol, thereby addressing the above-mentioned problems by applying synthesised nano-based catalysts. Prior to photocatalytic reduction studies, catalysts such as TiO2, Co-doped TiO2, Co-doped TiO2/rGO, ZnO, Co-doped ZnO and Co-doped ZnO/rGO were synthesized and characterized using various spectroscopic and imaging techniques such as Powder X-Ray Diffraction (PXRD), Scanning Electron Microscopy (SEM), Transmission Electron Micrograph (TEM), X-ray Photoelectron Spectroscopy (XPS), Brunner- Emmet- Teller measurement (BET), Thermogravimetry Analysis (TGA) and UV-Vis Diffuse Reflectance Spectroscopy (UV-Vis-DRS). The conversion yield of CO2 to methanol on TiO2, Co-doped TiO2 and Co-doped TiO2/rGO reached 32.3 μmol/gcat, 730 μmol/gcat and 936 μmol/gcat, respectively, after 7 h of irradiation. Theoretical studies via Density functional theory (DFT) revealed that doping TiO2 with Co ions facilitated the formation of adsorbed carbonate or CO2•- species, as CO2 adsorbs onto Co-doped TiO2 surface with binding energy (BE) of -18.12 KJ/mol. The photocatalytic activities of ZnO-based nanomaterials found that Co-doped ZnO/rGO with high ratio of Co, reduced graphene (rGO) and large surface area (10.62 m2g-1) possessed higher CH3OH (30.1 μmol/g) in comparison with Co-doped ZnO (27.3 μmol/g) and ZnO (7.5 μmol/g). The research will deepen the understanding that TiO2 based photocatalyst show higher activity and the mole ratio (Ti/Zn:Co) influences nanocomposites performance and provide new ideas for designing efficient photocatalysts.
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Date Issued: 2020

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Synthesis and application of fluorescent triazolyl-coumarin based chemosensors

- Schoeman, Stiaan

Authors: Schoeman, Stiaan
Date: 2020
Subjects: Chemistry
Language: English
Type: Thesis , Masters , MSc
Identifier: http://hdl.handle.net/10948/47454 , vital:39992
Description: The search for a fluorescent chemosensor with high selectivity and sensitivity that can be used for the detection of trace amounts of a toxic transition metal or heavy metal ions have gained immense popularity in recent years. Coumarin derivatives have been widely used as the basis of these fluorescent chemosensors by which a 1,2,3-triazole ring is used as the binding site for such metal ions. The benefits of chemosensors include nearly eliminating the need for tedious sample preparation and highly skilled operators. Therefore, enabling quantitative and qualitative measurement in both a lab setting and on-site. In addition, chemosensors provide a more sensitive and selective detection method at low-cost. A variety of chemosensors were designed and synthesized, in which some synthesis steps were refined to obtain better yields and purer products. Chemosensors designed, in this study, can be divided into novel triazolyl-coumarin derivatives without a spacer 1C – 1D and with a spacer between the coumarin and triazole ring (2D and 2E). 1C – 1D were characterized by 1H NMR, 13C NMR and IR and photophysical properties were investigated in DMF. 2D and 2E could not be purified and further investigation was discontinued. An overall enhancement was observed for the chemosensors 1C – 1D in the presence of 24 different ions that were tested. 1C had a quenching effect in the presence of Cd2+, however, competition studies revealed that 1C is not selective in the presence of competing metal cations. Molecular modelling studies were performed on sensors 1C – 1G in the presence of various ions. The molecular modelling studies provided invaluable insights into the binding of the selected metal ions as well as revealed a variety of binding sites. In addition, the space-filled depictions offered insights into the overlapping during binding which had an effect in the electrostatic potential maps of the chemosensors..
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Date Issued: 2020

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Synthesis of 2,4-Xylidine in continuous flow systems

- Sagandira, Mellisa Brenda

Authors: Sagandira, Mellisa Brenda
Date: 2020
Subjects: Chemistry, Physical and theoretical -- Research , Chemistry
Language: English
Type: Thesis , Masters , MSc
Identifier: http://hdl.handle.net/10948/49270 , vital:41616
Description: The continuous flow synthesis of 2,4-xylidine, an important compound in the fine chemical, pharmaceutical as well as the dyes and pigments industries was investigated in this study utilizing 1,3-dimethylbenzene as starting material. The first step involves the highly exothermic nitration of 1,3-dimethylbenzene with mixed acid to afford two nitro isomers, namely 1,3-dimethyl-2-nitrobenzene and 2,4-dimethyl-1-nitrobenzene. Since 2,4-xylidine is the targeted isomer, it is important to get a higher proportion of its nitration precursor 2,4-dimethyl-1-nitrobenzene. A safe and efficient synthesis of 2,4-dimethyl-1-nitrobenzene was therefore developed in continuous flow. This was aided by the micro reactor’s large surface area-to-volume ratio, one of the many features of continuous flow synthesis that enable rapid dissipation of heat allowing exothermic reactions to be conducted safely at ambient or higher temperatures. Two nitration protocols were developed using different micro reactors, a sonicated 1 ml PTFE tube reactor and 2 ml Uniqsis chip reactor. Using a sonicated PTFE tube reactor at room temperature and 15 min residence time, 2,4-dimethyl-1-nitrobenzene was afforded in 100 % conversion and 80 % selectivity. An increase in selectivity to 95 % and 90 % conversion towards 2,4-dimethyl-1-nitrobenzene was achieved using a 2 ml Uniqsis chip reactor at room temperature in 6 min residence time. This was accounted for due to efficient mixing of the two phases brought about by the reactor’s mixing structures, which are designed to create turbulent mixing. Scale-up synthesis of 2,4-dimethyl-1-nitrobenzene was conducted in a 4.5 ml LTF-XXL-ST-04 reactor at room temperature and 6 min residence time affording 90 % conversion and 95 % selectivity with a throughput of 16.6 g/h. Subsequently, reduction of 2,4-dimethyl-1-nitrobenzene to afford 2,4-xylidine was investigated in a 1 ml PTFE tube reactor (0.8 mm ID) using hydrazine in the presence of iron (III) 2,4-pentanedionate catalyst. Maximum conversion of 75 % was achieved at 170 °C in 15 min residence time. A more efficient reduction protocol was developed in a 2.7 ml packed column reactor (10 mm ID) using hydrazine in the presence of Pd/C at 50 °C and 2.5 min residence time affording 94 % conversion towards 2,4-xylidine. Lastly, multistep synthesis of 2,4-xylidine was performed using optimum conditions found using the 2 ml Uniqsis chip reactor and 2.7 ml packed column reactor with the incorporation of a phase separator. Joining the two reactors into a single continuous step afforded 100 % conversion and 95 % selectivity towards 2,4-xylidine with 8 min total residence time. Nitration of other organic compounds followed by reduction of the resultant nitro products was also investigated under respective optimum conditions determined for nitration of 1,3-dimethylbenzene and reduction of 2,4-dimethyl-1-nitrobenzene.
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Date Issued: 2020

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Synthesis of L-menthyl glyoxylate, an important intermediate in the manufacture of ARVS, using flow chemistry technology

- Moyo, McQuillan

Authors: Moyo, McQuillan
Date: 2017
Subjects: Chemistry , Pharmaceutical chemistry , Organic compounds -- Synthesis
Language: English
Type: Thesis , Masters , MSc
Identifier: http://hdl.handle.net/10948/12019 , vital:27018
Description: Herein an alternative approach to the conventional batch synthesis of L-menthyl glyoxylate hydrate (MGH), an important intermediate in the synthesis of drugs of importance is reported, through flow chemistry technology. MGH was initially synthesized in batch and various reaction parameters optimized. It was found to proceed to completion after 6 hours of esterifying glyoxylic acid with excess alcohol (L-menthol) in the presence of a catalyst, ideally amberlyst-15 (an ion exchange resin) at 105 °C giving a yield of 72 %. The batch reaction conditions were adopted in a continuous flow synthesis setup, using the Labtrix Start system, in which reaction conditions were optimized. The optimization of glyoxylic acid conversion (92 %) in the Labtrix Start system gave reaction conditions that resulted in low MGH selectivity (25 %) whereas the optimization for MGH selectivity (100 %) gave a conversion a poor glyoxylic acid conversion (15 %). The FlowSyn system fitted with a column reactor gave the best results, in which the optimum conditions were an excess of L-menthol (1.5 M, 6.0 equiv.), temperature (80 °C) and a residence time of 2.5 minutes with a high selectivity (77 %) and average conversion (50 %). The optimized reaction conditions for conversion and selectivity on the different flow systems did not vary significantly and similar trends were observed for the systems. It was shown that an increase in temperature, mole equivalents and residence time led to an increase in MGH conversion in all flow systems. The scale up of the esterification reaction from the Labtrix Start system (19 μL microreactor) to the FlowSyn system fitted with a 2 mL reactor chip, showed that the reaction proceeds with a slight drop in selectivity from 100 % to 92 % while conversion dropped from 15 to 12 %. On the contrary, a significant drop in conversion and selectivity were observed when the FlowSyn column reactor was up-scaled to the Elite-tubular furnace, owing to the poor mixing in the larger channel size reactor.
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Date Issued: 2017

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The kinetics and associated equilibria of high oxidation state osmium complexes

- McFadzean, Belinda Julie

Authors: McFadzean, Belinda Julie
Date: 2007
Subjects: Chemical equilibrium , Osmium , Chemical kinetics , Chemistry
Language: English
Type: Thesis , Doctoral , PhD
Identifier: vital:10371 , http://hdl.handle.net/10948/732 , Chemical equilibrium , Osmium , Chemical kinetics , Chemistry
Description: The reduction of osmium tetroxide by a series of alcohols was studied spectrophotometrically. The reaction was observed to occur in two steps, unlike previously reported studies on this reaction. The identities of both reactants and products were established via a range of techniques. Equilibrium and kinetic data were gathered and reaction models were evaluated using equilibrium and kinetic modelling software. The following complexation reaction model emerged that simulates both the equilibrium and kinetic data. Os(VIII) + RCH2OHOs(VI) + RCHO2 Os(VIII) + Os(VI)k+2k1Complexk-2 Conditional rate constants and equilibrium constants were generated. Rate constants for the alcohol reactions were correlated with the Taft σ* constant. The ρ* value obtained (-1.4) is consistent with a hydride transfer mechanism coupled with synchronous removal of the hydroxyl proton. The identity of the osmium(VIII)-osmium(VI) complex has been suggested. Thermodynamic parameters were also reported. The rate constants for benzyl alcohol and 2-chloroethanol deviated from those predicted by the Taft plot. An explanation of enhanced resonance effects is offered for benzyl alcohol and an alternative reaction mechanism, involving proton abstraction, is offered for 2-chloroethanol. The reaction of the oxidation products of alcohols, namely ketones, with osmium tetroxide produced rate constants that were, perhaps surprisingly, far larger than those of the alcohols. A reaction mechanism for the oxidation of the ketones is suggested, which involves the enolate ion as the reactive starting reagent.
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Date Issued: 2007

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