Ruthenium and palladium assisted silver transport in silicon carbide
- Authors: O'Connell, Jacques Herman
- Date: 2012
- Subjects: Gas cooled reactors , Ruthenium , Palladium , Silicon carbide
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10404 , http://hdl.handle.net/10948/d1010960 , Gas cooled reactors , Ruthenium , Palladium , Silicon carbide
- Full Text:
- Date Issued: 2012
- Authors: O'Connell, Jacques Herman
- Date: 2012
- Subjects: Gas cooled reactors , Ruthenium , Palladium , Silicon carbide
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10404 , http://hdl.handle.net/10948/d1010960 , Gas cooled reactors , Ruthenium , Palladium , Silicon carbide
- Full Text:
- Date Issued: 2012
Studies towards the synthesis of novel tridentate ligands for use in ruthenium metathesis catalysts
- Authors: Millward, Tanya
- Date: 2009
- Subjects: Ligands , Catalysis , Metathesis (Chemistry) , Ruthenium , Complex compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4360 , http://hdl.handle.net/10962/d1005025 , Ligands , Catalysis , Metathesis (Chemistry) , Ruthenium , Complex compounds
- Description: This work has focussed on the preparation of a variety of tridentate ligands, designed to form ruthenium complexes as potential metathesis catalysts. Various approaches to the tridentate, malonate-tethered imidazolidine system have been investigated, and a promising route to accessing ligands of this type is discussed. A tridentate malonate-tethered pyridine ligand has been successfully prepared and its dithallium salt has been accessed by hydrolysis with thallium carbonate; approaches to a longer-chain analogue have also been investigated. A thallium pyridine-2,6- dicarboxylate ligand has been has been successfully prepared, as have a range of pyridine diamine ligands, with various alkyl and aromatic substituents on the amine donor atoms. Preliminary investigations into the potential of these compounds as ligands for alkylidene ruthenium complexes are reported using molecular modelling techniques. The geometries and steric energies of the ligands and their corresponding complexes have been analysed, and results obtained from two different software packages are compared. Finally, some preliminary complexation studies have been undertaken.
- Full Text:
- Date Issued: 2009
- Authors: Millward, Tanya
- Date: 2009
- Subjects: Ligands , Catalysis , Metathesis (Chemistry) , Ruthenium , Complex compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4360 , http://hdl.handle.net/10962/d1005025 , Ligands , Catalysis , Metathesis (Chemistry) , Ruthenium , Complex compounds
- Description: This work has focussed on the preparation of a variety of tridentate ligands, designed to form ruthenium complexes as potential metathesis catalysts. Various approaches to the tridentate, malonate-tethered imidazolidine system have been investigated, and a promising route to accessing ligands of this type is discussed. A tridentate malonate-tethered pyridine ligand has been successfully prepared and its dithallium salt has been accessed by hydrolysis with thallium carbonate; approaches to a longer-chain analogue have also been investigated. A thallium pyridine-2,6- dicarboxylate ligand has been has been successfully prepared, as have a range of pyridine diamine ligands, with various alkyl and aromatic substituents on the amine donor atoms. Preliminary investigations into the potential of these compounds as ligands for alkylidene ruthenium complexes are reported using molecular modelling techniques. The geometries and steric energies of the ligands and their corresponding complexes have been analysed, and results obtained from two different software packages are compared. Finally, some preliminary complexation studies have been undertaken.
- Full Text:
- Date Issued: 2009
The kinetics and associated reactions of ruthenium(VIII)
- Authors: Van Aswegen, Werner
- Date: 2009
- Subjects: Ruthenium , Ruthenium compounds , Alcohols
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10392 , http://hdl.handle.net/10948/1130 , http://hdl.handle.net/10948/d1008611 , Ruthenium , Ruthenium compounds , Alcohols
- Description: This study investigated the reduction reaction of ruthenium tetroxide by various aliphatic alcohols in acidic medium. UV-Vis spectroscopy still plays an essential role in the analysis and study of volatile ruthenium tetroxide and was used in this study to collect kinetic data. This data was analyzed using graphical and computational methods, such as Mauser diagrams and kinetic simulation software. From the results obtained it is proposed that the reaction occurs by the following two-step reaction model: Ru(VIII) k1 Ru(VI) Ru(VI) k2 k-2 Ru(III) Molar extinction coefficients and conditional rate constants were calculated using kinetic simulating software and a hydride transfer mechanism was proposed. The temperature dependence of this reduction reaction was also investigated and thermodynamic parameters calculated. Ruthenium concentrations were determined using a method employing UV-Vis spectroscopy. The method proved to be a reliable, sensitive and simple technique.
- Full Text:
- Date Issued: 2009
- Authors: Van Aswegen, Werner
- Date: 2009
- Subjects: Ruthenium , Ruthenium compounds , Alcohols
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10392 , http://hdl.handle.net/10948/1130 , http://hdl.handle.net/10948/d1008611 , Ruthenium , Ruthenium compounds , Alcohols
- Description: This study investigated the reduction reaction of ruthenium tetroxide by various aliphatic alcohols in acidic medium. UV-Vis spectroscopy still plays an essential role in the analysis and study of volatile ruthenium tetroxide and was used in this study to collect kinetic data. This data was analyzed using graphical and computational methods, such as Mauser diagrams and kinetic simulation software. From the results obtained it is proposed that the reaction occurs by the following two-step reaction model: Ru(VIII) k1 Ru(VI) Ru(VI) k2 k-2 Ru(III) Molar extinction coefficients and conditional rate constants were calculated using kinetic simulating software and a hydride transfer mechanism was proposed. The temperature dependence of this reduction reaction was also investigated and thermodynamic parameters calculated. Ruthenium concentrations were determined using a method employing UV-Vis spectroscopy. The method proved to be a reliable, sensitive and simple technique.
- Full Text:
- Date Issued: 2009
The reactions of ruthenium (ii) polypyridyl complexes
- Authors: Zheng, Sipeng
- Date: 2009
- Subjects: Ruthenium , Ruthenium compounds , Chemical reactions
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10374 , http://hdl.handle.net/10948/1089 , Ruthenium , Ruthenium compounds , Chemical reactions
- Description: Ruthenium (II) polypyridine complexes in general have been extensively studied because of their unique redox and photochemical properties. A typical example of such complexes is tris(2,2’-bipyridyl) ruthenium (II). In this study, this complex was synthesized and then characterized using electronic spectroscopy and cyclic voltammetry. It was also shown that the ruthenium concentration could be accurately determined using ICP-MS. It was found that the complex is very stable in various chemical environments. It was observed from spectrophotometric investigations that persulphate and lead dioxide easily oxidize Ru(bpy)3 2+ to Ru(bpy)3 3+ in the presence of heat and H2SO4, respectively. It was also observed that the oxidation between Ru(bpy)3 2+ and cerium (IV) occurred at approximately 3:2 [Ce(IV)]/[Ru(II)] mole ratio. The resultant Ru(bpy)3 3+ solution was unstable in the presence of light and recovery of Ru(bpy)3 2+ occurred gradually. The regeneration of Ru(bpy)3 2+ from Ru(bpy)3 3+ was found to be a multistep process, which appears to involve the formation of an intermediate species. The following reaction model was found to best explain the kinetic data obtained: Ru(bpy)3 2+ + Ce(IV) → Ru(bpy)3 3+ Ru(bpy)3 3+ → Ru(bpy)3 2+ Ru(bpy)3 3+ → Ru* intermediate Ru* intermediate → Ru(bpy)3 2+ Theoretical rate constants were also calculated for the same process under the experimental conditions. The comparison between the experimental and theoretical results gave good agreement. In addition, the factors that influence the rate of the regeneration of Ru(bpy)3 2+ from Ru(bpy)3 3+ were also discussed.
- Full Text:
- Date Issued: 2009
- Authors: Zheng, Sipeng
- Date: 2009
- Subjects: Ruthenium , Ruthenium compounds , Chemical reactions
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10374 , http://hdl.handle.net/10948/1089 , Ruthenium , Ruthenium compounds , Chemical reactions
- Description: Ruthenium (II) polypyridine complexes in general have been extensively studied because of their unique redox and photochemical properties. A typical example of such complexes is tris(2,2’-bipyridyl) ruthenium (II). In this study, this complex was synthesized and then characterized using electronic spectroscopy and cyclic voltammetry. It was also shown that the ruthenium concentration could be accurately determined using ICP-MS. It was found that the complex is very stable in various chemical environments. It was observed from spectrophotometric investigations that persulphate and lead dioxide easily oxidize Ru(bpy)3 2+ to Ru(bpy)3 3+ in the presence of heat and H2SO4, respectively. It was also observed that the oxidation between Ru(bpy)3 2+ and cerium (IV) occurred at approximately 3:2 [Ce(IV)]/[Ru(II)] mole ratio. The resultant Ru(bpy)3 3+ solution was unstable in the presence of light and recovery of Ru(bpy)3 2+ occurred gradually. The regeneration of Ru(bpy)3 2+ from Ru(bpy)3 3+ was found to be a multistep process, which appears to involve the formation of an intermediate species. The following reaction model was found to best explain the kinetic data obtained: Ru(bpy)3 2+ + Ce(IV) → Ru(bpy)3 3+ Ru(bpy)3 3+ → Ru(bpy)3 2+ Ru(bpy)3 3+ → Ru* intermediate Ru* intermediate → Ru(bpy)3 2+ Theoretical rate constants were also calculated for the same process under the experimental conditions. The comparison between the experimental and theoretical results gave good agreement. In addition, the factors that influence the rate of the regeneration of Ru(bpy)3 2+ from Ru(bpy)3 3+ were also discussed.
- Full Text:
- Date Issued: 2009
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