The kinetics and associated equilibria of high oxidation state osmium complexes
- 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.
- Full Text:
- Date Issued: 2007
- 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.
- Full Text:
- Date Issued: 2007
Phase equilibria in three component systems alcohol-hydrocarbon-water
- Authors: Siswana, Msimelelo Patrick
- Date: 1992
- Subjects: Chemical equilibrium , Liquid-liquid equilibrium , Alcohol as fuel , Hydrocarbons , Water chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4327 , http://hdl.handle.net/10962/d1004988 , Chemical equilibrium , Liquid-liquid equilibrium , Alcohol as fuel , Hydrocarbons , Water chemistry
- Description: The fuel industry in many parts of the world is blending alcohols with motor fuel either to extend the fuel or to improve its octane rating or both. Unfortunately alcohols are hygroscopic and as a result, water becomes a component of the fuel. This can lead to phase separation and the formation of a water-rich layer which could have serious corrosion consequences. In an attempt to understand the phase-splitting in alcohol-petrol-water blends, phase equilibria in ternary systems (alcohol-hydrocarbon-water) have been determined by experiment. The phase equilibria in these ternary systems are also discussed in terms of modern theories of liquid mixtures and the UNIQUAC theory is applied to the "ethanol + benzene + water" ternary system. The alcohols are all the C₁, C₂, C₃ and C₄ alcohols, and the hydrocarbons include those typically found in petrol, e.g. cyclohexane, benzene and substituted benzenes.
- Full Text:
- Date Issued: 1992
- Authors: Siswana, Msimelelo Patrick
- Date: 1992
- Subjects: Chemical equilibrium , Liquid-liquid equilibrium , Alcohol as fuel , Hydrocarbons , Water chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4327 , http://hdl.handle.net/10962/d1004988 , Chemical equilibrium , Liquid-liquid equilibrium , Alcohol as fuel , Hydrocarbons , Water chemistry
- Description: The fuel industry in many parts of the world is blending alcohols with motor fuel either to extend the fuel or to improve its octane rating or both. Unfortunately alcohols are hygroscopic and as a result, water becomes a component of the fuel. This can lead to phase separation and the formation of a water-rich layer which could have serious corrosion consequences. In an attempt to understand the phase-splitting in alcohol-petrol-water blends, phase equilibria in ternary systems (alcohol-hydrocarbon-water) have been determined by experiment. The phase equilibria in these ternary systems are also discussed in terms of modern theories of liquid mixtures and the UNIQUAC theory is applied to the "ethanol + benzene + water" ternary system. The alcohols are all the C₁, C₂, C₃ and C₄ alcohols, and the hydrocarbons include those typically found in petrol, e.g. cyclohexane, benzene and substituted benzenes.
- Full Text:
- Date Issued: 1992
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