Interaction of sulfur dioxide and cyanide with cobalt (II) tetrasulfophthalocyanine in aqueous media
- Thamae, Mamothibe, Nyokong, Tebello
- Authors: Thamae, Mamothibe , Nyokong, Tebello
- Date: 2002
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289595 , vital:56652 , xlink:href="https://doi.org/10.1016/S0277-5387(01)00968-8"
- Description: Kinetic and equilibrium studies for the coordination of cyanide or sulfur dioxide to the cobalt(II) tetrasulfophthalocyanine ([CoTSPc]4−) complex are reported. The equilibrium constant for the coordination of the cyanide under pH 11 conditions and an oxygen atmosphere, and the formation of [(CN−)2Co(III)TSPc]5− species, was found to be 2.1×101 dm3 mol−1 and the rate constant, kf was found to be 7.4 dm3 mol−1 s−1. Similarly, the coordination of SO2 to [CoTSPc]4− occurred with an equilibrium constant of 8.7×101 dm3 mol−1 and a rate constant of 2.1×102 dm3 mol−1 s−1, at pH 11. These rate and equilibrium constants represent the coordination of the second cyanide or sulfur dioxide ligands to the [CoTSPc]4− species. Coordination of the first ligand occurred faster than that of the second ligand in both cases. The coordination is accompanied by the oxidation of the central Co(II) metal with the formation of a Co(III) tetrasulfophthalocyanine species.
- Full Text:
- Date Issued: 2002
Interaction of sulfur dioxide and cyanide with cobalt (II) tetrasulfophthalocyanine in aqueous media
- Authors: Thamae, Mamothibe , Nyokong, Tebello
- Date: 2002
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289595 , vital:56652 , xlink:href="https://doi.org/10.1016/S0277-5387(01)00968-8"
- Description: Kinetic and equilibrium studies for the coordination of cyanide or sulfur dioxide to the cobalt(II) tetrasulfophthalocyanine ([CoTSPc]4−) complex are reported. The equilibrium constant for the coordination of the cyanide under pH 11 conditions and an oxygen atmosphere, and the formation of [(CN−)2Co(III)TSPc]5− species, was found to be 2.1×101 dm3 mol−1 and the rate constant, kf was found to be 7.4 dm3 mol−1 s−1. Similarly, the coordination of SO2 to [CoTSPc]4− occurred with an equilibrium constant of 8.7×101 dm3 mol−1 and a rate constant of 2.1×102 dm3 mol−1 s−1, at pH 11. These rate and equilibrium constants represent the coordination of the second cyanide or sulfur dioxide ligands to the [CoTSPc]4− species. Coordination of the first ligand occurred faster than that of the second ligand in both cases. The coordination is accompanied by the oxidation of the central Co(II) metal with the formation of a Co(III) tetrasulfophthalocyanine species.
- Full Text:
- Date Issued: 2002
pH study of the electrocatalytic SO2 detection at a glassy carbon electrode modified with iron (II) tetrasulfophthalocyanine
- Thamae, Mamothibe, Westbroek, Philippe, Nyokong, Tebello
- Authors: Thamae, Mamothibe , Westbroek, Philippe , Nyokong, Tebello
- Date: 2002
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/304786 , vital:58490 , xlink:href="https://doi.org/10.1007/s00604-002-0914-8"
- Description: The electrocatalytic determination of SO2 is studied as a function of pH at a glassy carbon electrode modified with iron(II)tetrasulfophthalocyanine ([Fe(II)TSPc]4−). It was found in the literature that depending on pH, SO2·xH2O, HSO3 − and/or SO3 2− are the main compounds in solution, that these compounds behave differently at the electrode surface, and that the condition of the electrode surface is stable over the entire pH-range. The use of SO2(g) or sodium sulfite as starting material did result in identical curves except in the pH range from 7.5–9.0. A possible explanation could be given by proposing that SO2·xH2O is very unstable in the presence of SO3 2−. In strongly acidic medium, SO2·xH2O is the main compound, which can be oxidized as well as reduced with exchange of two electrons. HSO3 − is the main compound at pH = 4 and can also be oxidized and reduced with exchange of, respectively, two and four electrons. In alkaline solution sulfite is the main compound and can only be oxidized, also under exchange of two electrons. Detection limits are in the range of 4.0 ± 0.1 × 10−5 and 7.5 ± 0.1 × 10−5 mol L−1, dependent of pH and of the type of reaction (oxidation or reduction) used.
- Full Text:
- Date Issued: 2002
- Authors: Thamae, Mamothibe , Westbroek, Philippe , Nyokong, Tebello
- Date: 2002
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/304786 , vital:58490 , xlink:href="https://doi.org/10.1007/s00604-002-0914-8"
- Description: The electrocatalytic determination of SO2 is studied as a function of pH at a glassy carbon electrode modified with iron(II)tetrasulfophthalocyanine ([Fe(II)TSPc]4−). It was found in the literature that depending on pH, SO2·xH2O, HSO3 − and/or SO3 2− are the main compounds in solution, that these compounds behave differently at the electrode surface, and that the condition of the electrode surface is stable over the entire pH-range. The use of SO2(g) or sodium sulfite as starting material did result in identical curves except in the pH range from 7.5–9.0. A possible explanation could be given by proposing that SO2·xH2O is very unstable in the presence of SO3 2−. In strongly acidic medium, SO2·xH2O is the main compound, which can be oxidized as well as reduced with exchange of two electrons. HSO3 − is the main compound at pH = 4 and can also be oxidized and reduced with exchange of, respectively, two and four electrons. In alkaline solution sulfite is the main compound and can only be oxidized, also under exchange of two electrons. Detection limits are in the range of 4.0 ± 0.1 × 10−5 and 7.5 ± 0.1 × 10−5 mol L−1, dependent of pH and of the type of reaction (oxidation or reduction) used.
- Full Text:
- Date Issued: 2002
Cobalt (II) porphyrazine catalysed reduction of nitrite
- Thamae, Mamothibe, Nyokong, Tebello
- Authors: Thamae, Mamothibe , Nyokong, Tebello
- Date: 1999
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293162 , vital:57061 , xlink:href="https://doi.org/10.1016/S0022-0728(99)00224-7"
- Description: Studies on the catalytic reduction of nitrite on carbon electrodes modified with Co(II) tetra-2,3-pyridinoporphyrazine (CoTppa, 1), N,N′,N′′,N′′′-tetramethyltetra-2,3-pyridinoporphyrazine ([CoTm-2,3-tppa]4+, 2) and Co(II) N,N′,N′′,N′′′-tetramethyltetra-3,4-pyridinoporphyrazine ([CoTm-3,4-tppa]4+, 3) are reported. There is a close correspondence between the proximity of the methyl groups to the porphyrazine ring and the catalytic activity of the porphyrazine complexes. Bulk electrolysis gave ammonia and hydroxylamine as some of the products. The catalytic activity of the cationic complex, 3, towards the detection of low concentrations of nitrite (less than 10−9 M) in water containing sodium sulfate, was compared with the activities of the anionic cobalt(II) tetrasulfophthalocyanine ([CoTSPc]4−, 4) and the mixed [CoIITm-3,4-tppa]4+·[CoTSPc]4− (5) complexes. Complex 5 showed the best catalytic activity of the three in that large currents were obtained for very low concentrations of nitrite.
- Full Text:
- Date Issued: 1999
- Authors: Thamae, Mamothibe , Nyokong, Tebello
- Date: 1999
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293162 , vital:57061 , xlink:href="https://doi.org/10.1016/S0022-0728(99)00224-7"
- Description: Studies on the catalytic reduction of nitrite on carbon electrodes modified with Co(II) tetra-2,3-pyridinoporphyrazine (CoTppa, 1), N,N′,N′′,N′′′-tetramethyltetra-2,3-pyridinoporphyrazine ([CoTm-2,3-tppa]4+, 2) and Co(II) N,N′,N′′,N′′′-tetramethyltetra-3,4-pyridinoporphyrazine ([CoTm-3,4-tppa]4+, 3) are reported. There is a close correspondence between the proximity of the methyl groups to the porphyrazine ring and the catalytic activity of the porphyrazine complexes. Bulk electrolysis gave ammonia and hydroxylamine as some of the products. The catalytic activity of the cationic complex, 3, towards the detection of low concentrations of nitrite (less than 10−9 M) in water containing sodium sulfate, was compared with the activities of the anionic cobalt(II) tetrasulfophthalocyanine ([CoTSPc]4−, 4) and the mixed [CoIITm-3,4-tppa]4+·[CoTSPc]4− (5) complexes. Complex 5 showed the best catalytic activity of the three in that large currents were obtained for very low concentrations of nitrite.
- Full Text:
- Date Issued: 1999
- «
- ‹
- 1
- ›
- »