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
Comparison of plant diversity in protected and communal lands in the Bushbuckridge lowveld savanna, South Africa
- Authors: Shackleton, Charlie M
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181885 , vital:43777 , xlink:href="https://doi.org/10.1016/S0006-3207(00)00001-X"
- Description: Patterns of higher plant species richness and beta diversity were assessed using standard Modified-Whittaker plots in relation to land use, slope position and mean annual rainfall across a rainfall gradient in the savanna areas of the Bushbuckridge lowveld, South Africa. In particular, comparison of communal areas with adjacent protected areas was important in showing the impacts of potential changes in land use within an overarching catchment management plan. Although most of the protected areas considered preservation of biodiversity as their primary goal, they were characterised by significantly fewer plant species than the adjacent, highly utilised, communal lands, at both the plot and point scale. Slope position also had a significant effect on plant species richness, with eutrophic bottomlands having c. 30% more species than the dystrophic toplands. This adds weight to the need for greater public awareness for the judicious use and management of the sensitive bottomlands, which fringe the primary drainage lines that are vital for sustained supplies of good quality surface water in this semi-arid environment. The total number of species increased with increasing mean annual rainfall across the rainfall gradient. This suggests that, if the catchment management plan aims to identify additional areas for conservation, the higher rainfall areas should be the first to be assessed. Species turnover was greater along the rainfall gradient than the catenal gradient between toplands and bottomlands.
- Full Text:
- Date Issued: 2000
- Authors: Shackleton, Charlie M
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181885 , vital:43777 , xlink:href="https://doi.org/10.1016/S0006-3207(00)00001-X"
- Description: Patterns of higher plant species richness and beta diversity were assessed using standard Modified-Whittaker plots in relation to land use, slope position and mean annual rainfall across a rainfall gradient in the savanna areas of the Bushbuckridge lowveld, South Africa. In particular, comparison of communal areas with adjacent protected areas was important in showing the impacts of potential changes in land use within an overarching catchment management plan. Although most of the protected areas considered preservation of biodiversity as their primary goal, they were characterised by significantly fewer plant species than the adjacent, highly utilised, communal lands, at both the plot and point scale. Slope position also had a significant effect on plant species richness, with eutrophic bottomlands having c. 30% more species than the dystrophic toplands. This adds weight to the need for greater public awareness for the judicious use and management of the sensitive bottomlands, which fringe the primary drainage lines that are vital for sustained supplies of good quality surface water in this semi-arid environment. The total number of species increased with increasing mean annual rainfall across the rainfall gradient. This suggests that, if the catchment management plan aims to identify additional areas for conservation, the higher rainfall areas should be the first to be assessed. Species turnover was greater along the rainfall gradient than the catenal gradient between toplands and bottomlands.
- Full Text:
- Date Issued: 2000
Electrocatalytic behavior of substituted cobalt phthalocyanines towards the oxidation of cysteine
- Maree, Suzanne, Nyokong, Tebello
- Authors: Maree, Suzanne , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293268 , vital:57070 , xlink:href="https://doi.org/10.1016/S0022-0728(00)00281-3"
- Description: Ring substituted cobalt phthalocyanine complexes of the form CoPc(X)4, (where X=NH2, NO2, C(CH3)3, SO3H and COOH) are compared for their catalytic activities towards the oxidation of cysteine. The potential for the electrocatalytic oxidation of cysteine is closely related to the CoIII/CoII couple of the CoPc(X)4 complexes in acidic media and to the CoII/CoI couple in basic media. The catalytic currents and the oxidation potential for cysteine are dependent on the pH of the solution, the potential becoming less positive as the pH increases and the catalytic currents decreasing with increase in pH, for the same concentration of cysteine. The magnitudes of the catalytic currents (after ten scans) for cysteine oxidation at pH 8.3 and on electrodes modified with the CoPc(X)4 complexes increased with the nature of the ring substituent as follows: NO2 less than NH2 less than SO3H less than C(CH3)3 less than COOH.
- Full Text:
- Date Issued: 2000
- Authors: Maree, Suzanne , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293268 , vital:57070 , xlink:href="https://doi.org/10.1016/S0022-0728(00)00281-3"
- Description: Ring substituted cobalt phthalocyanine complexes of the form CoPc(X)4, (where X=NH2, NO2, C(CH3)3, SO3H and COOH) are compared for their catalytic activities towards the oxidation of cysteine. The potential for the electrocatalytic oxidation of cysteine is closely related to the CoIII/CoII couple of the CoPc(X)4 complexes in acidic media and to the CoII/CoI couple in basic media. The catalytic currents and the oxidation potential for cysteine are dependent on the pH of the solution, the potential becoming less positive as the pH increases and the catalytic currents decreasing with increase in pH, for the same concentration of cysteine. The magnitudes of the catalytic currents (after ten scans) for cysteine oxidation at pH 8.3 and on electrodes modified with the CoPc(X)4 complexes increased with the nature of the ring substituent as follows: NO2 less than NH2 less than SO3H less than C(CH3)3 less than COOH.
- Full Text:
- Date Issued: 2000
Electrocatalytic behavior of substituted cobalt phthalocyanines towards the oxidation of cysteine
- Maree, Suzanne, Nyokong, Tebello
- Authors: Maree, Suzanne , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293185 , vital:57063 , xlink:href="https://doi.org/10.1016/S0022-0728(00)00281-3"
- Description: Ring substituted cobalt phthalocyanine complexes of the form CoPc(X)4, (where X=NH2, NO2, C(CH3)3, SO3H and COOH) are compared for their catalytic activities towards the oxidation of cysteine. The potential for the electrocatalytic oxidation of cysteine is closely related to the CoIII/CoII couple of the CoPc(X)4 complexes in acidic media and to the CoII/CoI couple in basic media. The catalytic currents and the oxidation potential for cysteine are dependent on the pH of the solution, the potential becoming less positive as the pH increases and the catalytic currents decreasing with increase in pH, for the same concentration of cysteine. The magnitudes of the catalytic currents (after ten scans) for cysteine oxidation at pH 8.3 and on electrodes modified with the CoPc(X)4 complexes increased with the nature of the ring substituent as follows: NO2 less than NH2 less than SO3H less than C(CH3)3 less than COOH.
- Full Text:
- Date Issued: 2000
- Authors: Maree, Suzanne , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293185 , vital:57063 , xlink:href="https://doi.org/10.1016/S0022-0728(00)00281-3"
- Description: Ring substituted cobalt phthalocyanine complexes of the form CoPc(X)4, (where X=NH2, NO2, C(CH3)3, SO3H and COOH) are compared for their catalytic activities towards the oxidation of cysteine. The potential for the electrocatalytic oxidation of cysteine is closely related to the CoIII/CoII couple of the CoPc(X)4 complexes in acidic media and to the CoII/CoI couple in basic media. The catalytic currents and the oxidation potential for cysteine are dependent on the pH of the solution, the potential becoming less positive as the pH increases and the catalytic currents decreasing with increase in pH, for the same concentration of cysteine. The magnitudes of the catalytic currents (after ten scans) for cysteine oxidation at pH 8.3 and on electrodes modified with the CoPc(X)4 complexes increased with the nature of the ring substituent as follows: NO2 less than NH2 less than SO3H less than C(CH3)3 less than COOH.
- Full Text:
- Date Issued: 2000
Electrocatalytic properties of vitamin B12 towards oxidation and reduction of nitric oxide
- Vilakazi, Sibulelo Lea, Nyokong, Tebello
- Authors: Vilakazi, Sibulelo Lea , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293196 , vital:57064 , xlink:href="https://doi.org/10.1016/S0013-4686(00)00628-9"
- Description: This paper reports on the catalytic behaviour of cyanocobalamin (VB12) towards the reduction and oxidation of nitric oxide. When VB12 is adsorbed on glassy carbon electrodes, it catalyses the reduction of nitric oxide (NO) in pH 4 and 9 buffers. In the absence of NO, cyclic voltammetry shows that VB12 is reduced by a one-step two-electron reduction from CoIII to the CoI species. Addition of NO at pH 9 to solutions of VB12 resulted in the splitting of the cyclic voltammetry peaks as a result of a consecutive one-electron reduction of the central CoIII metal in VB12 to CoII and finally to CoI. The catalytic peak for oxidation of NO on a glassy carbon electrode modified with VB12 was observed at 1.21 V versus Ag∣AgCl, at pH 9. The products of the catalytic reduction of nitric oxide include ammonia and hydroxylamine.
- Full Text:
- Date Issued: 2000
- Authors: Vilakazi, Sibulelo Lea , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293196 , vital:57064 , xlink:href="https://doi.org/10.1016/S0013-4686(00)00628-9"
- Description: This paper reports on the catalytic behaviour of cyanocobalamin (VB12) towards the reduction and oxidation of nitric oxide. When VB12 is adsorbed on glassy carbon electrodes, it catalyses the reduction of nitric oxide (NO) in pH 4 and 9 buffers. In the absence of NO, cyclic voltammetry shows that VB12 is reduced by a one-step two-electron reduction from CoIII to the CoI species. Addition of NO at pH 9 to solutions of VB12 resulted in the splitting of the cyclic voltammetry peaks as a result of a consecutive one-electron reduction of the central CoIII metal in VB12 to CoII and finally to CoI. The catalytic peak for oxidation of NO on a glassy carbon electrode modified with VB12 was observed at 1.21 V versus Ag∣AgCl, at pH 9. The products of the catalytic reduction of nitric oxide include ammonia and hydroxylamine.
- Full Text:
- Date Issued: 2000
Interaction between iron (II) tetrasulfophthalocyanine and the neurotransmitters, serotonin and dopamine
- Oni, Joshua, Nyokong, Tebello
- Authors: Oni, Joshua , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293223 , vital:57066 , xlink:href="https://doi.org/10.1016/S0277-5387(00)00421-6"
- Description: This work reports on the kinetics of interaction of iron(II) tetrasulfophthalocyanine, [FeTSPc]4−, with dopamine (DA) and serotonin (5-HT). The interaction results in the coordination of dopamine and serotonin to [FeTSPc]4−, followed by internal electron transfer and the formation of [(DA+)FeITSPc]4− and [(5-HT+) FeITSPc]4− complexes, respectively. The rate constants for the coordination of dopamine or serotonin to [FeTSPc]4− and the formation of the FeITSPc species were found to be kf=6.8 and 9.3 dm3 mol−1 s−1, respectively. The equilibrium constants were 2.2×103 and 1.5×103 dm3 mol−1, respectively, for the interaction of dopamine or serotonin to [FeTSPc]4−.
- Full Text:
- Date Issued: 2000
- Authors: Oni, Joshua , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293223 , vital:57066 , xlink:href="https://doi.org/10.1016/S0277-5387(00)00421-6"
- Description: This work reports on the kinetics of interaction of iron(II) tetrasulfophthalocyanine, [FeTSPc]4−, with dopamine (DA) and serotonin (5-HT). The interaction results in the coordination of dopamine and serotonin to [FeTSPc]4−, followed by internal electron transfer and the formation of [(DA+)FeITSPc]4− and [(5-HT+) FeITSPc]4− complexes, respectively. The rate constants for the coordination of dopamine or serotonin to [FeTSPc]4− and the formation of the FeITSPc species were found to be kf=6.8 and 9.3 dm3 mol−1 s−1, respectively. The equilibrium constants were 2.2×103 and 1.5×103 dm3 mol−1, respectively, for the interaction of dopamine or serotonin to [FeTSPc]4−.
- Full Text:
- Date Issued: 2000
Interaction of nitric oxide with cobalt (II) tetrasulfophthalocyanine
- Vilakazi, Sibulelo, Nyokong, Tebello
- Authors: Vilakazi, Sibulelo , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293235 , vital:57067 , xlink:href="https://doi.org/10.1016/S0277-5387(99)00373-3"
- Description: The interaction of nitric oxide (NO) with cobalt(II) tetrasulfophthalocyanine [Co(II)TSPc]4−) has been studied. Coordination of NO is accompanied by electron transfer from the central metal in [Co(II)TSPc]4−, the resulting complex being represented as [(NO−)Co(III)TSPc]4−. The rate constant for the formation of this species is kf=142±7 dm3 mol−1 s−1 and an equilibrium constant of 3.0±0.5×105 dm3 mol−1 was obtained. When adsorbed to a glassy carbon electrode, [Co(II)TSPc]4− catalyses the oxidation and reduction of NO, with a detection limit of the order of 10−9 mol dm−3. Ammonia and hydroxylamine are some of the reduction products obtained for the reduction of NO on [Co(II)TSPc]4−-modified glassy carbon electrodes.
- Full Text:
- Date Issued: 2000
- Authors: Vilakazi, Sibulelo , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293235 , vital:57067 , xlink:href="https://doi.org/10.1016/S0277-5387(99)00373-3"
- Description: The interaction of nitric oxide (NO) with cobalt(II) tetrasulfophthalocyanine [Co(II)TSPc]4−) has been studied. Coordination of NO is accompanied by electron transfer from the central metal in [Co(II)TSPc]4−, the resulting complex being represented as [(NO−)Co(III)TSPc]4−. The rate constant for the formation of this species is kf=142±7 dm3 mol−1 s−1 and an equilibrium constant of 3.0±0.5×105 dm3 mol−1 was obtained. When adsorbed to a glassy carbon electrode, [Co(II)TSPc]4− catalyses the oxidation and reduction of NO, with a detection limit of the order of 10−9 mol dm−3. Ammonia and hydroxylamine are some of the reduction products obtained for the reduction of NO on [Co(II)TSPc]4−-modified glassy carbon electrodes.
- Full Text:
- Date Issued: 2000
Photocatalytic properties of neodymium diphthalocyanine towards the transformation of 4-chlorophenol
- Nensala, Ngudiankama, Nyokong, Tebello
- Authors: Nensala, Ngudiankama , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/${Handle} , vital:58491 , xlink:href="https://doi.org/10.1016/S1381-1169(00)00283-1"
- Description: Photolysis of aqueous solutions of 4-chlorophenol (4-Cp) in the presence of solid neodymium diphthalocyanine ([Pc(−2)NdPc(−2)]−) and oxygen using visible and ultraviolet (UV) radiation resulted in the formation of a number of products. For photolysis in the visible region, phenol, benzoquinone, hydroquinone were observed as intermediates and 4-chlorocatechol (4-CC) as the main product; intermediates similar to those observed for visible photolysis were obtained. Langmuir–Hinshelwood kinetic model was used for treatment of photochemical data.
- Full Text:
- Date Issued: 2000
Photocatalytic properties of neodymium diphthalocyanine towards the transformation of 4-chlorophenol
- Authors: Nensala, Ngudiankama , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/${Handle} , vital:58491 , xlink:href="https://doi.org/10.1016/S1381-1169(00)00283-1"
- Description: Photolysis of aqueous solutions of 4-chlorophenol (4-Cp) in the presence of solid neodymium diphthalocyanine ([Pc(−2)NdPc(−2)]−) and oxygen using visible and ultraviolet (UV) radiation resulted in the formation of a number of products. For photolysis in the visible region, phenol, benzoquinone, hydroquinone were observed as intermediates and 4-chlorocatechol (4-CC) as the main product; intermediates similar to those observed for visible photolysis were obtained. Langmuir–Hinshelwood kinetic model was used for treatment of photochemical data.
- Full Text:
- Date Issued: 2000
Stump size and the number of coppice shoots for selected savanna tree species
- Authors: Shackleton, Charlie M
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181896 , vital:43778 , xlink:href="https://doi.org/10.1016/S0254-6299(15)31074-7"
- Description: Management of coppice dynamics of indigenous savanna trees could assist in increasing the regrowth rates or number of coppice shoots produced. This would be useful in natural resource management programmes to promote sustainable resource management. This study examined the influence of cutting height, stem size and surface area on the number of coppice shoots produced for twelve savanna species from a communal land in the Bushbuckndge lowveld. All species exhibited a strong coppicing ability following cutting. The number of shoots per stump was most frequently related to cutting height, although this was not always the most significant predictor. There were clear differences between species with respect to the number of shoots per unit surface area, the highest being for Albizia harveyii and the least Piliostlgma thonningii. The taller the potential height of a species, the fewer were the coppice shoots per stump surface area.
- Full Text:
- Date Issued: 2000
- Authors: Shackleton, Charlie M
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181896 , vital:43778 , xlink:href="https://doi.org/10.1016/S0254-6299(15)31074-7"
- Description: Management of coppice dynamics of indigenous savanna trees could assist in increasing the regrowth rates or number of coppice shoots produced. This would be useful in natural resource management programmes to promote sustainable resource management. This study examined the influence of cutting height, stem size and surface area on the number of coppice shoots produced for twelve savanna species from a communal land in the Bushbuckndge lowveld. All species exhibited a strong coppicing ability following cutting. The number of shoots per stump was most frequently related to cutting height, although this was not always the most significant predictor. There were clear differences between species with respect to the number of shoots per unit surface area, the highest being for Albizia harveyii and the least Piliostlgma thonningii. The taller the potential height of a species, the fewer were the coppice shoots per stump surface area.
- Full Text:
- Date Issued: 2000
Comparative photosensitised transformation of polychlorophenols with different sulphonated metallophthalocyanine complexes in aqueous medium
- Ozoemena, Kenneth, Kuznetsova, Nina, Nyokong, Tebello
- Authors: Ozoemena, Kenneth , Kuznetsova, Nina , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291520 , vital:56883 , xlink:href="https://doi.org/10.1016/S1381-1169(01)00243-6"
- Description: The relative efficiencies for the oxidation of trichlorophenol (TCP) and pentachlorophenol (PCP), sensitised by sulphonated phthalocyanine complexes containing Zn, Al, Sn and Si as central metals, were studied in aqueous solutions. For the first time, sulphonated silicon and tin phthalocyanines were synthesised and their activity towards photosensitisation of singlet oxygen and photo-oxidation of polychlorophenols was examined. The efficiency of the sensitised photo-oxidative degradation of polychlorophenols depends not only on singlet oxygen quantum yield of sensitiser, but also on its stability. The influence of substrate structure and the pH of the solution on the photo-oxidation efficiency, as well as on the sensitiser photodegradation were studied. It was found that the contribution of the Type II (singlet oxygen-mediated) mechanism to the relative efficiency of the photosensitised photo-oxidation of the phenol, decreased from phenol to p-chlorophenol, TCP and PCP, whereas Type I radical pathway increased. The results obtained for PCP give evidence that electron transfer from the excited sensitiser to the substrate in its unionised form is responsible for enhanced sensitiser photodegradation.
- Full Text:
- Date Issued: 2001
- Authors: Ozoemena, Kenneth , Kuznetsova, Nina , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291520 , vital:56883 , xlink:href="https://doi.org/10.1016/S1381-1169(01)00243-6"
- Description: The relative efficiencies for the oxidation of trichlorophenol (TCP) and pentachlorophenol (PCP), sensitised by sulphonated phthalocyanine complexes containing Zn, Al, Sn and Si as central metals, were studied in aqueous solutions. For the first time, sulphonated silicon and tin phthalocyanines were synthesised and their activity towards photosensitisation of singlet oxygen and photo-oxidation of polychlorophenols was examined. The efficiency of the sensitised photo-oxidative degradation of polychlorophenols depends not only on singlet oxygen quantum yield of sensitiser, but also on its stability. The influence of substrate structure and the pH of the solution on the photo-oxidation efficiency, as well as on the sensitiser photodegradation were studied. It was found that the contribution of the Type II (singlet oxygen-mediated) mechanism to the relative efficiency of the photosensitised photo-oxidation of the phenol, decreased from phenol to p-chlorophenol, TCP and PCP, whereas Type I radical pathway increased. The results obtained for PCP give evidence that electron transfer from the excited sensitiser to the substrate in its unionised form is responsible for enhanced sensitiser photodegradation.
- Full Text:
- Date Issued: 2001
Construction and characterization of carbon paste ultra-microelectrodes
- Oni, Joshua, Westbroek, Philippe, Nyokong, Tebello
- Authors: Oni, Joshua , Westbroek, Philippe , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291531 , vital:56884 , xlink:href="https://doi.org/10.1016/S1388-2481(01)00212-0"
- Description: The construction and characterization of carbon paste ultra-microelectrodes is reported. Besides a disc-shaped electrode, a carbon paste band electrode is studied. It was found that for both electrode configurations steady-state currents were obtained but that with the type of electrode material used for the band electrode, the upper limit of ultra-microelectrode dimensions, which could be used was 100–150 μm. Smaller dimensions for the band electrodes resulted in a high resistance due to the limited conductivity of the carbon paste, when using the optimal paste composition. With cyclic voltammetry, the oxidation of [Fe(CN)6]4− was studied at individual constructed electrodes and at ensembles of individual electrodes. Detection limits of less than 10−6moll−1 were obtained. Using the data of the same curves it was possible to test if the electrodes have errors and about 20% of the constructed electrodes did not pass this test. Finally it was found that these electrodes show good stability.
- Full Text:
- Date Issued: 2001
- Authors: Oni, Joshua , Westbroek, Philippe , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291531 , vital:56884 , xlink:href="https://doi.org/10.1016/S1388-2481(01)00212-0"
- Description: The construction and characterization of carbon paste ultra-microelectrodes is reported. Besides a disc-shaped electrode, a carbon paste band electrode is studied. It was found that for both electrode configurations steady-state currents were obtained but that with the type of electrode material used for the band electrode, the upper limit of ultra-microelectrode dimensions, which could be used was 100–150 μm. Smaller dimensions for the band electrodes resulted in a high resistance due to the limited conductivity of the carbon paste, when using the optimal paste composition. With cyclic voltammetry, the oxidation of [Fe(CN)6]4− was studied at individual constructed electrodes and at ensembles of individual electrodes. Detection limits of less than 10−6moll−1 were obtained. Using the data of the same curves it was possible to test if the electrodes have errors and about 20% of the constructed electrodes did not pass this test. Finally it was found that these electrodes show good stability.
- Full Text:
- Date Issued: 2001
Effect of oligomerization on the photochemical properties of silicon octaphenoxyphthalocyanine
- Maree, M David, Nyokong, Tebello
- Authors: Maree, M David , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291542 , vital:56885 , xlink:href="https://doi.org/10.1016/S1010-6030(01)00485-3"
- Description: The photochemical properties of silicon octaphenoxyphthalocyanines (SiOPPc) oligomerized were studied in dimethylsulfoxide (DMSO) solutions. Oligomers containing 2–5 and 9 SiOPPc rings linked with terephthalate linkages were synthesized. Singlet oxygen quantum yields were found to be in the range 0.11–0.34, and increased with the number of rings up to five rings, a decrease in the quantum yield was observed for nine rings. This is explained in terms of the high aggregation of the oligomer containing nine rings.
- Full Text:
- Date Issued: 2001
- Authors: Maree, M David , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291542 , vital:56885 , xlink:href="https://doi.org/10.1016/S1010-6030(01)00485-3"
- Description: The photochemical properties of silicon octaphenoxyphthalocyanines (SiOPPc) oligomerized were studied in dimethylsulfoxide (DMSO) solutions. Oligomers containing 2–5 and 9 SiOPPc rings linked with terephthalate linkages were synthesized. Singlet oxygen quantum yields were found to be in the range 0.11–0.34, and increased with the number of rings up to five rings, a decrease in the quantum yield was observed for nine rings. This is explained in terms of the high aggregation of the oligomer containing nine rings.
- Full Text:
- Date Issued: 2001
Electrooxidation of cresols on carbon electrodes modified with phthalocyaninato and octabutoxyphthalocyaninato cobalt (II) complexes
- Grootboom, Natasha, Nyokong, Tebello
- Authors: Grootboom, Natasha , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293207 , vital:57065 , xlink:href="https://doi.org/10.1016/S0003-2670(00)01351-9"
- Description: Glassy carbon electrodes (GCE) modified with cobalt(II) phthalocyanine (CoPc-GCE) and cobalt(II) octabutoxyphthalocyanine (CoOBuPc-GCE) were employed for the electrochemical analysis of ortho-, meta-, and para-cresols. The oxidation potential of p-cresol was shifted towards less positive values to a larger extent, when compared to m- and o-cresols, on CoOBuPc-GCE. However, the GCE was less stable when modified with CoOBuPc than with CoPc. This is explained using the possible differences in the orientation of the adsorbed phthalocyanine molecules on the electrode. Bulk electrolysis of p-cresol at anodic potentials (1.0 V versus Ag|AgCl) on carbon electrodes modified with CoPc resulted in the formation of radicals which coupled to form trimeric products. On unmodified carbon electrodes, coupling of the radicals resulted in dimeric products following bulk electrolysis. The products formed following bulk electrolysis were characterized by liquid chromatography coupled with mass spectrometry.
- Full Text:
- Date Issued: 2001
- Authors: Grootboom, Natasha , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293207 , vital:57065 , xlink:href="https://doi.org/10.1016/S0003-2670(00)01351-9"
- Description: Glassy carbon electrodes (GCE) modified with cobalt(II) phthalocyanine (CoPc-GCE) and cobalt(II) octabutoxyphthalocyanine (CoOBuPc-GCE) were employed for the electrochemical analysis of ortho-, meta-, and para-cresols. The oxidation potential of p-cresol was shifted towards less positive values to a larger extent, when compared to m- and o-cresols, on CoOBuPc-GCE. However, the GCE was less stable when modified with CoOBuPc than with CoPc. This is explained using the possible differences in the orientation of the adsorbed phthalocyanine molecules on the electrode. Bulk electrolysis of p-cresol at anodic potentials (1.0 V versus Ag|AgCl) on carbon electrodes modified with CoPc resulted in the formation of radicals which coupled to form trimeric products. On unmodified carbon electrodes, coupling of the radicals resulted in dimeric products following bulk electrolysis. The products formed following bulk electrolysis were characterized by liquid chromatography coupled with mass spectrometry.
- Full Text:
- Date Issued: 2001
Managing regrowth of an indigenous savanna tree species (Terminalia sericea) for fuelwood: The influence of stump dimensions and post-harvest coppice pruning
- Authors: Shackleton, Charlie M
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181672 , vital:43757 , xlink:href="https://doi.org/10.1016/S0961-9534(00)00086-6"
- Description: Most African savannas are subjected to harvesting of wood, especially for fuelwood, charcoal and construction timber. A key attribute of the resilience and productivity of savannas is the ability of damaged trees to regrow from the remaining stump. Survival of the cut stem and growth rate of the resultant coppice shoots is influenced by several factors, including size of the tree, cutting height and the root/shoot ratio after felling. Some of these can be manipulated to maximise subsequent regrowth, but this is little understood for most African savanna species. This study investigated the influence of original tree size, height of cut and post-harvest pruning on regrowth of Terminalia sericea. Regrowth was monitored as the number of coppice shoots, the mean coppice shoot length and the cumulative coppice shoot length per cut stump over four growing seasons. There was a positive relationship between cutting height and number of coppice shoots, but height of cut did not significantly affect mean or cumulative coppice shoot length. Larger stems produced more coppice and had greater mean and cumulative coppice shoot lengths than smaller stems. Post-harvest pruning increased the mean shoot length, but not the cumulative shoot length. After four growing seasons mean shoot length for the single shoot pruning treatment (one shoot left) was 54% greater than for the no prune treatment, whilst the double shoot pruning (two shoots left) was 40% greater. Extrapolated harvest intervals for fuelwood poles were 3–4 years for large stems, 4–5 years for medium-sized stems, and 4–9 years for small stems.
- Full Text:
- Date Issued: 2001
- Authors: Shackleton, Charlie M
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181672 , vital:43757 , xlink:href="https://doi.org/10.1016/S0961-9534(00)00086-6"
- Description: Most African savannas are subjected to harvesting of wood, especially for fuelwood, charcoal and construction timber. A key attribute of the resilience and productivity of savannas is the ability of damaged trees to regrow from the remaining stump. Survival of the cut stem and growth rate of the resultant coppice shoots is influenced by several factors, including size of the tree, cutting height and the root/shoot ratio after felling. Some of these can be manipulated to maximise subsequent regrowth, but this is little understood for most African savanna species. This study investigated the influence of original tree size, height of cut and post-harvest pruning on regrowth of Terminalia sericea. Regrowth was monitored as the number of coppice shoots, the mean coppice shoot length and the cumulative coppice shoot length per cut stump over four growing seasons. There was a positive relationship between cutting height and number of coppice shoots, but height of cut did not significantly affect mean or cumulative coppice shoot length. Larger stems produced more coppice and had greater mean and cumulative coppice shoot lengths than smaller stems. Post-harvest pruning increased the mean shoot length, but not the cumulative shoot length. After four growing seasons mean shoot length for the single shoot pruning treatment (one shoot left) was 54% greater than for the no prune treatment, whilst the double shoot pruning (two shoots left) was 40% greater. Extrapolated harvest intervals for fuelwood poles were 3–4 years for large stems, 4–5 years for medium-sized stems, and 4–9 years for small stems.
- Full Text:
- Date Issued: 2001
Photochemical studies of tetra-2, 3-pyridinoporphyrazines
- Seotsanyana-Mokhosi, Itumeleng, Kuznetsova, Nina, Nyokong, Tebello
- Authors: Seotsanyana-Mokhosi, Itumeleng , Kuznetsova, Nina , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291580 , vital:56889 , xlink:href="https://doi.org/10.1016/S1010-6030(01)00427-0"
- Description: Tetra-2,3-pyridinoporphyrazines and the corresponding water-soluble N,N′,N′′,N′′′-tetramethyl-tetra-2,3-pyridinoporphyrazine complexes, containing central metal atoms; M=Ge, Sn, Si and Zn, were synthesized and their photochemical properties were investigated. The reductive quenching of pyridinoporphyrazines excited states, enhanced relative to phthalocyanines, was considered as the first photochemical step of dyes phototransformation in dimethylformamide (DMF) and dimethylsulfoxide (DMSO) solutions under irradiation with visible light. Efficiency of singlet oxygen photosensitization decreases significantly in the row phthalocyanines, unquaternized, quaternized tetra-2,3-pyridinoporphyrazine metallocomplexes.
- Full Text:
- Date Issued: 2001
- Authors: Seotsanyana-Mokhosi, Itumeleng , Kuznetsova, Nina , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291580 , vital:56889 , xlink:href="https://doi.org/10.1016/S1010-6030(01)00427-0"
- Description: Tetra-2,3-pyridinoporphyrazines and the corresponding water-soluble N,N′,N′′,N′′′-tetramethyl-tetra-2,3-pyridinoporphyrazine complexes, containing central metal atoms; M=Ge, Sn, Si and Zn, were synthesized and their photochemical properties were investigated. The reductive quenching of pyridinoporphyrazines excited states, enhanced relative to phthalocyanines, was considered as the first photochemical step of dyes phototransformation in dimethylformamide (DMF) and dimethylsulfoxide (DMSO) solutions under irradiation with visible light. Efficiency of singlet oxygen photosensitization decreases significantly in the row phthalocyanines, unquaternized, quaternized tetra-2,3-pyridinoporphyrazine metallocomplexes.
- Full Text:
- Date Issued: 2001
Silicon octaphenoxyphthalocyanines
- Maree, M David, Kuznetsova, Nina, Nyokong, Tebello
- Authors: Maree, M David , Kuznetsova, Nina , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291591 , vital:56890 , xlink:href="https://doi.org/10.1016/S1010-6030(01)00409-9"
- Description: Photochemical properties of series of axially substituted silicon octaphenoxyphthalocyanines with aryloxy, siloxy, aminoalkoxy, esters of carboxylic acids and sulphonic acid esters residues as axial ligands were studied in dimethylsulfoxide (DMSO) solution. It was found, that under Q-band excitation axial ligands in compounds studied have the propensity to be changed by hydroxyl groups with quantum yields in the range 10−5 to 10−2 depending on the nature of the axial ligand. Axial substituent phototransformation was followed by slow photobleaching of dihydroxysilicon octaphenoxyphthalocyanine (photoproduct) in self-sensitized singlet oxygen mediated oxidation of the macrocycle. Singlet oxygen quantum yields were found to be in the range 0.15–0.20 for majority of the phthalocyanines (Pc) studied.
- Full Text:
- Date Issued: 2001
- Authors: Maree, M David , Kuznetsova, Nina , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291591 , vital:56890 , xlink:href="https://doi.org/10.1016/S1010-6030(01)00409-9"
- Description: Photochemical properties of series of axially substituted silicon octaphenoxyphthalocyanines with aryloxy, siloxy, aminoalkoxy, esters of carboxylic acids and sulphonic acid esters residues as axial ligands were studied in dimethylsulfoxide (DMSO) solution. It was found, that under Q-band excitation axial ligands in compounds studied have the propensity to be changed by hydroxyl groups with quantum yields in the range 10−5 to 10−2 depending on the nature of the axial ligand. Axial substituent phototransformation was followed by slow photobleaching of dihydroxysilicon octaphenoxyphthalocyanine (photoproduct) in self-sensitized singlet oxygen mediated oxidation of the macrocycle. Singlet oxygen quantum yields were found to be in the range 0.15–0.20 for majority of the phthalocyanines (Pc) studied.
- Full Text:
- Date Issued: 2001
Simultaneous voltammetric determination of dopamine and serotonin on carbon paste electrodes modified with iron (II) phthalocyanine complexes
- Oni, Joshua, Nyokong, Tebello
- Authors: Oni, Joshua , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291603 , vital:56891 , xlink:href="https://doi.org/10.1016/S0003-2670(01)00822-4"
- Description: Carbon paste electrodes (CPE) containing iron(II) phthalocyanine (FePc) and iron(II) tetrasulfophthalocyanine ([FeTSPc]4−) were used for the detection of dopamine (DA) and serotonin (5-HT). Both complexes showed catalytic activity towards the detection of DA and 5-HT. The catalytic activities of [FeTSPc]4− and FePc are compared with those of [CoTSPc]4−, [NiTSPc] 4−, CoPc and NiPc complexes and with those of metal(II) tetraaminophthalocyanines (MTAPc, where M=Ni, Co or Fe) complexes. A significant improvement in the reversibility of the DA oxidation couple was observed on [FeTSPc]4− and FePc modified CPE. [FeTSPc]4− and other [MTSPc]4− modified electrodes inhibited the detection of ascorbic acid (AA), a major interferent in the detection of DA. Simultaneous detection of DA and 5-HT on [FeTSPc]4− modified CPE, in the presence of AA, showed that AA does not interfere with the determination of both species. Also no interference between DA and 5-HT was observed.
- Full Text:
- Date Issued: 2001
- Authors: Oni, Joshua , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291603 , vital:56891 , xlink:href="https://doi.org/10.1016/S0003-2670(01)00822-4"
- Description: Carbon paste electrodes (CPE) containing iron(II) phthalocyanine (FePc) and iron(II) tetrasulfophthalocyanine ([FeTSPc]4−) were used for the detection of dopamine (DA) and serotonin (5-HT). Both complexes showed catalytic activity towards the detection of DA and 5-HT. The catalytic activities of [FeTSPc]4− and FePc are compared with those of [CoTSPc]4−, [NiTSPc] 4−, CoPc and NiPc complexes and with those of metal(II) tetraaminophthalocyanines (MTAPc, where M=Ni, Co or Fe) complexes. A significant improvement in the reversibility of the DA oxidation couple was observed on [FeTSPc]4− and FePc modified CPE. [FeTSPc]4− and other [MTSPc]4− modified electrodes inhibited the detection of ascorbic acid (AA), a major interferent in the detection of DA. Simultaneous detection of DA and 5-HT on [FeTSPc]4− modified CPE, in the presence of AA, showed that AA does not interfere with the determination of both species. Also no interference between DA and 5-HT was observed.
- Full Text:
- Date Issued: 2001
Voltammetric determination of nitric oxide on cobalt phthalocyanine modified microelectrodes
- Vilakazi, Sibulelo Lea, Nyokong, Tebello
- Authors: Vilakazi, Sibulelo Lea , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291629 , vital:56893 , xlink:href="https://doi.org/10.1016/S0022-0728(01)00583-6"
- Description: The catalytic activity of a carbon fiber microelectrode modified with cobalt phthalocyanine (CoPc-ME) for the detection of nitric oxide in the presence of possible interfering molecules (dopamine and serotonin) is examined. A linear plot is observed for the variation of the catalytic currents with NO concentration in the presence of excess dopamine and serotonin, showing that NO may be determined in the presence of these molecules. However, oxidation currents due to serotonin were found to decrease with increase in NO concentration. The CoPc-ME could also detect NO added to blood or its components, the oxidation currents for NO, however, decreased rapidly with time. The decrease in currents was slower in blood serum, followed by whole blood, with a faster decrease being observed in blood plasma.
- Full Text:
- Date Issued: 2001
- Authors: Vilakazi, Sibulelo Lea , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291629 , vital:56893 , xlink:href="https://doi.org/10.1016/S0022-0728(01)00583-6"
- Description: The catalytic activity of a carbon fiber microelectrode modified with cobalt phthalocyanine (CoPc-ME) for the detection of nitric oxide in the presence of possible interfering molecules (dopamine and serotonin) is examined. A linear plot is observed for the variation of the catalytic currents with NO concentration in the presence of excess dopamine and serotonin, showing that NO may be determined in the presence of these molecules. However, oxidation currents due to serotonin were found to decrease with increase in NO concentration. The CoPc-ME could also detect NO added to blood or its components, the oxidation currents for NO, however, decreased rapidly with time. The decrease in currents was slower in blood serum, followed by whole blood, with a faster decrease being observed in blood plasma.
- Full Text:
- Date Issued: 2001
Growth patterns of Pterocarpus angolensis in savannas of the South African lowveld
- Authors: Shackleton, Charlie M
- Date: 2002
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/182373 , vital:43824 , xlink:href="https://doi.org/10.1016/S0378-1127(01)00676-4"
- Description: Pterocarpus angolensis D.C. is one of the most valuable indigenous timber species on the African continent south of the equator. Because of its high value, it is actively sought after in a number of countries, and wild populations are diminishing. However, attempts at artificial germination and growth trials have yielded poor results, thus, emphasis needs to be placed on sustainable management of existing populations. Success of in situ management will be enhanced if based on reliable data and knowledge regarding the growth patterns of this species within specific localities and countries. Such comprehensive data are lacking for several countries, including South Africa. This paper presents empirical data on a number of studies investigating the growth patterns of P. angolensis in the central lowveld savannas of South Africa, including phenology, annual diameter increment, size class structure, size of reproductive maturity, and morphometric relationships. The size class profile indicated that there was adequate recruitment of P. angolensis, but with constricted through growth from the suffrutex stage to the sapling stage. A small proportion of individuals attained reproductive maturity at 8 cm diameter, but most were bigger. All stems were reproductively mature by 26 cm diameter. This is below the minimum size for harvesting which is dictated by the need for a well developed heartwood. Annual growth was strongly related to stem size and rainfall during the growing season. Basal area increment of small stems was approximately four times greater than mature stems, and declined with increasing stem size. Over the 6-year-period and across all stem sizes, mean diameter increment was 4.5 mm per year. This rate is towards the lower end of the range of reported growth rates from other countries, and poses particular challenges for the sustainable management of this species in South African savannas.
- Full Text:
- Date Issued: 2002
- Authors: Shackleton, Charlie M
- Date: 2002
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/182373 , vital:43824 , xlink:href="https://doi.org/10.1016/S0378-1127(01)00676-4"
- Description: Pterocarpus angolensis D.C. is one of the most valuable indigenous timber species on the African continent south of the equator. Because of its high value, it is actively sought after in a number of countries, and wild populations are diminishing. However, attempts at artificial germination and growth trials have yielded poor results, thus, emphasis needs to be placed on sustainable management of existing populations. Success of in situ management will be enhanced if based on reliable data and knowledge regarding the growth patterns of this species within specific localities and countries. Such comprehensive data are lacking for several countries, including South Africa. This paper presents empirical data on a number of studies investigating the growth patterns of P. angolensis in the central lowveld savannas of South Africa, including phenology, annual diameter increment, size class structure, size of reproductive maturity, and morphometric relationships. The size class profile indicated that there was adequate recruitment of P. angolensis, but with constricted through growth from the suffrutex stage to the sapling stage. A small proportion of individuals attained reproductive maturity at 8 cm diameter, but most were bigger. All stems were reproductively mature by 26 cm diameter. This is below the minimum size for harvesting which is dictated by the need for a well developed heartwood. Annual growth was strongly related to stem size and rainfall during the growing season. Basal area increment of small stems was approximately four times greater than mature stems, and declined with increasing stem size. Over the 6-year-period and across all stem sizes, mean diameter increment was 4.5 mm per year. This rate is towards the lower end of the range of reported growth rates from other countries, and poses particular challenges for the sustainable management of this species in South African savannas.
- Full Text:
- Date Issued: 2002
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