| 1. |
- Berglund, Johan, et al.
(author)
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Reaction of Peroxomonosulfate Radical with Manganese(II) in Acidic Aqueous Solution. A Pulse Radiolysis Study
- 1994
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In: Journal of the Chemical Society - Faraday Transactions. - : Royal Society of Chemistry (RSC). - 0956-5000 .- 1364-5455. ; 90:21, s. 3309-3313
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Journal article (peer-reviewed)abstract
- The reaction between the SO5– radical and MnII has been proposed to be the most important process for regeneration of MnIII in the MnIII/II-catalysed autoxidation of SIV in acidic aqueous solution. In the present study, the second-order rate constant for this reaction has been determined at pH 3. 0 and 10 mmol dm–3 ionic strength by use of pulse radiolysis. The study was performed in the presence of excess SIV. Under these conditions MnII is distributed among the complexes Mn2+(aq), [Mn(HSO3)]+ and [Mn(SO3)Mn]2+. The rate of reaction decreases as a function of increasing [MnII]total which is rationalized qualitatively by a mechanism involving three parallel reactions between SO5– and the MnII complexes, with rate constants k16, k17 and k18, respectively. Mn2++ SO5– [graphic omitted] Mn3++ HSO5–(16), [Mn(HSO3)]++ SO5– [graphic omitted] [Mn(HSO3)]2+ HSO5–(17), [Mn(SO3)Mn]2++ SO5– [graphic omitted] [Mn(SO3)Mn]3++ HSO5–(18), For increasing total concentrations of MnII, formation of the sulfito-bridged complex is favoured which implies that k18 < k16, k17. Values of the second-order rate constant in the range 2 × 10 108–2 × 1010 dm3 mol–1 s–1 have been determined, depending on which MnII species is predominant. Subsequent slow processes are observed following the formation of MnIII. These reactions have been attributed to the disproportionation of MnIII and reactions between the MnIII species and excess SIV. The implications of the present results for the MnIII/II catalysed autoxidation of SIV are discussed.
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| 2. |
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| 3. |
- Bowman, Lawrence E., et al.
(author)
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A single photon timing instrument that covers a broad temporal range in the reversed timing configuration
- 1993
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In: Review of Scientific Instruments. - : AIP Publishing. - 0034-6748 .- 1089-7623. ; 64:2, s. 338-341
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Journal article (peer-reviewed)abstract
- A versatile single-photon timing instrument based on the reversed timing configuration has been constructed. Unlike similar instruments, the apparatus described here is capable of recording a broad range of excited-state decay times owing to a switched fiber optic delay. This allows the user to readily collect time-resolved luminescence data over a variable time window in the reversed-timing configuration. With proper adjustment of the appropriate components, one can acquire a luminescence decay over a variable time range from less than 1 ns to nearly 1 μs. The full width at half-maximum of the instrument response function is 42 ps. The utility of a switched fiber optic delay is discussed and the device's construction is described.
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| 4. |
- Severin, Kathryn G., et al.
(author)
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Characterization of titanium and zirconium valerate sol-gel films
- 1994
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In: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 6:7, s. 890-898
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Journal article (peer-reviewed)abstract
- FTIR and XPS have been used to characterize titanium and zirconium valerate thin films prepared using sol-gel techniques. Films were prepared by hydrolysis of titanium(IV) isopropoxide or zirconium(IV) n-propoxide in excess valeric acid at room temperature. Film solution chemistry, from precursors to cast films, was followed with FTIR. The structure and chemical composition of films spin cast from fresh and day-old solutions were determined. Results of these studies suggest that all films consist of a metal-oxygen polymer backbone coordinated with bidentate valerate ligands. No evidence for the presence of alkoxide ligands has been found. A small amount of water is present in all cast films. While solution aging experiments indicate that the zirconium film structure does not change with solution reaction time, carboxylate ligand concentrations are higher in titanium films made from aged solutions. Titanium films made from aged solutions contain slightly less than 1.5 valerate ligands/titanium atom. Zirconium films are more highly carboxylated with almost two valerate groups per metal center.
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