| Автор | Becker, Robert H. |
| Автор | Bartlett, Wenzel P. |
| Автор | Urbansky, Edward T. |
| Автор | Margerum, Dale W. |
| Дата выпуска | 2002 |
| dc.description | A pulsed-accelerated-flow (PAF) spectrometer (model V) capable of non-ambient temperature studies of fast reaction kinetics is described. The PAF method uses accelerated flow mixing of reactants during short time periods to enable the resolution of mixing and reaction rate constants. A new mixing/observation cell and cell supports are designed to permit measurement of reaction kinetics from 40 °C to below 0 °C. The cell consists of two machined PEEK [(â OC6H4OC6H4COC6H4â )n] pieces joined together to give an internal solution distribution system, which greatly reduces the number of connections needed compared to previous instruments to bring the reactants together. The reaction between W(CN)8<sup>4â </sup> and IrCl6<sup>2â </sup> in 0.50 M H2SO4 is studied at 0.0, 25.0, and 40.0 °C. Second-order rate constants of 0.650 à 10<sup>8</sup> M<sup>â 1</sup> s<sup>â 1</sup>, 1.05 à 10<sup>8</sup> M<sup>â 1</sup> s<sup>â 1</sup>, and 1.29 à 10<sup>8</sup> M<sup>â 1</sup> s<sup>â 1</sup> are obtained, respectively. These data give activation parameters of Î H<sup>â ¡</sup> = 10.0 ± 0.8 kJ mol<sup>â 1</sup> and Î S<sup>â ¡</sup> = â 58 ± 3 J mol<sup>â 1</sup> K<sup>â 1</sup>. Activation parameters for reverse bromine hydrolysis (HOBr + Br<sup>â </sup> + H<sup>+</sup> â Br2 + H2O) were determined from rate constants measured from 0.0 to 40.0 °C. These were used to calculate the activation parameters for the forward bromine hydrolysis (Î H<sup>â ¡</sup> = 66 ± 1 kJ mol<sup>â 1</sup> and Î S<sup>â ¡</sup> = 10 ± 20 J mol<sup>â 1</sup> K<sup>â 1</sup>). The temperature dependence of the extremely rapid BrCl hydrolysis reaction (in equilibrium with BrCl2<sup>â </sup>) is determined as well. For reactions at temperatures of 25.0 °C, 10.0 °C, and 0.0 °C the values are 3.3 à 10<sup>6</sup> s<sup>â 1</sup>, 2.06 à 10<sup>6</sup> s<sup>â 1</sup>, and 1.75 à 10<sup>6</sup> s<sup>â 1</sup>, respectively. These values correspond to activation parameters of Î H<sup>â ¡</sup> = 15 ± 7 kJ mol<sup>â 1</sup> and Î S<sup>±</sup> = â 71 ± 24 J mol<sup>â 1</sup> K<sup>â 1</sup> for BrCl hydrolysis. |
| Формат | application.pdf |
| Издатель | Royal Society of Chemistry |
| Название | Pulsed-accelerated-flow studies of the temperature dependence of fast reactionsBased on the presentation given at Dalton Discussion No. 4, 10–13th January 2002, Kloster Banz, Germany. |
| Тип | research-article |
| DOI | 10.1039/b107341a |
| Electronic ISSN | 1364-5447 |
| Print ISSN | 1472-7773 |
| Журнал | Journal of the Chemical Society, Dalton Transactions |
| Первая страница | 695 |
| Последняя страница | 700 |
| Аффилиация | Becker Robert H.; Department of Chemistry, Purdue University |
| Аффилиация | BartlettCurrent address: Dow Chemical, Freeport, TX 77541, USA. Wenzel P.; Department of Chemistry, Purdue University |
| Аффилиация | UrbanskyCurrent address: United States Environmental Protection Agency, National Risk Management Research Laboratory, Cincinnati, OH 45268, USA. Edward T.; Department of Chemistry, Purdue University |
| Аффилиация | Margerum Dale W.; Department of Chemistry, Purdue University |
| Выпуск | 5 |
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