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Reaction dynamics of iridium bromide...
~
Hoag, Craig Michael.
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Reaction dynamics of iridium bromide complexes in aqueous solution.
紀錄類型:
書目-語言資料,印刷品 : Monograph/item
正題名/作者:
Reaction dynamics of iridium bromide complexes in aqueous solution./
作者:
Hoag, Craig Michael.
面頁冊數:
183 p.
附註:
Chair: Robert J. Hanrahan.
Contained By:
Dissertation Abstracts International61-08B.
標題:
Chemistry, Physical. -
電子資源:
http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=9984429
ISBN:
9780599914186
Reaction dynamics of iridium bromide complexes in aqueous solution.
Hoag, Craig Michael.
Reaction dynamics of iridium bromide complexes in aqueous solution.
- 183 p.
Chair: Robert J. Hanrahan.
Thesis (Ph.D.)--University of Florida, 2000.
A stopped-flow apparatus was used to measure the rate of reaction IrBr 63- with Br2. Using second order kinetics, it was found to be 3.11 x 106 M-1 s-1.
ISBN: 9780599914186Subjects--Topical Terms:
560527
Chemistry, Physical.
Reaction dynamics of iridium bromide complexes in aqueous solution.
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Thesis (Ph.D.)--University of Florida, 2000.
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A stopped-flow apparatus was used to measure the rate of reaction IrBr 63- with Br2. Using second order kinetics, it was found to be 3.11 x 106 M-1 s-1.
520
$a
A spectraphotometric study of aqueous solutions of IrBr6 3- showed that IrBr63- converts to IrBr5H2O2- upon standing, and that IrBr63- is also unstable when dissolved in aqueous 25 mM NaBr solution. The spectra taken periodically over time immediately after conversion of the iridium (III) complexes to the (IV) oxidation state changes from the three sharp peaks of IrBr62- to a single broad peak characteristic of IrBr5H2O -. The species IrBr63- converted to IrBr5H2O2- with a half-life consistent with the literature value of 19 minutes.
520
$a
An alternate competition kinetic method was used to determine the rate constant for reaction of IrBr63- with OH radical. The rate constant for the reaction of IrBr63- with OH radical was determined to be 2.8 x 109 M -1 s-1, assuming 50% conversion of IrBr 63- to IrBr5H2O2- . Also, using the standard competition method, the rate constant was measured as 2.6 x 109 M-1 s -1, based on the assumption of 50% conversion to IrBr5 H2O2-.
520
$a
A mechanism for the pulse radiolysis of aqueous solutions of IrBr 62- was investigated using a Gear integrator. From computations of reactant and product concentrations, the simulated change in the absorbance at 634 nm over time was computed and compared to experimental measurements.
520
$a
The stopped-flow apparatus was used to study the reaction of Br 2 with IrBr5H2O2-; both forward and reverse rate constants were determined by kinetic simulation using a Gear integrator. The values determined were kforward = 4.1 x 10 3 M-1 s-1 and kreverse = 2.0 x 107 M-1 s-1.
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