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Pulse radiolysis study of the oxidation of the I− ions with the radical anions Br2 ·− in an aqueous solution: formation and properties of the radical anion BrI·−

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Abstract

The radiation chemical redox transformations in solutions of bromides in the presence of minor additives of iodides were studied by pulse radiolysis. The change in the concentrations of the Br− and I− ions changes the ratio of the formed short-lived radical anions Br2 ·−, BrI·−, and I2 ·−. The spectrum of the mixed radical anion BrI·− contains a broad optical band at 370 nm with ɛ370 = 9650 L mol−1 cm−1. The reduction potential of the BrI·−/Br−, I− pair is 1.25 V. The rate constants for the forward and backward reactions Br2 ·− + I− ⇌ BrI·− + Br− are k f = 4.3·109 and k r = 1.0·105 L mol−1 s−1, respectively; for the reactions BrI·− ⇌ Br− + I·, k f = 5.7·108 s−1 and k r = 1.0·1010 L mol−1 s−1.

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Authors and Affiliations

  1. Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, 31 Leninsky prosp., 119991, Moscow, Russian Federation

    B. G. Ershov & A. V. Gordeeva

  2. Hahn-Meitner Institute, 100 Gluniker Str., 14109, Berlin, Germany

    E. Janata

Authors
  1. B. G. Ershov
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  2. E. Janata
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  3. A. V. Gordeeva
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Correspondence to B. G. Ershov.

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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1787–1792, September, 2008.

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Ershov, B.G., Janata, E. & Gordeeva, A.V. Pulse radiolysis study of the oxidation of the I− ions with the radical anions Br2 ·− in an aqueous solution: formation and properties of the radical anion BrI·− . Russ Chem Bull 57, 1821–1826 (2008). https://doi.org/10.1007/s11172-008-0245-y

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  • DOI: https://doi.org/10.1007/s11172-008-0245-y

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