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Issue 16, 1997
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Kinetics of the HO2+BrO reaction overthe temperature range 233–348 K

Abstract

The reaction BrO+HO 2 →products is the rate-limiting step in a key catalytic ozone destruction cycle in the lower stratosphere. In this study a discharge-flow reactor coupled with molecular beam mass spectrometry has been used to study the BrO+HO 2 reaction over the temperature range 233–348 K. Rate constants were measured under pseudo-first-order conditions in separate experiments with first HO 2 and then BrO in excess in an effort to identify possible complications in the reaction conditions. At 298 K, the rate constant was determined to be (1.73±0.61)×10 -11 cm 3 molecule -1 s -1 with HO 2 in excess and (2.05±0.64)×10 -11 cm 3 molecule -1 s -1 with BrO in excess. The combined results of the temperature-dependent experiments gave the following fit to the Arrhenius expression: k=(3.13±0.33)×10 -12 exp(536±206/T) where the quoted uncertainties represent two standard deviations. The reaction mechanism is discussed in light of recent ab initio results on the thermochemistry of isomers of possible reaction intermediates.

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Article type: Paper
DOI: 10.1039/A701583F
Citation: J. Chem. Soc., Faraday Trans., 1997,93, 2683-2691
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    Kinetics of the HO2+BrO reaction over the temperature range 233–348 K

    Z. Li, R. R. Friedl and S. P. Sander, J. Chem. Soc., Faraday Trans., 1997, 93, 2683
    DOI: 10.1039/A701583F

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