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Issue 16, 1997

Kinetics of the HO2+BrO reaction over the 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.

Article information


J. Chem. Soc., Faraday Trans., 1997,93, 2683-2691
Article type
Paper

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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