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Volume 130, 2005
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Kinetics and product studies of the reaction of Br, Cl, and NO with ClOOCl using discharge-flow mass spectrometry

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Abstract

The kinetics of the reactions Cl + ClOOCl → products (5), Br + ClOOCl → products (7), and NO + ClOOCl → products (8) have been studied as a function of temperature at 1 Torr total pressure using a discharge-flow mass spectrometric technique. The measured rate coefficients, expressed in Arrhenius form, are k5 = (7.60 ± 0.56) × 10−11exp((65.4 ± 17.9)/T) cm3 s−1 for 217 K < T < 298 K, and k7 = (5.88 ± 0.50) × 10−12 exp(−173 ± 20/T) cm3 s−1 for 223 K < T< 298 K. The observed temperature dependencies of these rate coefficients indicate a common direct halogen atom abstraction mechanism. Mass spectral product studies indicate that BrCl is the only major Br-containing product from reaction (7). Extensive product studies were used to estimate that the peroxide form of the ClO-dimer is formed in >90% yield from the ClO self-reaction. No evidence for the formation of ClOClO and ClClO2 was observed. No reaction between NO and ClOOCl was observed and an upper limit of k8 < 1 × 10−15 cm3 s−1 for 220 K < T< 298 K was determined.

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Publication details

The article was received on 05 Jan 2005, accepted on 10 Feb 2005 and first published on 14 Jun 2005


Article type: Paper
DOI: 10.1039/B500179J
Citation: Faraday Discuss., 2005,130, 89-110
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    Kinetics and product studies of the reaction of Br, Cl, and NO with ClOOCl using discharge-flow mass spectrometry

    T. Ingham, S. P. Sander and R. R. Friedl, Faraday Discuss., 2005, 130, 89
    DOI: 10.1039/B500179J

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