Temperature and pressure dependence of the rate coefficient for the reaction between ClO and CH3O2 in the gas-phase (original) (raw)
* Corresponding authors
a The Centre for Atmospheric Science, The School of Earth, Atmospheric and Environmental Science, The University of Manchester, Simon Building, Brunswick Street, Manchester, UK
E-mail: C.Percival@manchester.ac.uk
b Biogeochemistry Research Centre, School of Chemistry, The University of Bristol, Cantock's Close BS8 1TS, UK
c Centre for Atmospheric Science, Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge
Abstract
A temperature and pressure kinetic study for the CH3O2 + ClO reaction has been performed using the turbulent flow technique with a chemical ionisation mass spectrometry detection system. An Arrhenius expression was obtained for the overall rate coefficient of CH3O2 + ClO reaction: _k_10(T) = (1.96+0.28−0.24) × 10−11 exp[(−626 ± 35)/T] cm3 molecule−1 s−1 where the uncertainty associated with the rate coefficient is given at the one standard deviation level. Over a range of pressure (100–200 Torr) and temperature (298–223 K) no pressure dependence is observed. The smaller rate coefficients measured at lower temperatures compared with both previous low temperature studies are believed to arise through the reduction of secondary chemistry and greater sensitivity in terms of reactant detection (hence much lower initial concentrations were employed). These new data reduce the effectiveness of ozone loss cycles involving reaction of CH3O2 + ClO in the polar stratosphere by around a factor of 1.5 and restrict the importance of the reaction to the tropical and extra-tropical clean marine environments in the troposphere.
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Article information
DOI
https://doi.org/10.1039/C2CP22834C
Article type
Paper
Submitted
06 Sep 2011
Accepted
03 Jan 2012
First published
03 Feb 2012
Download Citation
Phys. Chem. Chem. Phys., 2012,14, 3425-3434
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Temperature and pressure dependence of the rate coefficient for the reaction between ClO and CH3O2 in the gas-phase
K. E. Leather, A. Bacak, R. Wamsley, A. T. Archibald, A. Husk, D. E. Shallcross and C. J. Percival,Phys. Chem. Chem. Phys., 2012, 14, 3425DOI: 10.1039/C2CP22834C
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