Temperature and pressure dependence of the rate coefficient for the reaction between ClO and CH3O2 in the gas-phase

被引:10
|
作者
Leather, Kimberley E. [1 ]
Bacak, Asan [1 ]
Wamsley, Ruth [1 ]
Archibald, Alexander T. [2 ,3 ]
Husk, Alexander [3 ]
Shallcross, Dudley E. [2 ]
Percival, Carl J. [1 ]
机构
[1] Univ Manchester, Sch Earth Atmospher & Environm Sci, Ctr Atmospher Sci, Manchester M13 9PL, Lancs, England
[2] Univ Bristol, Sch Chem, Biogeochem Res Ctr, Bristol BS8 1TS, Avon, England
[3] Univ Cambridge, Dept Chem, Ctr Atmospher Sci, Cambridge CB2 1EW, England
关键词
LASER-INDUCED FLUORESCENCE; PRODUCT BRANCHING RATIOS; ORGANIC PEROXY-RADICALS; DISCHARGE-FLOW; BOUNDARY-LAYER; RATE CONSTANTS; AB-INITIO; KINETICS; OZONE; IO;
D O I
10.1039/c2cp22834c
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
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(-0.24)(+0.28)) x 10(-11) exp[(-626 +/- 35)/T] cm(3) 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.
引用
收藏
页码:3425 / 3434
页数:10
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