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

Literature Information

Publication Date 2012-02-03
DOI 10.1039/C2CP22834C
Impact Factor 3.676
Authors

Kimberley E. Leather, Asan Bacak, Ruth Wamsley, Alexander Husk, Dudley E. Shallcross, Carl J. Percival


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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: k10(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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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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