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Kinetics of the OH + NO2 reaction: rate coefficients (217-333 K, 16-1200 mbar) and fall-off parameters for N2 and O2 bath gases

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Amedro,  Damien
Atmospheric Chemistry, Max Planck Institute for Chemistry, Max Planck Society;

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Bunkan,  Arne J. C.
Atmospheric Chemistry, Max Planck Institute for Chemistry, Max Planck Society;

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Berasategui,  Matias
Atmospheric Chemistry, Max Planck Institute for Chemistry, Max Planck Society;

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Crowley,  John N.
Atmospheric Chemistry, Max Planck Institute for Chemistry, Max Planck Society;

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Citation

Amedro, D., Bunkan, A. J. C., Berasategui, M., & Crowley, J. N. (2019). Kinetics of the OH + NO2 reaction: rate coefficients (217-333 K, 16-1200 mbar) and fall-off parameters for N2 and O2 bath gases. Atmospheric Chemistry and Physics, 19(16), 10643-10657. doi:10.5194/acp-19-10643-2019.


Cite as: https://hdl.handle.net/21.11116/0000-0004-CD3D-2
Abstract
The radical terminating, termolecular reaction between OH and NO2 exerts great influence on the NOy∕NOx ratio and O3 formation in the atmosphere. Evaluation panels (IUPAC and NASA) recommend rate coefficients for this reaction that disagree by as much as a factor of 1.6 at low temperature and pressure. In this work, the title reaction was studied by pulsed laser photolysis and laser-induced fluorescence over the pressure range 16–1200 mbar and temperature range 217–333 K in N2 bath gas, with experiments at 295 K (67–333 mbar) for O2. In situ measurement of NO2 using two optical absorption set-ups enabled generation of highly precise, accurate rate coefficients in the fall-off pressure range, appropriate for atmospheric conditions.

We found, in agreement with previous work, that O2 bath gas has a lower collision efficiency than N2 with a relative collision efficiency to N2 of 0.74. Using the Troe-type formulation for termolecular reactions we present a new set of parameters with k0(N2) = 2.6×10−30
 cm6 molecule−2 s−1, k0(O2) = 2.0×10−30 cm6 molecule−2 s−1, m=3.6, k∞=6.3×10−11 cm3 molecule−1 s−1, and Fc=0.39 and compare our results to previous studies in N2 and O2 bath gases.