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Pressure and Temperature Dependencies of Rate Coefficients for the Reaction OH + NO₂ + M → Products

Winiberg, Frank A. F. and Zuraski, Kristen and Liu, Yingdi and Sander, Stanley P. and Percival, Carl J. (2020) Pressure and Temperature Dependencies of Rate Coefficients for the Reaction OH + NO₂ + M → Products. Journal of Physical Chemistry A, 124 (49). pp. 10121-10131. ISSN 1089-5639.

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The OH + NO₂ reaction is a critically important process for radical chain termination in the atmosphere with a major impact on the ozone budgets of the troposphere and stratosphere. Rate constants for the reaction of OH + NO₂ + M → products have been measured under conditions relevant to the upper troposphere/lower stratosphere with a laser photolysis–laser-induced fluorescence (LP-LIF) technique augmented by in situ optical spectroscopy for quantification of [NO₂]. The experiments are carried out over the temperature range of 230–293 K and the pressure range 50–750 Torr of N₂ and air and as a function of [O₂]. The observed rate coefficients in N₂ agree with the newest experimental literature data sets and are within experimental uncertainty of current recommended literature values at 293 K but are systematically higher by up to 22% at 700 Torr and 230 K. The efficacy of different falloff parametrizations has been examined and compared to those in literature sources. The collisional quenching efficiency of O₂ was found to be in excellent agreement with current literature sources, and rate coefficients determined in air at 293 and 245 K were observed to be within uncertainty of the rate coefficients measured in N₂ bath gas. This work has improved confidence in the literature rate coefficients under conditions of the lower troposphere (∼760 Torr, 280–310 K) toward the stratosphere (10–100 Torr, 220–250 K).

Item Type:Article
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URLURL TypeDescription
Winiberg, Frank A. F.0000-0003-2801-5581
Zuraski, Kristen0000-0003-3149-6611
Sander, Stanley P.0000-0003-1424-3620
Percival, Carl J.0000-0003-2525-160X
Alternate Title:Pressure and Temperature Dependencies of Rate Coefficients for the Reaction OH + NO2 + M → Products
Additional Information:© 2020 American Chemical Society. Received: September 30, 2020; Revised: October 29, 2020; Published: December 1, 2020. K.Z. was supported by an appointment to the NASA Postdoctoral Program at the NASA Jet Propulsion Laboratory, administered by Universities Space Research Association under a contract with NASA. Support from the NASA Upper Atmosphere Research and Tropospheric Composition Programs is gratefully acknowledged. The authors declare no competing financial interest.
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NASA Postdoctoral ProgramUNSPECIFIED
Issue or Number:49
Record Number:CaltechAUTHORS:20201210-133602227
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Official Citation:Pressure and Temperature Dependencies of Rate Coefficients for the Reaction OH + NO2 + M → Products. Frank A. F. Winiberg, Kristen Zuraski, Yingdi Liu, Stanley P. Sander, and Carl J. Percival. The Journal of Physical Chemistry A 2020 124 (49), 10121-10131; DOI: 10.1021/acs.jpca.0c08920
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:107014
Deposited By: Tony Diaz
Deposited On:10 Dec 2020 21:51
Last Modified:10 Dec 2020 21:51

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