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Kinetics and product yields of the acetyl peroxy + HO₂ radical reaction studied by photoionization mass spectrometry

Dodson, Leah G. and Shen, Linhan and Savee, John D. and Eddingsaas, Nathan C. and Welz, Oliver and Taatjes, Craig A. and Osborn, David L. and Sander, Stanley P. and Okumura, Mitchio (2014) Kinetics and product yields of the acetyl peroxy + HO₂ radical reaction studied by photoionization mass spectrometry. In: 247th ACS National Meeting & Exposition, 16-20 March 2014, Dallas, TX.

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The acetyl peroxy radical (CH₃C(O)O₂) is a key intermediate in the oxidn. of carbonyl-contg. hydrocarbons in the troposphere. Reaction of acetyl peroxy radicals with HO₂ has been suggested as a source of OH radicals in low-NOₓ conditions. Previous work on this reaction obsd. only two product channels forming (1) peracetic acid and (2) acetic acid. Recent expts. have shown that there is a third channel that generates the radicals OH and acetoxy: CH₃C(O)O₂ + HO₂ → (1) CH₃C(O)OOH + O₂ (2) CH₃C(O)OH + O₃ (3) CH₃C(O)O + O₂ + OH This last pathway to OH formation would then contribute to the apparent isoprene OH recycling suggested by discrepancies between atm. models and field observations of OH. There have, however, been significant disagreements among expts. on the yield of OH in this reaction. We report our preliminary studies of acetyl peroxy reaction with itself and HO₂. Expts. were conducted at the Advanced Light Source synchrotron at the Lawerence Berkeley National Lab. using tunable VUV ionizing radiation coupled to the Sandia National Lab. pulsed-laser-photolysis multiplexed photoionization mass spectrometer to detect time-resolved photofragmets of reactants, intermediates, and products. From these results, we report new values for the branching fractions of the three product channels in the acetyl peroxy + HO₂ radical reaction.

Item Type:Conference or Workshop Item (Paper)
Related URLs:
URLURL TypeDescription Website
Dodson, Leah G.0000-0001-5960-056X
Shen, Linhan0000-0003-3871-655X
Savee, John D.0000-0002-6881-935X
Eddingsaas, Nathan C.0000-0003-1539-5415
Taatjes, Craig A.0000-0002-9271-0282
Osborn, David L.0000-0003-4304-8218
Sander, Stanley P.0000-0003-1424-3620
Okumura, Mitchio0000-0001-6874-1137
Additional Information:© 2014 American Chemical Society.
Record Number:CaltechAUTHORS:20140429-131752018
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:45314
Deposited By: Tony Diaz
Deposited On:29 Apr 2014 20:28
Last Modified:27 Feb 2023 22:54

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