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A Product Yield Study of the Reaction of HO2 Radicals with Ethyl Peroxy (C2H5O2), Acetyl Peroxy (CH3C(O)O2), and Acetonyl Peroxy (CH3C(O)CH2O2) Radicals
Abstract
The reaction between HO 2 and RO 2 radicals represents an important chemical sink for HO x radicals in the atmosphere. On the basis of a few product yield studies, these reactions are believed to form hydroperoxides almost exclusively (R8a), although several different reaction channels may be thermodynamically accessible (R8a−d): RO 2 + HO 2 → ROOH + O 2 (R8a); RO 2 + HO 2 → ROH + O 3 (R8b); RO 2 + HO 2 → RO + OH + O 2 (R8c); and RO 2 + HO 2 → R‘CHO + H 2 O + O 2 (R8d). Branching ratios for reaction R8 were measured for three organic peroxy radicals: ethyl peroxy (C 2 H 5 O 2 ), acetyl peroxy (CH 3 C(O)O 2 ), and acetonyl peroxy (CH 3 C(O)CH 2 O 2 ) radicals. Product yields were measured using a combination of long-path Fourier transform infrared spectroscopy and high-performance liquid chromatography with fluorescence detection. Measured branching ratios for the reaction of the three organic peroxy radicals with HO 2 are as follows: ethyl peroxy, Y 8a - ETH > 0.93 ± 0.10, Y 8b - ETH = Y 8c - ETH = Y 8d - ETH = 0; acetyl peroxy, Y 8a - ACT = 0.40 ± 0.16, Y 8b - ACT = 0.20 ± 0.08, Y 8c - ACT = 0.40 ± 0.16, and Y 8d - ACT = 0; acetonyl peroxy, Y 8a - ACN = 0.33 ± 0.10, Y 8b - ACN = Y 8d - ACN = 0, and Y 8c - ACN = 0.67 ± 0.20. The atmospheric implications of these branching ratios are discussed.
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Metadata
- Authors
- Hasson, A. S., Tyndall, G. S., & Orlando, J. J.
- Venue
- The Journal of Physical Chemistry A
- Publisher
- American Chemical Society (ACS)
- Published
- 2004-06-22
- Volume
- 108
- Issue
- 28
- Pages
- 5979-5989
- ISSN
- 1089-5639 (ISSN-L)
- 1520-5215
- OpenAlex
- W2255563666
- Cited by
- 191
- References
- 0
- FWCI
- 3.63
- Type
- journal article
- Language
- en
- Open access
- closed
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