A product yield study of the reaction of HO 2 radicals with ethyl peroxy (C 2H 5O 2), acetyl peroxy (CH 3C(O)O 2), and acetonyl peroxy (CH 3C(O)CH 2O 2) radicals

Alam S. Hasson; Geoffrey S. Tyndall; John J. Orlando

doi:10.1021/jp048873t

A product yield study of the reaction of HO ₂ radicals with ethyl peroxy (C ₂H ₅O ₂), acetyl peroxy (CH ₃C(O)O ₂), and acetonyl peroxy (CH ₃C(O)CH ₂O ₂) radicals

Alam S. Hasson
, Geoffrey S. Tyndall
, John J. Orlando

Experimental Science Section

Research output: Contribution to journal › Article › peer-review

175 Scopus citations

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 ₂O + O ₂ (R8d). Branching ratios for reaction R8 were measured for three organic peroxy radicals: ethyl peroxy (C ₂H ₅O ₂), acetyl peroxy (CH ₃C(O)O ₂), and acetonyl peroxy (CH ₃C(O)CH ₂O 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.

Original language	English
Pages (from-to)	5979-5989
Number of pages	11
Journal	Journal of Physical Chemistry A
Volume	108
Issue number	28
DOIs	https://doi.org/10.1021/jp048873t
State	Published - Jul 15 2004

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@article{0c999c17e6fe4949a3baa8f4488518cf,

title = "A product yield study of the reaction of HO 2 radicals with ethyl peroxy (C 2H 5O 2), acetyl peroxy (CH 3C(O)O 2), and acetonyl peroxy (CH 3C(O)CH 2O 2) 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 2O + O 2 (R8d). Branching ratios for reaction R8 were measured for three organic peroxy radicals: ethyl peroxy (C 2H 5O 2), acetyl peroxy (CH 3C(O)O 2), and acetonyl peroxy (CH 3C(O)CH 2O 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.",

author = "Hasson, \{Alam S.\} and Tyndall, \{Geoffrey S.\} and Orlando, \{John J.\}",

year = "2004",

month = jul,

day = "15",

doi = "10.1021/jp048873t",

language = "English",

volume = "108",

pages = "5979--5989",

journal = "Journal of Physical Chemistry A",

issn = "1089-5639",

publisher = "American Chemical Society",

number = "28",

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TY - JOUR

T1 - A product yield study of the reaction of HO 2 radicals with ethyl peroxy (C 2H 5O 2), acetyl peroxy (CH 3C(O)O 2), and acetonyl peroxy (CH 3C(O)CH 2O 2) radicals

AU - Hasson, Alam S.

AU - Tyndall, Geoffrey S.

AU - Orlando, John J.

PY - 2004/7/15

Y1 - 2004/7/15

N2 - 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 2O + O 2 (R8d). Branching ratios for reaction R8 were measured for three organic peroxy radicals: ethyl peroxy (C 2H 5O 2), acetyl peroxy (CH 3C(O)O 2), and acetonyl peroxy (CH 3C(O)CH 2O 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.

AB - 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 2O + O 2 (R8d). Branching ratios for reaction R8 were measured for three organic peroxy radicals: ethyl peroxy (C 2H 5O 2), acetyl peroxy (CH 3C(O)O 2), and acetonyl peroxy (CH 3C(O)CH 2O 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.

UR - https://www.scopus.com/pages/publications/3242875153

U2 - 10.1021/jp048873t

DO - 10.1021/jp048873t

M3 - Article

AN - SCOPUS:3242875153

SN - 1089-5639

VL - 108

SP - 5979

EP - 5989

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 28

ER -

A product yield study of the reaction of HO ₂ radicals with ethyl peroxy (C ₂H ₅O ₂), acetyl peroxy (CH ₃C(O)O ₂), and acetonyl peroxy (CH ₃C(O)CH ₂O ₂) radicals

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