Branching ratios for the reaction of selected carbonyl-containing peroxy radicals with hydroperoxy radicals

Alam S. Hasson; Geoffrey S. Tyndall; John J. Orlando; Sukhdeep Singh; Samuel Q. Hernandez; Sean Campbell; Yesenia Ibarra

doi:10.1021/jp211799c

Branching ratios for the reaction of selected carbonyl-containing peroxy radicals with hydroperoxy radicals

Alam S. Hasson
, Geoffrey S. Tyndall
, John J. Orlando
, Sukhdeep Singh
, Samuel Q. Hernandez
, Sean Campbell
, Yesenia Ibarra

Experimental Science Section

California State University Fresno
National Center for Atmospheric Research
University of California at Davis
University of California at Los Angeles
University of California at Irvine

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

45 Scopus citations

Abstract

An important chemical sink for organic peroxy radicals (RO ₂) in the troposphere is reaction with hydroperoxy radicals (HO ₂). Although this reaction is typically assumed to form hydroperoxides as the major products (R1a), acetyl peroxy radicals and acetonyl peroxy radicals have been shown to undergo other reactions (R1b) and (R1c) with substantial branching ratios: RO ₂ + HO ₂ → ROOH + O ₂ (R1a), RO ₂ + HO ₂ → ROH + O ₃ (R1b), RO ₂ + HO ₂ → RO + OH + O ₂ (R1c). Theoretical work suggests that reactions (R1b) and (R1c) may be a general feature of acyl peroxy and α-carbonyl peroxy radicals. In this work, branching ratios for R1a-R1c were derived for six carbonyl-containing peroxy radicals: C ₂H ₅C(O)O ₂, C ₃H ₇C(O)O ₂, CH ₃C(O)CH ₂O ₂, CH ₃C(O)CH(O ₂)CH ₃, CH ₂ClCH(O ₂)C(O)CH ₃, and CH ₂ClC(CH ₃)(O ₂)CHO. Branching ratios for reactions of Cl-atoms with butanal, butanone, methacrolein, and methyl vinyl ketone were also measured as a part of this work. Product yields were determined using a combination of long path Fourier transform infrared spectroscopy, high performance liquid chromatography with fluorescence detection, gas chromatography with flame ionization detection, and gas chromatography-mass spectrometry. The following branching ratios were determined: C ₂H ₅C(O)O ₂, Y _R1a = 0.35 ± 0.1, Y _R1b = 0.25 ± 0.1, and Y _R1c = 0.4 ± 0.1; C ₃H ₇C(O)O ₂, Y _R1a = 0.24 ± 0.15, Y _R1b = 0.29 ± 0.1, and Y _R1c = 0.47 ± 0.15; CH ₃C(O)CH ₂O ₂, Y _R1a = 0.75 ± 0.13, Y _R1b = 0, and Y _R1c = 0.25 ± 0.13; CH ₃C(O)CH(O ₂)CH ₃, Y _R1a = 0.42 ± 0.1, Y _R1b = 0, and Y _R1c = 0.58 ± 0.1; CH ₂ClC(CH ₃)(O ₂)CHO, Y _R1a = 0.2 ± 0.2, Y _R1b = 0, and Y _R1c = 0.8 ± 0.2; and CH ₂ClCH(O ₂)C(O)CH ₃, Y _R1a = 0.2 ± 0.1, Y _R1b = 0, and Y _R1c = 0.8 ± 0.2. The results give insights into possible mechanisms for cycling of OH radicals in the atmosphere.

Original language	English
Pages (from-to)	6264-6281
Number of pages	18
Journal	Journal of Physical Chemistry A
Volume	116
Issue number	24
DOIs	https://doi.org/10.1021/jp211799c
State	Published - Jun 21 2012

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@article{25faaa9af48844c1b367e17510036aa0,

title = "Branching ratios for the reaction of selected carbonyl-containing peroxy radicals with hydroperoxy radicals",

abstract = "An important chemical sink for organic peroxy radicals (RO 2) in the troposphere is reaction with hydroperoxy radicals (HO 2). Although this reaction is typically assumed to form hydroperoxides as the major products (R1a), acetyl peroxy radicals and acetonyl peroxy radicals have been shown to undergo other reactions (R1b) and (R1c) with substantial branching ratios: RO 2 + HO 2 → ROOH + O 2 (R1a), RO 2 + HO 2 → ROH + O 3 (R1b), RO 2 + HO 2 → RO + OH + O 2 (R1c). Theoretical work suggests that reactions (R1b) and (R1c) may be a general feature of acyl peroxy and α-carbonyl peroxy radicals. In this work, branching ratios for R1a-R1c were derived for six carbonyl-containing peroxy radicals: C 2H 5C(O)O 2, C 3H 7C(O)O 2, CH 3C(O)CH 2O 2, CH 3C(O)CH(O 2)CH 3, CH 2ClCH(O 2)C(O)CH 3, and CH 2ClC(CH 3)(O 2)CHO. Branching ratios for reactions of Cl-atoms with butanal, butanone, methacrolein, and methyl vinyl ketone were also measured as a part of this work. Product yields were determined using a combination of long path Fourier transform infrared spectroscopy, high performance liquid chromatography with fluorescence detection, gas chromatography with flame ionization detection, and gas chromatography-mass spectrometry. The following branching ratios were determined: C 2H 5C(O)O 2, Y R1a = 0.35 ± 0.1, Y R1b = 0.25 ± 0.1, and Y R1c = 0.4 ± 0.1; C 3H 7C(O)O 2, Y R1a = 0.24 ± 0.15, Y R1b = 0.29 ± 0.1, and Y R1c = 0.47 ± 0.15; CH 3C(O)CH 2O 2, Y R1a = 0.75 ± 0.13, Y R1b = 0, and Y R1c = 0.25 ± 0.13; CH 3C(O)CH(O 2)CH 3, Y R1a = 0.42 ± 0.1, Y R1b = 0, and Y R1c = 0.58 ± 0.1; CH 2ClC(CH 3)(O 2)CHO, Y R1a = 0.2 ± 0.2, Y R1b = 0, and Y R1c = 0.8 ± 0.2; and CH 2ClCH(O 2)C(O)CH 3, Y R1a = 0.2 ± 0.1, Y R1b = 0, and Y R1c = 0.8 ± 0.2. The results give insights into possible mechanisms for cycling of OH radicals in the atmosphere.",

author = "Hasson, \{Alam S.\} and Tyndall, \{Geoffrey S.\} and Orlando, \{John J.\} and Sukhdeep Singh and Hernandez, \{Samuel Q.\} and Sean Campbell and Yesenia Ibarra",

year = "2012",

month = jun,

day = "21",

doi = "10.1021/jp211799c",

language = "English",

volume = "116",

pages = "6264--6281",

journal = "Journal of Physical Chemistry A",

issn = "1089-5639",

publisher = "American Chemical Society",

number = "24",

}

TY - JOUR

T1 - Branching ratios for the reaction of selected carbonyl-containing peroxy radicals with hydroperoxy radicals

AU - Hasson, Alam S.

AU - Tyndall, Geoffrey S.

AU - Orlando, John J.

AU - Singh, Sukhdeep

AU - Hernandez, Samuel Q.

AU - Campbell, Sean

AU - Ibarra, Yesenia

PY - 2012/6/21

Y1 - 2012/6/21

N2 - An important chemical sink for organic peroxy radicals (RO 2) in the troposphere is reaction with hydroperoxy radicals (HO 2). Although this reaction is typically assumed to form hydroperoxides as the major products (R1a), acetyl peroxy radicals and acetonyl peroxy radicals have been shown to undergo other reactions (R1b) and (R1c) with substantial branching ratios: RO 2 + HO 2 → ROOH + O 2 (R1a), RO 2 + HO 2 → ROH + O 3 (R1b), RO 2 + HO 2 → RO + OH + O 2 (R1c). Theoretical work suggests that reactions (R1b) and (R1c) may be a general feature of acyl peroxy and α-carbonyl peroxy radicals. In this work, branching ratios for R1a-R1c were derived for six carbonyl-containing peroxy radicals: C 2H 5C(O)O 2, C 3H 7C(O)O 2, CH 3C(O)CH 2O 2, CH 3C(O)CH(O 2)CH 3, CH 2ClCH(O 2)C(O)CH 3, and CH 2ClC(CH 3)(O 2)CHO. Branching ratios for reactions of Cl-atoms with butanal, butanone, methacrolein, and methyl vinyl ketone were also measured as a part of this work. Product yields were determined using a combination of long path Fourier transform infrared spectroscopy, high performance liquid chromatography with fluorescence detection, gas chromatography with flame ionization detection, and gas chromatography-mass spectrometry. The following branching ratios were determined: C 2H 5C(O)O 2, Y R1a = 0.35 ± 0.1, Y R1b = 0.25 ± 0.1, and Y R1c = 0.4 ± 0.1; C 3H 7C(O)O 2, Y R1a = 0.24 ± 0.15, Y R1b = 0.29 ± 0.1, and Y R1c = 0.47 ± 0.15; CH 3C(O)CH 2O 2, Y R1a = 0.75 ± 0.13, Y R1b = 0, and Y R1c = 0.25 ± 0.13; CH 3C(O)CH(O 2)CH 3, Y R1a = 0.42 ± 0.1, Y R1b = 0, and Y R1c = 0.58 ± 0.1; CH 2ClC(CH 3)(O 2)CHO, Y R1a = 0.2 ± 0.2, Y R1b = 0, and Y R1c = 0.8 ± 0.2; and CH 2ClCH(O 2)C(O)CH 3, Y R1a = 0.2 ± 0.1, Y R1b = 0, and Y R1c = 0.8 ± 0.2. The results give insights into possible mechanisms for cycling of OH radicals in the atmosphere.

AB - An important chemical sink for organic peroxy radicals (RO 2) in the troposphere is reaction with hydroperoxy radicals (HO 2). Although this reaction is typically assumed to form hydroperoxides as the major products (R1a), acetyl peroxy radicals and acetonyl peroxy radicals have been shown to undergo other reactions (R1b) and (R1c) with substantial branching ratios: RO 2 + HO 2 → ROOH + O 2 (R1a), RO 2 + HO 2 → ROH + O 3 (R1b), RO 2 + HO 2 → RO + OH + O 2 (R1c). Theoretical work suggests that reactions (R1b) and (R1c) may be a general feature of acyl peroxy and α-carbonyl peroxy radicals. In this work, branching ratios for R1a-R1c were derived for six carbonyl-containing peroxy radicals: C 2H 5C(O)O 2, C 3H 7C(O)O 2, CH 3C(O)CH 2O 2, CH 3C(O)CH(O 2)CH 3, CH 2ClCH(O 2)C(O)CH 3, and CH 2ClC(CH 3)(O 2)CHO. Branching ratios for reactions of Cl-atoms with butanal, butanone, methacrolein, and methyl vinyl ketone were also measured as a part of this work. Product yields were determined using a combination of long path Fourier transform infrared spectroscopy, high performance liquid chromatography with fluorescence detection, gas chromatography with flame ionization detection, and gas chromatography-mass spectrometry. The following branching ratios were determined: C 2H 5C(O)O 2, Y R1a = 0.35 ± 0.1, Y R1b = 0.25 ± 0.1, and Y R1c = 0.4 ± 0.1; C 3H 7C(O)O 2, Y R1a = 0.24 ± 0.15, Y R1b = 0.29 ± 0.1, and Y R1c = 0.47 ± 0.15; CH 3C(O)CH 2O 2, Y R1a = 0.75 ± 0.13, Y R1b = 0, and Y R1c = 0.25 ± 0.13; CH 3C(O)CH(O 2)CH 3, Y R1a = 0.42 ± 0.1, Y R1b = 0, and Y R1c = 0.58 ± 0.1; CH 2ClC(CH 3)(O 2)CHO, Y R1a = 0.2 ± 0.2, Y R1b = 0, and Y R1c = 0.8 ± 0.2; and CH 2ClCH(O 2)C(O)CH 3, Y R1a = 0.2 ± 0.1, Y R1b = 0, and Y R1c = 0.8 ± 0.2. The results give insights into possible mechanisms for cycling of OH radicals in the atmosphere.

UR - https://www.scopus.com/pages/publications/84862676031

U2 - 10.1021/jp211799c

DO - 10.1021/jp211799c

M3 - Article

C2 - 22483091

AN - SCOPUS:84862676031

SN - 1089-5639

VL - 116

SP - 6264

EP - 6281

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 24

ER -

Branching ratios for the reaction of selected carbonyl-containing peroxy radicals with hydroperoxy radicals

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