Role of excited CF3CFHO radicals in the atmospheric chemistry of HFC-134a

T. J. Wallington; M. D. Hurley; J. M. Fracheboud; J. J. Orlando; G. S. Tyndall; J. Sehested; T. E. Møgelberg; O. J. Nielsen

Role of excited CF₃CFHO radicals in the atmospheric chemistry of HFC-134a

T. J. Wallington^*, M. D. Hurley, J. M. Fracheboud, J. J. Orlando, G. S. Tyndall, J. Sehested, T. E. Møgelberg, O. J. Nielsen

^*Corresponding author af dette arbejde

129 Citationer (Scopus)

Abstract

The atmospheric degradation of HFC-134a (CF₃CFH₂) proceeds via the formation of CF₃CFHO radicals. Long path length FTIR environmental chamber techniques were used to study the atmospheric fate of CF₃-CFHO radicals. Two competing reaction pathways were identified for CF₃CFHO radicals: reaction with O₂, CF₃CFHO + O₂ → CF₃C(O)F + HO₂, and decomposition via C-C bond scission, CF₃CFHO + M → CF₃ + HC(O)F + M. CF₃CFHO radicals were produced by two different reactions: either via the self-reaction of CF₃CFHO₂ radicals or via the CF₃CFHO₂ + NO reaction. It was found that decomposition was much more important when CF₃CFHO radicals were produced via the CF₃CFHO₂ + NO reaction than when they were produced via the self-reaction of CF₃CFHO₂ radicals. We ascribe this observation to the formation of vibrationally excited CF₃CFHO* radicals in the CF₃CFHO₂ + NO reaction. Rapid decomposition of CF₃-CFHO* radicals limits the formation of CF₃C(O)F and hence CF₃COOH in the atmospheric degradation of HFC-134a. We estimate that the CF₃COOH yield from atmospheric oxidation of HFC-134a is 7-20%. Vibrationally excited alkoxy radicals may play an important role in the atmospheric chemistry of other organic compounds.

Originalsprog	Engelsk
Tidsskrift	Journal of Physical Chemistry
Vol/bind	100
Udgave nummer	46
Sider (fra-til)	18116-18122
Antal sider	7
ISSN	0022-3654
Status	Udgivet - 14 nov. 1996

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@article{1782228be4cb401ba2d9186736ec951c,

title = "Role of excited CF3CFHO radicals in the atmospheric chemistry of HFC-134a",

abstract = "The atmospheric degradation of HFC-134a (CF3CFH2) proceeds via the formation of CF3CFHO radicals. Long path length FTIR environmental chamber techniques were used to study the atmospheric fate of CF3-CFHO radicals. Two competing reaction pathways were identified for CF3CFHO radicals: reaction with O2, CF3CFHO + O2 → CF3C(O)F + HO2, and decomposition via C-C bond scission, CF3CFHO + M → CF3 + HC(O)F + M. CF3CFHO radicals were produced by two different reactions: either via the self-reaction of CF3CFHO2 radicals or via the CF3CFHO2 + NO reaction. It was found that decomposition was much more important when CF3CFHO radicals were produced via the CF3CFHO2 + NO reaction than when they were produced via the self-reaction of CF3CFHO2 radicals. We ascribe this observation to the formation of vibrationally excited CF3CFHO* radicals in the CF3CFHO2 + NO reaction. Rapid decomposition of CF3-CFHO* radicals limits the formation of CF3C(O)F and hence CF3COOH in the atmospheric degradation of HFC-134a. We estimate that the CF3COOH yield from atmospheric oxidation of HFC-134a is 7-20%. Vibrationally excited alkoxy radicals may play an important role in the atmospheric chemistry of other organic compounds.",

author = "Wallington, {T. J.} and Hurley, {M. D.} and Fracheboud, {J. M.} and Orlando, {J. J.} and Tyndall, {G. S.} and J. Sehested and M{\o}gelberg, {T. E.} and Nielsen, {O. J.}",

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language = "English",

volume = "100",

pages = "18116--18122",

journal = "Journal of Physical Chemistry",

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T1 - Role of excited CF3CFHO radicals in the atmospheric chemistry of HFC-134a

AU - Wallington, T. J.

AU - Hurley, M. D.

AU - Fracheboud, J. M.

AU - Orlando, J. J.

AU - Tyndall, G. S.

AU - Sehested, J.

AU - Møgelberg, T. E.

AU - Nielsen, O. J.

PY - 1996/11/14

Y1 - 1996/11/14

N2 - The atmospheric degradation of HFC-134a (CF3CFH2) proceeds via the formation of CF3CFHO radicals. Long path length FTIR environmental chamber techniques were used to study the atmospheric fate of CF3-CFHO radicals. Two competing reaction pathways were identified for CF3CFHO radicals: reaction with O2, CF3CFHO + O2 → CF3C(O)F + HO2, and decomposition via C-C bond scission, CF3CFHO + M → CF3 + HC(O)F + M. CF3CFHO radicals were produced by two different reactions: either via the self-reaction of CF3CFHO2 radicals or via the CF3CFHO2 + NO reaction. It was found that decomposition was much more important when CF3CFHO radicals were produced via the CF3CFHO2 + NO reaction than when they were produced via the self-reaction of CF3CFHO2 radicals. We ascribe this observation to the formation of vibrationally excited CF3CFHO* radicals in the CF3CFHO2 + NO reaction. Rapid decomposition of CF3-CFHO* radicals limits the formation of CF3C(O)F and hence CF3COOH in the atmospheric degradation of HFC-134a. We estimate that the CF3COOH yield from atmospheric oxidation of HFC-134a is 7-20%. Vibrationally excited alkoxy radicals may play an important role in the atmospheric chemistry of other organic compounds.

AB - The atmospheric degradation of HFC-134a (CF3CFH2) proceeds via the formation of CF3CFHO radicals. Long path length FTIR environmental chamber techniques were used to study the atmospheric fate of CF3-CFHO radicals. Two competing reaction pathways were identified for CF3CFHO radicals: reaction with O2, CF3CFHO + O2 → CF3C(O)F + HO2, and decomposition via C-C bond scission, CF3CFHO + M → CF3 + HC(O)F + M. CF3CFHO radicals were produced by two different reactions: either via the self-reaction of CF3CFHO2 radicals or via the CF3CFHO2 + NO reaction. It was found that decomposition was much more important when CF3CFHO radicals were produced via the CF3CFHO2 + NO reaction than when they were produced via the self-reaction of CF3CFHO2 radicals. We ascribe this observation to the formation of vibrationally excited CF3CFHO* radicals in the CF3CFHO2 + NO reaction. Rapid decomposition of CF3-CFHO* radicals limits the formation of CF3C(O)F and hence CF3COOH in the atmospheric degradation of HFC-134a. We estimate that the CF3COOH yield from atmospheric oxidation of HFC-134a is 7-20%. Vibrationally excited alkoxy radicals may play an important role in the atmospheric chemistry of other organic compounds.

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M3 - Journal article

AN - SCOPUS:33748481542

SN - 0022-3654

VL - 100

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JO - Journal of Physical Chemistry

JF - Journal of Physical Chemistry

IS - 46

ER -

Role of excited CF3CFHO radicals in the atmospheric chemistry of HFC-134a

Abstract

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Role of excited CF₃CFHO radicals in the atmospheric chemistry of HFC-134a