Atmospheric chemistry of t-CF3CH=CHCl: products and mechanisms of the gas-phase reactions with chlorine atoms and hydroxyl radicals

Mads Peter Sulbæk Andersen; Ole John Nielsen; M. D. Hurley; T. J. Wallington

doi:10.1039/c1cp22925g

Atmospheric chemistry of t-CF₃CH=CHCl: products and mechanisms of the gas-phase reactions with chlorine atoms and hydroxyl radicals

Mads Peter Sulbæk Andersen, Ole John Nielsen, M. D. Hurley, T. J. Wallington

Department of Chemistry

17 Citations (Scopus)

Abstract

FTIR-smog chamber techniques were used to study the products and mechanisms of the Cl atom and OH radical initiated oxidation of trans-3,3,3-trifluoro-1- chloro-propene, t-CF ₃CHCHCl, in 700 Torr of air or N ₂/O ₂ diluent at 296 ± 2 K. The reactions of Cl atoms and OH radicals with t-CF ₃CHCHCl occur via addition to the CC double bond; chlorine atoms add 15 ± 5% at the terminal carbon and 85 ± 5% at the central carbon, OH radicals add approximately 40% at the terminal carbon and 60% at the central carbon. The major products in the Cl atom initiated oxidation of t-CF ₃CHCHCl were CF ₃CHClCHO and CF ₃C(O)CHCl ₂, minor products were CF ₃CHO, HCOCl and CF ₃COCl. The yields of CF ₃C(O)CHCl ₂, CF ₃CHClCOCl and CF ₃COCl increased at the expense of CF ₃CHO, HCOCl and CF ₃CHClCHO as the O ₂ partial pressure was increased over the range 10-700 Torr. Chemical activation plays a significant role in the fate of CF ₃CH(O)CHCl ₂ and CF ₃CClHCHClO radicals. In addition to reaction with O ₂ to yield CF ₃COCl and HO ₂ the major competing fate of CF ₃CHClO is Cl elimination to give CF ₃CHO (not C-C bond scission as previously thought). As part of this study k(Cl + CF ₃C(O)CHCl ₂) = (2.3 ± 0.3) × 10 ^-14 and k(Cl + CF ₃CHClCHO) = (7.5 ± 2.0) × 10 ^-12 cm ³ molecule ^-1 s ^-1 were determined using relative rate techniques. Reaction with OH radicals is the major atmospheric sink for t-CF ₃CHCHCl. Chlorine atom elimination giving the enol CF ₃CHCHOH appears to be the sole atmospheric fate of the CF ₃CHCHClOH radicals. The yield of CF ₃COOH in the atmospheric oxidation of t-CF ₃CHCHCl will be negligible (<2%). The results are discussed with respect to the atmospheric chemistry and environmental impact of t-CF ₃CHCHCl.

Original language	English
Journal	Physical Chemistry Chemical Physics
Volume	14
Issue number	5
Pages (from-to)	1735-1748
Number of pages	14
ISSN	1463-9076
DOIs	https://doi.org/10.1039/c1cp22925g
Publication status	Published - 7 Feb 2012

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Atmospheric chemistry of t-CF₃CH=CHCl: products and mechanisms of the gas-phase reactions with chlorine atoms and hydroxyl radicals. / Andersen, Mads Peter Sulbæk ; Nielsen, Ole John; Hurley, M. D. et al.
In: Physical Chemistry Chemical Physics, Vol. 14, No. 5, 07.02.2012, p. 1735-1748.

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@article{25cb082bb1ca4498a60fd52dde03b476,

title = "Atmospheric chemistry of t-CF3CH=CHCl: products and mechanisms of the gas-phase reactions with chlorine atoms and hydroxyl radicals",

abstract = "FTIR-smog chamber techniques were used to study the products and mechanisms of the Cl atom and OH radical initiated oxidation of trans-3,3,3-trifluoro-1- chloro-propene, t-CF 3CHCHCl, in 700 Torr of air or N 2/O 2 diluent at 296 ± 2 K. The reactions of Cl atoms and OH radicals with t-CF 3CHCHCl occur via addition to the CC double bond; chlorine atoms add 15 ± 5% at the terminal carbon and 85 ± 5% at the central carbon, OH radicals add approximately 40% at the terminal carbon and 60% at the central carbon. The major products in the Cl atom initiated oxidation of t-CF 3CHCHCl were CF 3CHClCHO and CF 3C(O)CHCl 2, minor products were CF 3CHO, HCOCl and CF 3COCl. The yields of CF 3C(O)CHCl 2, CF 3CHClCOCl and CF 3COCl increased at the expense of CF 3CHO, HCOCl and CF 3CHClCHO as the O 2 partial pressure was increased over the range 10-700 Torr. Chemical activation plays a significant role in the fate of CF 3CH(O)CHCl 2 and CF 3CClHCHClO radicals. In addition to reaction with O 2 to yield CF 3COCl and HO 2 the major competing fate of CF 3CHClO is Cl elimination to give CF 3CHO (not C-C bond scission as previously thought). As part of this study k(Cl + CF 3C(O)CHCl 2) = (2.3 ± 0.3) × 10 -14 and k(Cl + CF 3CHClCHO) = (7.5 ± 2.0) × 10 -12 cm 3 molecule -1 s -1 were determined using relative rate techniques. Reaction with OH radicals is the major atmospheric sink for t-CF 3CHCHCl. Chlorine atom elimination giving the enol CF 3CHCHOH appears to be the sole atmospheric fate of the CF 3CHCHClOH radicals. The yield of CF 3COOH in the atmospheric oxidation of t-CF 3CHCHCl will be negligible (<2%). The results are discussed with respect to the atmospheric chemistry and environmental impact of t-CF 3CHCHCl.",

author = "Andersen, {Mads Peter Sulb{\ae}k} and Nielsen, {Ole John} and Hurley, {M. D.} and Wallington, {T. J.}",

year = "2012",

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doi = "10.1039/c1cp22925g",

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T1 - Atmospheric chemistry of t-CF3CH=CHCl

T2 - products and mechanisms of the gas-phase reactions with chlorine atoms and hydroxyl radicals

AU - Andersen, Mads Peter Sulbæk

AU - Nielsen, Ole John

AU - Hurley, M. D.

AU - Wallington, T. J.

PY - 2012/2/7

Y1 - 2012/2/7

N2 - FTIR-smog chamber techniques were used to study the products and mechanisms of the Cl atom and OH radical initiated oxidation of trans-3,3,3-trifluoro-1- chloro-propene, t-CF 3CHCHCl, in 700 Torr of air or N 2/O 2 diluent at 296 ± 2 K. The reactions of Cl atoms and OH radicals with t-CF 3CHCHCl occur via addition to the CC double bond; chlorine atoms add 15 ± 5% at the terminal carbon and 85 ± 5% at the central carbon, OH radicals add approximately 40% at the terminal carbon and 60% at the central carbon. The major products in the Cl atom initiated oxidation of t-CF 3CHCHCl were CF 3CHClCHO and CF 3C(O)CHCl 2, minor products were CF 3CHO, HCOCl and CF 3COCl. The yields of CF 3C(O)CHCl 2, CF 3CHClCOCl and CF 3COCl increased at the expense of CF 3CHO, HCOCl and CF 3CHClCHO as the O 2 partial pressure was increased over the range 10-700 Torr. Chemical activation plays a significant role in the fate of CF 3CH(O)CHCl 2 and CF 3CClHCHClO radicals. In addition to reaction with O 2 to yield CF 3COCl and HO 2 the major competing fate of CF 3CHClO is Cl elimination to give CF 3CHO (not C-C bond scission as previously thought). As part of this study k(Cl + CF 3C(O)CHCl 2) = (2.3 ± 0.3) × 10 -14 and k(Cl + CF 3CHClCHO) = (7.5 ± 2.0) × 10 -12 cm 3 molecule -1 s -1 were determined using relative rate techniques. Reaction with OH radicals is the major atmospheric sink for t-CF 3CHCHCl. Chlorine atom elimination giving the enol CF 3CHCHOH appears to be the sole atmospheric fate of the CF 3CHCHClOH radicals. The yield of CF 3COOH in the atmospheric oxidation of t-CF 3CHCHCl will be negligible (<2%). The results are discussed with respect to the atmospheric chemistry and environmental impact of t-CF 3CHCHCl.

AB - FTIR-smog chamber techniques were used to study the products and mechanisms of the Cl atom and OH radical initiated oxidation of trans-3,3,3-trifluoro-1- chloro-propene, t-CF 3CHCHCl, in 700 Torr of air or N 2/O 2 diluent at 296 ± 2 K. The reactions of Cl atoms and OH radicals with t-CF 3CHCHCl occur via addition to the CC double bond; chlorine atoms add 15 ± 5% at the terminal carbon and 85 ± 5% at the central carbon, OH radicals add approximately 40% at the terminal carbon and 60% at the central carbon. The major products in the Cl atom initiated oxidation of t-CF 3CHCHCl were CF 3CHClCHO and CF 3C(O)CHCl 2, minor products were CF 3CHO, HCOCl and CF 3COCl. The yields of CF 3C(O)CHCl 2, CF 3CHClCOCl and CF 3COCl increased at the expense of CF 3CHO, HCOCl and CF 3CHClCHO as the O 2 partial pressure was increased over the range 10-700 Torr. Chemical activation plays a significant role in the fate of CF 3CH(O)CHCl 2 and CF 3CClHCHClO radicals. In addition to reaction with O 2 to yield CF 3COCl and HO 2 the major competing fate of CF 3CHClO is Cl elimination to give CF 3CHO (not C-C bond scission as previously thought). As part of this study k(Cl + CF 3C(O)CHCl 2) = (2.3 ± 0.3) × 10 -14 and k(Cl + CF 3CHClCHO) = (7.5 ± 2.0) × 10 -12 cm 3 molecule -1 s -1 were determined using relative rate techniques. Reaction with OH radicals is the major atmospheric sink for t-CF 3CHCHCl. Chlorine atom elimination giving the enol CF 3CHCHOH appears to be the sole atmospheric fate of the CF 3CHCHClOH radicals. The yield of CF 3COOH in the atmospheric oxidation of t-CF 3CHCHCl will be negligible (<2%). The results are discussed with respect to the atmospheric chemistry and environmental impact of t-CF 3CHCHCl.

U2 - 10.1039/c1cp22925g

DO - 10.1039/c1cp22925g

M3 - Journal article

C2 - 22187719

SN - 1463-9076

VL - 14

SP - 1735

EP - 1748

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

IS - 5

ER -

Atmospheric chemistry of t-CF3CH=CHCl: products and mechanisms of the gas-phase reactions with chlorine atoms and hydroxyl radicals

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Atmospheric chemistry of t-CF₃CH=CHCl: products and mechanisms of the gas-phase reactions with chlorine atoms and hydroxyl radicals