Atmospheric chemistry of Z- and E-CF3CH=CHCF3

Freja F. Østerstrøm; Simone Thirstrup Andersen; Theis I. Sølling; Ole John Nielsen; Mads P. Sulbaek Andersen

doi:10.1039/C6CP07234H

Atmospheric chemistry of Z- and E-CF₃CH=CHCF₃

Freja F. Østerstrøm, Simone Thirstrup Andersen, Theis I. Sølling, Ole John Nielsen, Mads P. Sulbaek Andersen

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Abstract

The atmospheric fates of Z- and E-CF3CH=CHCF3 have been studied, investigating the kinetics and the products of the reactions of the two compounds with Cl atoms, OH radicals, OD radicals, and O3. FTIR smog chamber experiments measured: k(Cl + Z-CF3CH=CHCF3) = (2.59 ± 0.47) × 10−11, k(Cl + E-CF3CH=CHCF3) = (1.36 ± 0.27) × 10−11, k(OH + Z-CF3CH=CHCF3) = (4.21 ± 0.62) × 10−13, k(OH + E-CF3CH=CHCF3) = (1.72 ± 0.42) × 10−13, k(OD + Z-CF3CH=CHCF3) = (6.94 ± 1.25) × 10−13, k(OD + E-CF3CH=CHCF3) = (5.61 ± 0.98) × 10−13, k(O3 + Z-CF3CHCHCF3) = (6.25 ± 0.70) × 10−22, and k(O3 + E-CF3CH=CHCF3) = (4.14 ± 0.42) × 10−22 cm3 molecule−1 s−1 in 700 Torr of air/N2/O2 diluents at 296 ± 2 K. E-CF3CH=CHCF3 reacts with Cl atoms to give CF3CHClC(O)CF3 in a yield indistinguishable from 100%. Z-CF3CH=CHCF3 reacts with Cl atoms to give (95 ± 10)% CF3CHClC(O)CF3 and (7 ± 1)% E-CF3CH=CHCF3. CF3CHClC(O)CF3 reacts with Cl atoms to give the secondary product CF3C(O)Cl in a yield indistinguishable from 100%, with the observed co-products C(O)F2 and CF3O3CF3. The main atmospheric fate for Z- and E-CF3CH=CHCF3 is reaction with OH radicals. The atmospheric lifetimes of Z- and E-CF3CH=CHCF3 are estimated as 27 and 67 days, respectively. IR absorption cross sections are reported and the global warming potentials (GWPs) of Z- and E-CF3CH=CHCF3 for the 100 year time horizon are calculated to be GWP100 = 2 and 7, respectively. This study provides a comprehensive description of the atmospheric fate and impact of Z- and E-CF3CH=CHCF3.

Original language	English
Pages (from-to)	735-750
Number of pages	16
Journal	Physical chemistry chemical physics
Volume	19
Issue number	1
Early online date	29 Nov 2016
DOIs	https://doi.org/10.1039/C6CP07234H
Publication status	Published - 7 Jan 2017

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@article{b74026f5e2904965801c814e5b4b1d26,

title = "Atmospheric chemistry of Z- and E-CF3CH=CHCF3",

abstract = "The atmospheric fates of Z- and E-CF3CH=CHCF3 have been studied, investigating the kinetics and the products of the reactions of the two compounds with Cl atoms, OH radicals, OD radicals, and O3. FTIR smog chamber experiments measured: k(Cl + Z-CF3CH=CHCF3) = (2.59 ± 0.47) × 10−11, k(Cl + E-CF3CH=CHCF3) = (1.36 ± 0.27) × 10−11, k(OH + Z-CF3CH=CHCF3) = (4.21 ± 0.62) × 10−13, k(OH + E-CF3CH=CHCF3) = (1.72 ± 0.42) × 10−13, k(OD + Z-CF3CH=CHCF3) = (6.94 ± 1.25) × 10−13, k(OD + E-CF3CH=CHCF3) = (5.61 ± 0.98) × 10−13, k(O3 + Z-CF3CHCHCF3) = (6.25 ± 0.70) × 10−22, and k(O3 + E-CF3CH=CHCF3) = (4.14 ± 0.42) × 10−22 cm3 molecule−1 s−1 in 700 Torr of air/N2/O2 diluents at 296 ± 2 K. E-CF3CH=CHCF3 reacts with Cl atoms to give CF3CHClC(O)CF3 in a yield indistinguishable from 100%. Z-CF3CH=CHCF3 reacts with Cl atoms to give (95 ± 10)% CF3CHClC(O)CF3 and (7 ± 1)% E-CF3CH=CHCF3. CF3CHClC(O)CF3 reacts with Cl atoms to give the secondary product CF3C(O)Cl in a yield indistinguishable from 100%, with the observed co-products C(O)F2 and CF3O3CF3. The main atmospheric fate for Z- and E-CF3CH=CHCF3 is reaction with OH radicals. The atmospheric lifetimes of Z- and E-CF3CH=CHCF3 are estimated as 27 and 67 days, respectively. IR absorption cross sections are reported and the global warming potentials (GWPs) of Z- and E-CF3CH=CHCF3 for the 100 year time horizon are calculated to be GWP100 = 2 and 7, respectively. This study provides a comprehensive description of the atmospheric fate and impact of Z- and E-CF3CH=CHCF3.",

author = "{\O}sterstr{\o}m, {Freja F.} and Andersen, {Simone Thirstrup} and S{\o}lling, {Theis I.} and Nielsen, {Ole John} and {Sulbaek Andersen}, {Mads P.}",

note = "{\textcopyright} the Owner Societies 2017",

year = "2017",

month = jan,

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doi = "10.1039/C6CP07234H",

language = "English",

volume = "19",

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journal = "Physical chemistry chemical physics ",

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TY - JOUR

T1 - Atmospheric chemistry of Z- and E-CF3CH=CHCF3

AU - Østerstrøm, Freja F.

AU - Andersen, Simone Thirstrup

AU - Sølling, Theis I.

AU - Nielsen, Ole John

AU - Sulbaek Andersen, Mads P.

PY - 2017/1/7

Y1 - 2017/1/7

N2 - The atmospheric fates of Z- and E-CF3CH=CHCF3 have been studied, investigating the kinetics and the products of the reactions of the two compounds with Cl atoms, OH radicals, OD radicals, and O3. FTIR smog chamber experiments measured: k(Cl + Z-CF3CH=CHCF3) = (2.59 ± 0.47) × 10−11, k(Cl + E-CF3CH=CHCF3) = (1.36 ± 0.27) × 10−11, k(OH + Z-CF3CH=CHCF3) = (4.21 ± 0.62) × 10−13, k(OH + E-CF3CH=CHCF3) = (1.72 ± 0.42) × 10−13, k(OD + Z-CF3CH=CHCF3) = (6.94 ± 1.25) × 10−13, k(OD + E-CF3CH=CHCF3) = (5.61 ± 0.98) × 10−13, k(O3 + Z-CF3CHCHCF3) = (6.25 ± 0.70) × 10−22, and k(O3 + E-CF3CH=CHCF3) = (4.14 ± 0.42) × 10−22 cm3 molecule−1 s−1 in 700 Torr of air/N2/O2 diluents at 296 ± 2 K. E-CF3CH=CHCF3 reacts with Cl atoms to give CF3CHClC(O)CF3 in a yield indistinguishable from 100%. Z-CF3CH=CHCF3 reacts with Cl atoms to give (95 ± 10)% CF3CHClC(O)CF3 and (7 ± 1)% E-CF3CH=CHCF3. CF3CHClC(O)CF3 reacts with Cl atoms to give the secondary product CF3C(O)Cl in a yield indistinguishable from 100%, with the observed co-products C(O)F2 and CF3O3CF3. The main atmospheric fate for Z- and E-CF3CH=CHCF3 is reaction with OH radicals. The atmospheric lifetimes of Z- and E-CF3CH=CHCF3 are estimated as 27 and 67 days, respectively. IR absorption cross sections are reported and the global warming potentials (GWPs) of Z- and E-CF3CH=CHCF3 for the 100 year time horizon are calculated to be GWP100 = 2 and 7, respectively. This study provides a comprehensive description of the atmospheric fate and impact of Z- and E-CF3CH=CHCF3.

AB - The atmospheric fates of Z- and E-CF3CH=CHCF3 have been studied, investigating the kinetics and the products of the reactions of the two compounds with Cl atoms, OH radicals, OD radicals, and O3. FTIR smog chamber experiments measured: k(Cl + Z-CF3CH=CHCF3) = (2.59 ± 0.47) × 10−11, k(Cl + E-CF3CH=CHCF3) = (1.36 ± 0.27) × 10−11, k(OH + Z-CF3CH=CHCF3) = (4.21 ± 0.62) × 10−13, k(OH + E-CF3CH=CHCF3) = (1.72 ± 0.42) × 10−13, k(OD + Z-CF3CH=CHCF3) = (6.94 ± 1.25) × 10−13, k(OD + E-CF3CH=CHCF3) = (5.61 ± 0.98) × 10−13, k(O3 + Z-CF3CHCHCF3) = (6.25 ± 0.70) × 10−22, and k(O3 + E-CF3CH=CHCF3) = (4.14 ± 0.42) × 10−22 cm3 molecule−1 s−1 in 700 Torr of air/N2/O2 diluents at 296 ± 2 K. E-CF3CH=CHCF3 reacts with Cl atoms to give CF3CHClC(O)CF3 in a yield indistinguishable from 100%. Z-CF3CH=CHCF3 reacts with Cl atoms to give (95 ± 10)% CF3CHClC(O)CF3 and (7 ± 1)% E-CF3CH=CHCF3. CF3CHClC(O)CF3 reacts with Cl atoms to give the secondary product CF3C(O)Cl in a yield indistinguishable from 100%, with the observed co-products C(O)F2 and CF3O3CF3. The main atmospheric fate for Z- and E-CF3CH=CHCF3 is reaction with OH radicals. The atmospheric lifetimes of Z- and E-CF3CH=CHCF3 are estimated as 27 and 67 days, respectively. IR absorption cross sections are reported and the global warming potentials (GWPs) of Z- and E-CF3CH=CHCF3 for the 100 year time horizon are calculated to be GWP100 = 2 and 7, respectively. This study provides a comprehensive description of the atmospheric fate and impact of Z- and E-CF3CH=CHCF3.

U2 - 10.1039/C6CP07234H

DO - 10.1039/C6CP07234H

M3 - Article

SN - 1463-9076

VL - 19

SP - 735

EP - 750

JO - Physical chemistry chemical physics

JF - Physical chemistry chemical physics

IS - 1

ER -