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

Authors :
Østerstrøm, Freja F.
Andersen, Simone Thirstrup
Sølling, Theis I.
Nielsen, Ole John
Sulbaek Andersen, Mads P.
Source :
Physical Chemistry Chemical Physics (PCCP); 1/7/2017, Vol. 19 Issue 1, p735-750, 16p
Publication Year :
2017

Abstract

The atmospheric fates of Z- and E-CF<subscript>3</subscript>CH=CHCF<subscript>3</subscript> have been studied, investigating the kinetics and the products of the reactions of the two compounds with Cl atoms, OH radicals, OD radicals, and O<subscript>3</subscript>. FTIR smog chamber experiments measured: k(Cl + Z-CF<subscript>3</subscript>CH=CHCF<subscript>3</subscript>) = (2.59 ± 0.47) × 10<superscript>−11</superscript>, k(Cl + E-CF<subscript>3</subscript>CH=CHCF<subscript>3</subscript>) = (1.36 ± 0.27) × 10<superscript>−11</superscript>, k(OH + Z-CF<subscript>3</subscript>CH=CHCF<subscript>3</subscript>) = (4.21 ± 0.62) × 10<superscript>−13</superscript>, k(OH + E-CF<subscript>3</subscript>CH=CHCF<subscript>3</subscript>) = (1.72 ± 0.42) × 10<superscript>−13</superscript>, k(OD + Z-CF<subscript>3</subscript>CH=CHCF<subscript>3</subscript>) = (6.94 ± 1.25) × 10<superscript>−13</superscript>, k(OD + E-CF<subscript>3</subscript>CH=CHCF<subscript>3</subscript>) = (5.61 ± 0.98) × 10<superscript>−13</superscript>, k(O<subscript>3</subscript> + Z-CF<subscript>3</subscript>CH=CHCF<subscript>3</subscript>) = (6.25 ± 0.70) × 10<superscript>−22</superscript>, and k(O<subscript>3</subscript> + E-CF<subscript>3</subscript>CH=CHCF<subscript>3</subscript>) = (4.14 ± 0.42) × 10<superscript>−22</superscript> cm<superscript>3</superscript> molecule<superscript>−1</superscript> s<superscript>−1</superscript> in 700 Torr of air/N<subscript>2</subscript>/O<subscript>2</subscript> diluents at 296 ± 2 K. E-CF<subscript>3</subscript>CH=CHCF<subscript>3</subscript> reacts with Cl atoms to give CF<subscript>3</subscript>CHClC(O)CF<subscript>3</subscript> in a yield indistinguishable from 100%. Z-CF<subscript>3</subscript>CH=CHCF<subscript>3</subscript> reacts with Cl atoms to give (95 ± 10)% CF<subscript>3</subscript>CHClC(O)CF<subscript>3</subscript> and (7 ± 1)% E-CF<subscript>3</subscript>CH=CHCF<subscript>3</subscript>. CF<subscript>3</subscript>CHClC(O)CF<subscript>3</subscript> reacts with Cl atoms to give the secondary product CF<subscript>3</subscript>C(O)Cl in a yield indistinguishable from 100%, with the observed co-products C(O)F<subscript>2</subscript> and CF<subscript>3</subscript>O<subscript>3</subscript>CF<subscript>3</subscript>. The main atmospheric fate for Z- and E-CF<subscript>3</subscript>CH=CHCF<subscript>3</subscript> is reaction with OH radicals. The atmospheric lifetimes of Z- and E-CF<subscript>3</subscript>CH=CHCF<subscript>3</subscript> are estimated as 27 and 67 days, respectively. IR absorption cross sections are reported and the global warming potentials (GWPs) of Z- and E-CF<subscript>3</subscript>CH=CHCF<subscript>3</subscript> for the 100 year time horizon are calculated to be GWP<subscript>100</subscript> = 2 and 7, respectively. This study provides a comprehensive description of the atmospheric fate and impact of Z- and E-CF<subscript>3</subscript>CH=CHCF<subscript>3</subscript>. [ABSTRACT FROM AUTHOR]

Details

Language :
English
ISSN :
14639076
Volume :
19
Issue :
1
Database :
Complementary Index
Journal :
Physical Chemistry Chemical Physics (PCCP)
Publication Type :
Academic Journal
Accession number :
120338299
Full Text :
https://doi.org/10.1039/c6cp07234h