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Atmospheric chemistry of Z- and E-CF3CH&z.dbd;CHCF3Electronic supplementary information (ESI) available. See DOI: 10.1039/c6cp07234h
The atmospheric fates of Z - and E -CF 3 CH&z.dbd;CHCF 3 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 3 . FTIR smog chamber experiments measured: k (Cl + Z -CF 3 CH&z.dbd;CHCF 3 ) = (2.59 ±...
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| Main Authors: | , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Online Access: | Get full text |
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| Summary: | The atmospheric fates of
Z
- and
E
-CF
3
CH&z.dbd;CHCF
3
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
3
. FTIR smog chamber experiments measured:
k
(Cl +
Z
-CF
3
CH&z.dbd;CHCF
3
) = (2.59 ± 0.47) × 10
−11
,
k
(Cl +
E
-CF
3
CH&z.dbd;CHCF
3
) = (1.36 ± 0.27) × 10
−11
,
k
(OH +
Z
-CF
3
CH&z.dbd;CHCF
3
) = (4.21 ± 0.62) × 10
−13
,
k
(OH +
E
-CF
3
CH&z.dbd;CHCF
3
) = (1.72 ± 0.42) × 10
−13
,
k
(OD +
Z
-CF
3
CH&z.dbd;CHCF
3
) = (6.94 ± 1.25) × 10
−13
,
k
(OD +
E
-CF
3
CH&z.dbd;CHCF
3
) = (5.61 ± 0.98) × 10
−13
,
k
(O
3
+
Z
-CF
3
CH&z.dbd;CHCF
3
) = (6.25 ± 0.70) × 10
−22
, and
k
(O
3
+
E
-CF
3
CH&z.dbd;CHCF
3
) = (4.14 ± 0.42) × 10
−22
cm
3
molecule
−1
s
−1
in 700 Torr of air/N
2
/O
2
diluents at 296 ± 2 K.
E
-CF
3
CH&z.dbd;CHCF
3
reacts with Cl atoms to give CF
3
CHClC(O)CF
3
in a yield indistinguishable from 100%.
Z
-CF
3
CH&z.dbd;CHCF
3
reacts with Cl atoms to give (95 ± 10)% CF
3
CHClC(O)CF
3
and (7 ± 1)%
E
-CF
3
CH&z.dbd;CHCF
3
. CF
3
CHClC(O)CF
3
reacts with Cl atoms to give the secondary product CF
3
C(O)Cl in a yield indistinguishable from 100%, with the observed co-products C(O)F
2
and CF
3
O
3
CF
3
. The main atmospheric fate for
Z
- and
E
-CF
3
CH&z.dbd;CHCF
3
is reaction with OH radicals. The atmospheric lifetimes of
Z
- and
E
-CF
3
CH&z.dbd;CHCF
3
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
3
CH&z.dbd;CHCF
3
for the 100 year time horizon are calculated to be GWP
100
= 2 and 7, respectively. This study provides a comprehensive description of the atmospheric fate and impact of
Z
- and
E
-CF
3
CH&z.dbd;CHCF
3
.
The first determination of the atmospheric chemistry of
E
-CF
3
CH&z.dbd;CHCF
3
and of the Cl and O
3
initiated atmospheric chemistry of
Z
-CF
3
CH&z.dbd;CHCF
3
. |
|---|---|
| ISSN: | 1463-9076 1463-9084 |
| DOI: | 10.1039/c6cp07234h |