Journal
REACTION KINETICS MECHANISMS AND CATALYSIS
Volume 122, Issue 1, Pages 3-19Publisher
SPRINGER
DOI: 10.1007/s11144-017-1231-x
Keywords
Hydroiodofluorocarbons; Photolysis; Reaction with nitrate radical; Atmospheric implications; Cavity ring-down spectroscopy
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Funding
- Japan Society for the Promotion of Science (JSPS) [25340003]
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Hydroiodofluorocarbons (HIFCs) have recently attracted attention as new candidates for replacements for chlorofluorocarbons and bromofluorocarbons. Thus, it is very important for the practical and industrial use of HIFCs to know the atmospheric removal processes of HIFCs emitted into the atmosphere. In this study, the absorption spectra of difluoroiodomethane (CF2HI), 1,1,1-trifluoro-2-iodoethane (CF3CH2I), 1,1,1-trifluoro-3-iodopropane [CF3(CH2)(2)I] and 1,1,1-trifluoro-4-iodobutane [CF3(CH2)(3)I] were experimentally determined to estimate the lifetimes of the removals from the atmosphere by the sunlight photolysis. The absorption maxima for these HIFCs are at similar to 262 nm and their peak absorption cross sections range from 6.8 x 10(-19) to 8.5 x 10(-19) cm(2) molecule(-1). These results suggest that the lifetimes of the studied HIFCs by solar photolysis are ranged from 7.2 to 14 h. The reactions of NO3 with the four HIFCs were also investigated using time-resolved cavity ring-down spectroscopy. The rate constant values of (4.3 +/- 1.1), (5.5 +/- 2.7), (6.6 +/- 3.7), (9.5 +/- 3.1) x 10(-14) cm(3) molecule(-1) s(-1) have been determined for the reactions of NO3 with CF2HI, CF3CH2I, CF3(CH2)(2)I and CF3(CH2)(3)I at 298 K and 100 Torr of total pressure (the errors designate 2 sigma statistical uncertainty). The determined values of the rate constants suggest that the lifetimes of the studied four HIFCs with respect to reactions with NO3 range from 12 to 26 h.
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