TY - JOUR
T1 - Time resolved experiments on the Atmospheric Oxidation of C₂H₆ and some C₂ Hydrofluorocarbons
AU - Olkhov, Rouslan
AU - Smith, Ian
PY - 2003/1/1
Y1 - 2003/1/1
N2 - We report new time-resolved measurements relevant to the atmospheric oxidation of C2H6, CF3CF2H (HFC-125), CF3CH3 (HFC- 143a) and CF3CFH2 (HFC- 134a). The radicals R = C2H5, CF3CF2, CF3CH2 and CF3CFH were produced by photolysis of the corresponding iodides, RI, at 248 nm, using the output from a pulsed excimer laser, in the presence of a large excess of O-2 and with different concentrations of NO present. The loss of NO and the formation of the reaction products, CH3C(O) H (from C2H5 radicals), C(O) F-2 and FNO (from CF3CF2), and C(O) F-2 and HFCO (from CF3CFH) were followed, in real time, via absorption of infrared radiation provided by tuneable diode lasers. Our measurements essentially confirm previous conclusions, based mainly on continuous photolysis experiments, concerning the oxidation mechanisms for these compounds and also how they differ according to whether RO, the ethoxy or substituted ethoxy radical, is formed by mutual reaction of two alkyl peroxy radicals (RO2+ RO2) or by reaction of one of these radicals with NO (RO2+ NO). In addition, we report rate constants for the important atmospheric reactions of ethyl peroxy with NO at 298 K, and of fluorinated ethyl peroxy radicals with NO, for temperatures between 198 and 298 K.
AB - We report new time-resolved measurements relevant to the atmospheric oxidation of C2H6, CF3CF2H (HFC-125), CF3CH3 (HFC- 143a) and CF3CFH2 (HFC- 134a). The radicals R = C2H5, CF3CF2, CF3CH2 and CF3CFH were produced by photolysis of the corresponding iodides, RI, at 248 nm, using the output from a pulsed excimer laser, in the presence of a large excess of O-2 and with different concentrations of NO present. The loss of NO and the formation of the reaction products, CH3C(O) H (from C2H5 radicals), C(O) F-2 and FNO (from CF3CF2), and C(O) F-2 and HFCO (from CF3CFH) were followed, in real time, via absorption of infrared radiation provided by tuneable diode lasers. Our measurements essentially confirm previous conclusions, based mainly on continuous photolysis experiments, concerning the oxidation mechanisms for these compounds and also how they differ according to whether RO, the ethoxy or substituted ethoxy radical, is formed by mutual reaction of two alkyl peroxy radicals (RO2+ RO2) or by reaction of one of these radicals with NO (RO2+ NO). In addition, we report rate constants for the important atmospheric reactions of ethyl peroxy with NO at 298 K, and of fluorinated ethyl peroxy radicals with NO, for temperatures between 198 and 298 K.
UR - http://www.scopus.com/inward/record.url?scp=0042970580&partnerID=8YFLogxK
U2 - 10.1039/b305396m
DO - 10.1039/b305396m
M3 - Article
SN - 1463-9084
VL - 5
SP - 3436
EP - 3442
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
ER -