Journal of Physical Chemistry A, Vol.109, No.43, 9816-9826, 2005
Atmospheric chemistry of CF3CH2CH2OH: Kinetics, mechanisms and products of Cl atom and OH radical initiated oxidation in the presence and absence of NOX
Relative rate techniques were used to study the kinetics of the reactions of Cl atoms and OH radicals with CF3CH2C(O)H and CF3CH2CH2OH in 700 Torr of N-2 or air diluent at 296 2 K. The rate constants determined were k(Cl+CF3CH2C(O)H) = (1.81 +/- 0.27) x 10(-11), k(OH+CF3CH2C(O)H) = (2.57 +/- 0.44) x 10(-12), k(Cl+CF3CH2CH2OH) = (1.59 +/- 0.20) x 10(-11), and k(OH+CF3CH2CH2OH) = (6.91 +/- 0.91) x 10(-13) cm(3) molecule(-1) s(-1). Product studies of the chlorine initiated oxidation of CF3CH2CH2OH in the absence of NO show the sole primary product to be CF3CH2C(O)H. Product studies of the chlorine initiated oxidation of CF3CH2CH2OH in the presence of NO show the primary products to be CF3CH2C(O)H (81%), HC(O)OH (10%), and CF3C(O)H. Product studies of the chlorine initiated oxidation of CF3CH2C(O)H in the absence of NO show the primary products to be CF3C(O)H (76%), CF3CH2C(O)OH (14%), and CF3CH2C(O)OOH (<= 10%). As part of this work, an upper limit of k(O-3+CF3CH2CH2OH) < 2 x 10(-21) cm(3) molecule(-1)s(-1) was established. Results are discussed with respect to the atmospheric chemistry of fluorinated alcohols.