Long Path FTIR Spectroscopic Study of the Reactions of CF3O Radicals with Alkenes

Article abstract of DOI:10.1021/j100130a008

The reactions of CF3O radicals with alkenes have been studied using the long path FTIR method in the visible (λ >/= 400 nm) photolysis of mixtures containing CF3NO, NO, and alkene (in milliTorr range) in 700 Torr of O2/N2 at 297 +/- 2 K.Kinetic and spectroscopic evidence has been obtained for the occurrence of the addition reaction (a) CF3O* + >C=C< -> adduct, and the subsequent reactions involving the adducts, for several alkenes.Using the reaction (b) CF3O* + NO -> CF2O + FNO as the reference reaction, values for the relative rate constants, k_a/k_b have been determined to be 0.7 +/- 0.2(?), 0.9 +/- 0.2(?), 1.1 +/- 0.3(?), and 1.7 +/- 0.4(?) for CH2=CH2, CH3CH=CH2, trans-CH3CH=CHCH3, and (CH3)2C=C(CH3)2, respectively.Using the value of the rate constant for reaction b recently reported by Bavilacqua et al. (k_b = (2 +/- 1) x 10^-11 cm³ molecule^-1 s^-1), the values of the rate constant k_a have been calculated to be (1.4 +/- 0.8) x 10^-11, (1.8 +/- 1.0) x 10^-11, (2.2 +/- 1.3) x 10^-11, and (3.4 +/- 1.9) x 19^-11 cm³ molecule^-1 s^-1 for CH2=CH2, CH3CH=CH2, trans-CH3CH=CHCH3, and (CH3)2C=C(CH3)2, respectively.