UV absorption spectra, kinetics and mechanisms of the self-reaction of CHF2O2 radicals in the gas phase at 298 K

Kinetics of the gas‐phase reactions of chlorine atoms with CH2F2, CH3CCl3, and CF3CFH2 over the temperature range 253–553 K

“…The CF 3 CFH 2 internal calibrant reacts slowly with Cl atoms. The measured CF 3 CFH 2 concentration was corrected for loss using the measured loss of CH 4 and the value of k 3 /k 4 discussed herein. This correction never exceeded 3%.…”

“…Spectra of reaction mixtures of CH 2 F 2 and CH 4 were analyzed in the region 2800-3200 cm −1 . HCl is a reaction product, and H 2 O is always observable as a background contaminant in FTIR smog chamber experiments.…”

“…The rates of reactions (3) and (4) differ by approximately a factor of 100, precluding a direct measurement of k 3 /k 4 . Values of k 3 /k 4 were derived by measuring k 3 /k 2 , k 2 /k 1 , and k 1 /k 4 and using the equal- …”

“…The two highest temperature data points in shown in Fig. 2, for which a thermal reaction was observed, were derived from the loss of CF 2 H 2 versus loss of CH 4 . They are entirely consistent with the data obtained at lower temperature where no thermal reaction occurs.…”

“…Unfortunately, there are significant uncertainties in the kinetic data at ambient temperature and very limited information concerning the temperature dependence for such reactions. Measurements of k(Cl + CH 2 F 2 ) at 298 K by Tschuikow-Roux et al [3] and Nielsen et al [4] differ by a factor of 2, and the work by TschuikowRoux et al [3] provides the only information concerning the temperature dependence of the reaction. Measurements of k(Cl + CH 3 CCl 3 ) at 280-418 K by Cillien et al [5], Tschuikow-Roux et al [6], Platz et al [7], and Talhaoui et al [8] span a range of approximately 2.…”