Reactions of CCl, CCl2 and CClF radicals

Thermal decomposition of dichloroketene and its reaction with H atoms

“…ðIXÞ This k 1 À1 ðT Þ dependence disagrees with the only existing experimental value of the rate constant of the reaction of CCl 2 with CO, k À1 (298 K) = 5 · 10 À14 cm 3 molecule À1 s À1 , reported by Tiee et al [23]. The transition state theory model of the current study results in a significantly smaller value of 3.8 · 10 À18 cm 3 molecule À1 s À1 .…”

“…The transition state theory model of the current study results in a significantly smaller value of 3.8 · 10 À18 cm 3 molecule À1 s À1 . The k À1 value of [23] would require the CCl 2 + CO addition to be almost barrierless: a value of 1.2 kJ mol À1 is obtained for the barrier if the current reaction model is adjusted to provide match with the results of [23]. It should be noted that [23] is a very short (2.5 pages) communication and contains no description of the kinetic study; the value of k À1 is given in a table with one significant figure and is not mentioned in the text of the article.…”

“…), very little is known about its kinetics. Until 2003, [23,26] provided all the existing information on CCl 2 kinetics. In two recent experimental studies, we have obtained the rate constants of the reaction of CCl 2 biradical with molecular chlorine [27] and NO [28] as functions of temperature.…”

Theoretical study on the reactions of CF/CCl with O2

“…Therefore, it is probably incorrect to say that the initial association of CCl with O 2 is a barrierless process which Xiang et al claimed [5]. However, the measured rate constant of (1.6 ± 0.2) Â 10 À12 cm 3 mol À1 s À1 for the CF + O 2 reaction [2] is smaller than that for the CCl + O 2 reaction, (2.6-4.15) Â 10 À12 cm 3 mol À1 s À1 [3][4][5], as is not consistent with the present theoretical study. Thus, it is desirable to perform further accurate experimental measurements of the rate constants for the reactions of CF/CCl with O 2 .…”

“…By monitoring the reactant concentration [CCl] with LIF spectroscopy, Tiee et al also took a measurement of the rate constant for the same reaction to be 2.9 Â 10 À12 cm 3 mol À1 s À1 [4]. Recently, using laser photodissociation and time-resolved Fourier transform infrared (FTIR) emission spectroscopy, Xiang and his co-workers [5] found a nascent product CO, which was highly vibrationally excited in the CCl + O 2 reaction.…”