Vibrational relaxation and dissociation in the perfluoromethyl halides, CF3Cl, CF3Br, andCF3I

Abstract

The processes of vibrational relaxation and unimolecular dissociation of the perfluoromethyl halides CF 3 Cl, CF 3 Br, and CF 3

Pyrolysis of Furan at Low Pressures: Vibrational Relaxation, Unimolecular Dissociation, and Incubation Times

“…The complex relaxation exhibited here by furan and by other large molecules (see, for example, ref 16), can only be understood by a detailed master-equation analysis, which will be presented together with more examples in upcoming papers.…”

Falloff curves and mechanism of thermal decomposition of CF3I in shock waves

“…While the ARAS experiments used reactant concentrations as low as 1-4 ppm of CF 3 I in Ar 15 (or in Kr 13 ), the present work employs mixtures with 100-1500 ppm (mostly about 500 ppm). The present experiments were able to monitor CF 3 I concentrations with considerably reduced reactant concentrations in comparison to earlier shock tube work (employing reactant concentrations of 0.5-5% 6,9,14 ). Within the present range of reactant concentrations, the onset of secondary reactions can be monitored.…”

“…[1][2][3] On the other hand, with its weak C-I bond in the presence of strong C-F bonds, it represents a prototype of a unimolecular dissociation reaction of simple bond-fission character. [4][5][6][7][8][9][10][11][12][13][14][15] Furthermore, its secondary reactions are related to processes of importance in chemical lasers and laser-induced isotope separation. 16,17 The role of secondary reactions, in flow system studies of CF 3 I dissociation up to about 800 K, remained unclear for quite some while.…”

Practical Aspects of Thermal Dissociation and Recombination Reactions: The Reaction Systems CF3X(+M)↔CF3+X (+M) with X=F, Cl, Br, and I

“…Studies of the thermal dissociation of CF 4 at temperatures between 2000 and 3000 K and [Ar] between 5×10 −6 and 10 −4 mol cm −3 in [26, 34], according to Figure 1 locate the reaction between a second‐order and a first‐order process. The analogous applies to dissociation experiments for CF 3 Cl [35] . For the dissociation of CF 3 Br (see e. g. [35–37]), and even more that of CF 3 I, [27–29,35] the intermediate reaction order had to be accounted for.…”