Kinetics of the reactions of CCl3 with O and O2 and of CCl3O2 with NO at 295 K

✍ Scribed by K. R. Ryan; I. C. Plumb

• Publisher: John Wiley and Sons
• Year: 1984
• Tongue: English
• Weight: 605 KB
• Volume: 16
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550160508

✦ Synopsis

The reactions of CCl, with O(,P) and O2 and those of CC1302 with NO have been studied at 295 K using discharge flow methods with helium as the bath gas. The rate coefficient for the reaction of CCI, with 0 was found to be (4.2 2 0.6) x lo-'' cm3/s and that for CCI3O2 with NO was (18.6 2 2.8) x lo-'' cm3/s with both coefficients independent of [He]. For reaction between CCl, and 0, the rate coefficient was found to increase from 1.51 x cm3/s as the [He] increased from 3.5 x 10l6 cm-, to 2.7 x 1017 cm-,. There was no evidence for a direct two-body reaction, and it is concluded that the only product of this reaction is Cc1,0,. Examination of these results for CCl, + 0, in terms of current simplified falloff treatment suggests that the high-pressure limit for this reaction is -2.5 x lo-'' cm3/s, which may be compared with a direct measurement of the high-pressure limit of 5 x lo-" cm3/s. A value of (5.8 2 0.6) x lo-,' cm6/s has been obtained for k,, the coefficient in the lowpressure region. This value is compared with corresponding values found earlier for the (CH,, 0,) and (CF,, 0,) systems and with estimates based on unimolecular rate theory.