ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The reactions of CCl3 with O(3P) and O2 and those of CCl3O2 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 CCl3 with O was found to be (4.2 ± 0.6) × 10-11 cm3/s and that for CCl3O2 with NO was (18.6 ± 2.8) × 10-12 cm3/s with both coefficients independent of [He]. For reaction between CCl3 and O2 the rate coefficient was found to increase from 1.51 7times; 10-14 cm3/s to 7.88 × 10-14 cm3/s as the [He] increased from 3.5 × 1016 cm-3 to 2.7 × 1017 cm-3. There was no evidence for a direct two-body reaction, and it is concluded that the only product of this reaction is CCl3O2. Examination of these results for CCl3 + O2 in terms of current simplified falloff treatment suggests that the high-pressure limit for this reaction is ∼ 2.5 × 10-12 cm3/s, which may be compared with a direct measurement of the high-pressure limit of 5 × 10-12 cm3/s. A value of (5.8 ± 0.6) × 10-31 cm6/s has been obtained for k0, the coefficient in the low-pressure region. This value is compared with corresponding values found earlier for the (CH3, O2) and (CF3, O2) systems and with estimates based on unimolecular rate theory.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550160508
