ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The reaction mechanism of the halogen (Cl and Br)-atom initiated oxidation of C2H4 was studied using the long path FTIR spectroscopic method in 700 torr of air at 296 ± 2 K. Among the major halogen-containing products were X—CH2CHO, X—CH2CH2OH, and X—CH2CH2OOH (X = Cl or Br) which were shown to be formed via the self-reaction of the X—CH2CH2OO radicals, i.e., 2X—CH2CH2OO → 2X—CH2CH2O + O2; (a) 2X—CH2CH2OO → X—CH2CHO + X—CH2CH2OH + O2 and (b) followed by X—CH2CH2O + O2 → X—CH2CHO + HO2 and X—CH2CH2OO + HO2 → X—CH2CH2OOH + O2. From the observed yields of X—CH2CHO and X—CH2CH2OH the branching ratios for reactions (a) and (b) were determined to be ka/kb = 1.35 ± 0.07(2σ) for both X = Cl and Br. In addition, the O2-dependence of the rate constant for the Br + C2H4 reaction was determined by the relative rate technique as a function of O2 partial pressure from 140 to 700 torr at 700 torr total pressure of N2/O2 diluent. Rate constants for the reactions of Cl-atoms with Cl-CH2CHO and Br-atoms with Br-CH2CHO were also determined to be [4.3 ± 0.2(2sigma;)] × 10-11 and less than or equal to [1.83 ± 0.11(2σ)] × 10-13 cm3 molecule-1 s-1, respectively.
Additional Material:
10 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550240406
