ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
When Cl atoms react with CHClCHCl in the presence of O2 at 31°C, a long-chain oxidation occurs. The products are the geometrical isomer of the starting olefin and CHClO, HCl, CO, and CCl2O. The quantum yields of the oxygen-containing products are the same with both isomers and are Φ{CHClO} = 30, Φ{CO} = 11.7, and Φ{CCl2O} = 1.29. The chlorine atom adds to the olefin and is followed by O2 addition. The reaction then proceeds with k6a/k6b = 19 and k7a/k7 ∼ 0.5, where k7 ≡ k7a + k7b. The CCl2H radical oxidizes to regenerate the chain carrier.O(3P) reacts with CHClCHCl at 25°C with a rate coefficient of 6.6 × 108 M-1 sec-1 for trans-CHClCHCl and 2.8 × 108 M-1 sec-1 for cis-CHClCHCl. The reaction channels are with k1a/k1 = 0.23 and 0.28, respectively, for the cis and trans compounds. Reaction (1b) occurs 〈 4% of the time. Reaction (1c) leads to polymer production and presumably, via redissociation, to the geometrical isomer of the starting olefin. In the presence of O2 the same long-chain oxidation is observed as in the chlorine-atom initiated oxidation. The chain-initiating step is \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CHCl + O}_{\rm 2} \to {\rm HO + ClCO} \to {\rm Cl + CO} $$\end{document}
Additional Material:
9 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550070409
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