Journal of Physical Chemistry p. 3296 - 3300 (1984)
Update date:2022-08-16
Topics:
Alfassi, Zeev B.
Mosseri, Shlomo
The kinetics of the photolysis-induced free-radical reaction in carbon tetrachloride solution of cyclohexane in the absence and in the presence of oxygen were studied in the temperature range of 100-200 deg C.It was found that the influence of the oxygen on the chloroform formation is significant, and a new mechanism which explains the results was suggested.The rate constants for the reactions .CCl3 + O2 -> .CCl3O2 (k6), .CCl3O2 -> COCl2 + ClO (k7), and .CCl3O2 + C6H12 -> CHCl3 + .C6H11 + O2 (k8) were found as log (k6/(M-1s-1)) = 5.05 +/- 0.07 and log <(k8/k7)/(M-1s-1)> = (3.0808 +/- 0.0973) - (3.7080 +/- 0.1857)/θ, where θ = 2.303RT kcal/mol.
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