The Kinetics of Radiation-Induced Hydrogen Abstraction by CCl3 and CCl3O2 Radicals from Cyclohexane in the Liquid Phase

Article abstract of DOI:10.1021/j150659a031

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.