Kinetics of Radiation-Induced Hydrogen Abstraction by CCl3 Radicals in the Liquid Phase. Secondary Alcohols

Article abstract of DOI:10.1021/j150621a010

The dependence of the yield of products in the γ-radiation-induced free-radical reactions in carbon tetrachloride solutions of secondary alcohols on the alcohol concentration and the temperature was studied in the range of 0.05-0.6 M and 30-150 deg C.The rate constant for the reaction CCl3 + R₁R₂COH -> CHCl3 + R₁R₂COH (k₁) was found as logk₁ (M^-1 s^-1) = 8.63-9.1, where Τ = 2.303RT kcal mol^-1.The activation energy is 1.8 +/- 0.3 kcal mol^-1 lower than for secondary hydrogens in alkanes and about the same as for the tertiary hydrogens in 2,3-dimethylbutane.