Rate of Recombination of Radicals. III. Rate of Recombination of Ethyl Radicals

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Abstract
The rate constants for the recombination (k2) and the disproportionation (k3) of ethyl radicals have been determined by applying the theory of the rotating sector to the photolysis of diethyl ketone. The values of k2 are 1.5±1×1013, 2.0±0.5×1013, and 4.2±0.8×1013 cc mole—1 sec—1, at 50°C, 100°C, and 150°C, respectively. The ratio k3/k2 is taken to be 0.12 from other work. An Arrhenius plot of these results indicate an energy of activation for k2 of 2.0±1 kcal/mole. These results are shown to be in agreement with existing theories. A simplified transition state theory calculation of k2 is offered, based on the change in the number of degrees of freedom from radicals to activated complex.