The kinetics of the forward and reverse reactions for the equilibrium CF3OOCF3 <=* CF3OF + COF2 have been measured in the temperature range 480-580°K. The results are interpreted in terms of the mechanism CF3-OOCF3 *3.2CF30 (fa, fa); CF30 CFjO + F (fa, fa); CF30 + F CF3OF (fa, fa). Activation energies of 46.2 and 45.0 kcal mol-1 have been found for steps 1 and 6 leading to bond dissociation energies, evaluated at 298°K, of 46.7 ± 0.8 and 44.5 ± 0.8 kcal mol-1, respectively, for the central oxygen-oxygen bond in bistrifluoromethyl peroxide and the oxygen-fluorine bond in trifluoromethyl hypofluorite. General rate expressions have been determined, by a consideration of kinetic and thermodynamic data, for all six rate constants.

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The thermal decomposition of perchloric acid vapor has been studied from 200 to 439'. The reaction products over this temperature range have been found to be chlorine, water, and oxygen. From 200 to 350' the kinetics of the decomposition reaction have been studied by determining the rate of chlorine formation colorimetrically; from 350 to 439' the kinetics %-ere determined by a flow system technique. The results of the kinetic measurements are interpreted in terms of a heterogeneous reaction at the lower temperatures and a homogeneous one a t the higher temperatures. A mechanism for the homogeneous reaction is proposed. Recezved December 18, lDSlThe ?-radiolysis of dilute solutions of hydrogen iodide in cyclohexane-dlz leads to B(D-atom) K 1.7. There is a remarlrThis effect, attributed to dissociative electron ably large C?(H2), amounting to 2.2 molecules/100 e.v. a t 0.7 mole % HI.attachment, seriously complicates using halogens or halides as H-atom and free radical scavengers.