KINETICS OF GAMMA-RADIATION-INDUCED FREE-RADICAL CHAIN REACTIONS BETWEEN ALKANES AND CHLOROOLEFINS .I. SOLUTIONS OF TETRACHLOROETHYLENE IN ALKANES

The kinetics of γ-radiation-initiated free-radical chain condensation reactions in solutions of tetrachloroethylene in alkanes, RH (n-pentane, cyclopentane, and cyclohexane), resulting in the formation of alkyltrichloroethylenes, RC2Cl3, and HCl, have been studied in the temperature range 26-150°. The Arrhenius parameters for the addition of the alkyl radicals, R, to tetrachloroethylene have been determined. In pentane the rate of formation of the condensation products is proportional to the first power of the solute concentration. In cyclohexane, and to a lesser extent in cyclopentane, some deviation from the first-order dependence of the products on tetrachloroethylene concentration is observed at room temperature. At 150° this feature of the kinetics in cyclohexane disappears, presumably due to strong decrease in the steady-state concentration of the cyclohexyltetrachloroethyl radical. © 1969, American Chemical Society. All rights reserved.