Reaction of charged species in irradiated cyclohexane with added solutes as studied by steady state radiolysis. Relative rate constants for reaction of positive and negative species with different solutes

Abstract

The yield of scavenging of electrons in irradiated cyclohexane by CH₃Br and CH₃Cl and of the positive species by cyclopropane in the presence and absence of other solutes that react with one or both of the charged species has been studied. The observed concentration dependences of the scavenging yields are described in terms of an ion-pair picture; the diffusion coefficient of the positive species is much smaller than that of the negative species but much larger than that of a molecular ion. Relative rate constants for the reactions of several solutes with the positive and the negative species are determined from the concentration dependence of the scavenging yields. Using the known value for the absolute rate constant for the reaction of the excess electron with triphenylmethyl chloride, absolute rate constants are calculated.