Effect of Pressure on the Rates of Reaction of Radiolysis Intermediates in Liquid n-Hexane
The yield of hydrogen from pure hexane, G(H2) = 5.3 ± 0.2 was independent of pressure in the range 1 bar to 4.6 kbars. The G values of H2, HD, and D2 obtained from 11 mol% C6D14 in C6H14 were independent of pressure and were respectively, 4.85, 0.34, and 0.11. The electron and hydrogen atom scavenging efficiencies of carbon tetrachloride and hexadiene-1,3, and the hydrogen atom scavenging efficiency of hexene-1 were independent of pressure. The positive ion scavenging efficiencies of benzene and aniline increased with increasing pressure. The volume of activation for the hydrogen atom reaction with n-hexane is essentially the same as that for the reaction with hexene-1. The pressure dependence of the charge scavenging reactions has been interpreted in terms of the kinetics of spur processes. The treatment is consistent with the fact that the efficiency of the electron scavenging reactions is independent of pressure. The increased efficiency of positive ion reaction under pressure implies that the ratio of the diffusion coefficients of the radiolytic positive ion and electron, D+/D−, increases with increasing pressure.