The Radiolysis of Cyclohexane: Ii. Cyclohexane–cyclohexene Solutions and Pure Cyclohexene

Abstract

The γ-radiolysis of cyclohexane–cyclohexene solutions and of pure cyclohexene has been investigated. The previously determined yields of the two activated species in irradiated cyclohexane have been confirmed. G(c-C6H12′′) = 3.0 ± 0.3 and G(c-C6H12′) = 2.4 ± 0.3.The yields of the main products of cyclohexene radiolysis are G(H2) = 1.2, G(c-C6H12) = 1.0, G[(c-C6H9)2] = 1.4, and G(c-C6H10 → higher polymer) ≈ 4. There were smaller amounts of ethylene, acetylene, a C4 hydrocarbon (probably butadiene), cyclohexylcyclohexene, and dicyclohexyl.For the reactions[Formula: see text]and[Formula: see text]the value k7a/(k8ak6a)1/2 = 0.45 ± 0.08 was determined.The reaction mechanism that occurs during the radiolysis of cyclohexane–cyclohexene solutions is similar to that which occurs during the radiolysis of cyclohexane–benzene solutions (Part I of this series) with the additional consideration that cyclohexene itself is considerably decomposed during the radiolysis.

Radiolysis of Cyclohexane. V. Purified Liquid Cyclohexane and Solutions of Additives1

“…Cyclohexylcyclohexene has been described as a primary product6,6 and as a secondary product.4, 19 We observed it as a secondary product, arising from the cyclohexene formed in the radiolysis.…”

Anomaly of the Ortho/Para Ratio of Hydrogen Molecules Generated by γ-Irradiation of Solid Alkanes

“…It has been established by many researchers − that hydrogen molecules are generted mainly by hydrogen atom abstraction of hot and thermalized hydrogen atoms, which in turn are generated from alkanes, as The thermalized hydrogen atoms are scavenged by alkenes such as cyclohexene, whereas the hot hydrogen atoms are not. For elucidating the effect of the initial energy of hydrogen atoms on the ortho/para ratio, we examined the effect of cyclohexene on the ortho/para ratio for solid methylcyclohexane.…”

LET dependence of G values as a guide in determining the primary mechanisms of radiolysis. LET effects in cyclohexene

“…Disproportionation reactions can also be formulated. 13 Allylic cyclohexenyl radicals are also produced by hydrogen-atom abstraction from cyclohexene at the or-position. The absence among the products of measurable quantities of bicyclohexenyls other than 2,2'-, and of cyclohexyl cyclohexene-1 and -3, is taken as evidence that bond cleavage or hydrogen abstraction does not occur significantly except at the a-methylenic group.…”