Mechanism of the radiolytic decomposition of nitrous oxide in liquid cyclohexane

Abstract

In the radiolysis of cyclohexane + HCl solutions g(H 2) (where g means the yield due to the energy absorbed in the solvent only) is concentration dependent up to a plateau value of 7·1±0·10. The sum of G'(N 2)+ g(H 2) from cyclohexane+N 2O solutions follows the same curve as g(H 2) from cyclohexane+HCl solutions. In the radiolysis of cyclohexane+N 2O solutions the yields of cyclohexene and bicyclohexyl increase with scavenger concentration ultimately reaching plateaux at 3·7 and 2·45, respectively. The presence of HCl in cyclohexane increases the yields of bicyclohexyl with a scavenger concentration dependence identical with that obtained in the presence of nitrous oxide. The analysis of the oxygen containing products formed in the radiolytic decomposition of N 2O in cyclohexane gives water and cyclohexanol as the only detectable products. The sum of the yields of the two oxygen-containing products is equal to the nitrogen yields over the whole concentration range examined indicating that no secondary reactions contribute to N 2 formation. Assuming that the radiolysis of HCl solutions and N 2O solutions forms H 2 and N 2, respectively, via the same ionic processes a g(total ionization) = 5·3±0·1 is calculated for liquid cyclohexane.