DEVIATIONS FROM THE "MIXTURE LAW" IN THE RADIOLYSIS OF HYDROCARBON MIXTURES: II. YIELDS OF LIQUID PRODUCTS IN MIXTURES OF CYCLOHEXANE AND CYCLOPENTANE

The radiolytic yields of olefins and dimers have been measured in mixtures of cyclohexane and cyclopentane. While the dimeric products ((C6H11)2, C6H11·C5H9) show a bias towards C5 groups, the olefins show a bias towards C6 groups; the yield of cyclohexene at low concentrations of cyclohexane is more than twice the maximum predicted by the "mixture law". These results confirm earlier isotopic work which showed a higher reactivity of cyclohexane-d12 in cyclohexane-d12 – cyclopentane mixtures relative to that in cyclohexane-d12 – cyclohexane. The results also confirm the preferential change of identity of cyclohexyl radicals to cyclopentyl radicals, which leads to a predominance of C5 groups in the dimer.