THE RADIOLYSIS OF CYCLOHEXANE: IV. BINARY MIXTURES IN THE VAPOR PHASE

Abstract

The variation of the hydrogen yield with the composition of binary gaseous mixtures containing cyclohexane and benzene, cyclohexene, or propylene is qualitatively similar to that in the liquid phase.The quantitative experimental data were tested against several possible reaction mechanisms and two mechanisms gave straight-line plots.One mechanism involved scavenging of hydrogen atoms. The values of the kinetic parameters derived from this mechanism might not be unreasonable in the mixtures of cyclohexane with cyclohexene or propylene. The values for benzene, however, seem less likely.The second mechanism involved the transfer of energy (excitation or ionization) from cyclohexane to the second substance. The values of the ratio of the rate constants, k7/k6, of the reactions[Formula: see text]is about 103 times greater in the gas than in the liquid phase. Consideration of possible detailed mechanisms of reactions [6] and [7] indicates that this difference is reasonable if C6H12** is a positive ion rather than an excited molecule.