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Disproportionation-to-combination ratios for cyclohexyl-h11 and -d11 radicals in the gas phase as determined by the radiolysis of water vapor–cyclohexane mixtures

✍ Scribed by Noboru Fujisaki; Tino Gäumann


Publisher
John Wiley and Sons
Year
1979
Tongue
English
Weight
509 KB
Volume
11
Category
Article
ISSN
0538-8066

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✦ Synopsis


In the radiolysis of water vapor containing small concentrations of cyclohexane, the principal products which account for about 98% of all end products are found to be hydrogen, cyclohexene, and bicyclohexyl. Cyclohexene and bicyclohexyl yields were determined over a range of temperatures (70-200°C), total pressures (50-2400 torr), and total doses (0.15-2.0 Mrad). The disproportionation-combination ratio k;/kP for c -C ~H I I radicals could be determined as 0.56 f 0.01 from the ratio of cyclohexene to bicyclohexyl yield. By using c-CgD12, the ratio kflkf for c-CgDII radicals is found to be 0.38 f 0.01. Comparison of the reactivity pattern of CgHll and CgDll radicals leads to (k;/kF)/(kf/kF) = 1.47 f 0.02. The corresponding values for the reactions of c-C~H11 with c-CgD11 were also determined.