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Disproportionation‐to‐combination ratios for cyclohexyl‐ h 11 and ‐ d 11 radicals in the gas phase as determined by the radiolysis of water vapor–cyclohexane mixtures
Author(s) -
Fujisaki Noboru,
Gäumann Tino
Publication year - 1979
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550110402
Subject(s) - chemistry , radical , cyclohexene , disproportionation , radiolysis , cyclohexane , reactivity (psychology) , yield (engineering) , hydrogen , torr , analytical chemistry (journal) , radiation chemistry , photochemistry , chemical reaction , organic chemistry , catalysis , medicine , materials science , alternative medicine , physics , pathology , metallurgy , thermodynamics
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 d H / k c Hfor c ‐C 6 H 11 radicals could be determined as 0.56 ± 0.01 from the ratio of cyclohexene to bicyclohexyl yield. By using c ‐C 6 D 12 , the ratio k d D / k c Dfor c ‐C 6 D 11 radicals is found to be 0.38 ± 0.01. Comparison of the reactivity pattern of C 6 H 11 and C 6 D 11 radicals leads to ( k d H )/( k c H )/( k d D / k c D ) = 1.47 ± 0.02. The corresponding values for the reactions of c ‐C 6 H 11 with c ‐C 6 D 11 were also determined.