Elementary Rates of Decomposition of the Homologous Series Ethyl through 2-Octyl Radicals

摘要: The rates of decomposition the secondary alkyl radicals 2‐butyl, 2‐pentyl, 2‐hexyl, 2‐heptyl, and 2‐octyl were measured by an internal comparison method at 300°K. Activation to a level around 45 kcal mole−1 was addition H atom appropriate α‐olefin. validity assumption invariance thermochemical parameters, including bond‐dissociation energy D[3(—C)—(4—C)] for higher members radical series, established measurements made with 5‐Me‐2‐hexyl radicals. No evidence found any significant amount migration isomerization these excited radicals.Together earlier work, now exist homologous series ethyl through radicals.Theoretical rate constants agree well experimental values. Our verification relatively smaller molecules that all vibrational rotational degrees freedom must be treated as active is extended largest member this series. Within the...