抄録
The thermodynamic profile of the electron capture reaction for aliphatic nitro compounds has been studied. The temperature dependence of the electron capture coefficients indicated that each nitroalkane dissociated into anion and radical via the anion radical state. On the basis of the values of the electron affinities, EA, for nitrogen dioxide and alkyl radicals and those of the C-N bond dissociation energies, DC-N, from literature, it is expected that the dissociative reaction for each compound produces a nitrite ion and an alkyl radical endothermically and that the reaction energy, ΔE(=DC-NEANO22), is nearly equal to the activation energy, E*. The average difference between the activation energy (experimental value) and the reaction energy calculated was 0.3 kcal/mol for C1? C3 nitroalkanes. This result verifies the validity of the above assumption and indicates that the activation energy could be used to calculate the bond dissociation energy. The bond energies were calculated for C4, C5 nitroalkanes.
