Heats of formation and kinetics of decomposition of nitroalkanes

摘要: Heats of formation solid, liquid, and gaseous nitroalkanes have been shown mostly to obey group additivity. Group values obtained for carbon atoms attached one, two, three nitro groups. The heat 1,1,1,3,5,5,5,-heptanitropentane, either solid or cannot be fitted the scheme, even allowing gauche effects. differences between observed estimated 1,1,1-fluorodinitroalkanes 1,2-dinitroethane are larger than expected should further investigated. Activation energies calculated decomposition by five-center elimination HONO from mononitro- dinitroalkanes using thermochemistry activation reverse reactions. key data these estimates were previously reported nitroethane 1,2-dinitropropane. calculations also gave heats (in kcal/mole) nitroethylene 12.4, 1-nitropropylene 5.6, 2-nitropropylene 1.6. competing unimolecular reaction, CN bond fission, 1,1- 2,2-dinitropropane. Comparison Arrhenius parameters two processes, namely, shows that, geminate dinitroethanes dinitropropanes, fission is faster about 370°K and, mononitroalkanes all dinitroalkanes, above 770°K.