Heats of formation of C1?C4 alkyl nitrites (RONO) and their RO-NO bond dissociation energies
1974; Wiley; Volume: 6; Issue: 6 Linguagem: Inglês
10.1002/kin.550060610
ISSN1097-4601
AutoresL. Batt, Karl O. Christie, R. T. Milne, A. J. H. Summers,
Tópico(s)Chemical Reaction Mechanisms
ResumoThe heats of formation of C3 and C4 alkyl nitrites (RONO) have been determined via their heats of combustion by bomb calorimetry, thereby providing a complete set of values of ΔHºf for C1-C4 alkyl nitrites. The experimental values are in excellent agreement with values derived from group additivity rules. For branched compounds these calculations involve corrections for gauche interactions. In these cases, the gauche interactions are reflected in the activation energies E1 determined by recent kinetic studies, required for breaking the RO-NO bond. The heats of formation of the alkoxy radicals involved together with ΔHºf(NO) = 21.6 kcal/mole leads to the result D(RO-NO) = 41.5 ± 1 kcal/mole. The concordance between D(thermochemical) and D(kinetic), unlike previous kinetic studies, implies that E2 = 0 ± 1 kcal/mole.
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