The heats of formation of Cs and C, alkyl nitrites (RONO) have been determined via their heats of combustion by bomb calorimetry, thereby providing a complete set of values of AH'/ for CI-C, 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 El determined by recent kinetic studies, required for breaking the RO-NO bond.The hcats of formation of the alkoxy radicals involved together with AH",(NO) = 21.6 kcal/mole leads to the result D(R0-NO) = 41.5 f 1 kcal/mole. The concordance between D(thermochemica1) and D(kinetic), unlike previous kinetic studies, implies that E t = 0 =k 1 kcal/mole.
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