Thermal stability of primary amines

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Abstract
Tertiary‐amyl amine has been decomposed in single‐pulse shock‐tube experiments. Rate expressions for several of the important primary steps are This leads to D(CH3H) – D(NH2H) = −10.5 kJ and D[(CH3)3CH] – D[(CH3)2NH2CH] = + 6 kJ.The present and earlier comparative rate single‐pulse shock‐tube data when combined with high‐pressure hydrazine decomposition results‐(after correcting for fall off effects through RRKM calculations) gives where kr(…) is the recombination rate involving the appropriate radicals. This suggests that in this context amino radical behavior is analogous to that of alkyl radicals. If this agreement is exact, then Rate expressions for the primary step in the decomposition of a variety of primary amines have been computed. In the case of benzyl amine where data exist the agreement is satisfactory. The following differences in bond energies have been estimated: