Methyl hydrazine, pyrolysis

Thermochemical data for alkyl amino radicals show for alkylhydrazines a trend in D (N-N) for these compounds in which the N-N bond was strengthened by increasing the degree of substitution by methyl in NH2 NH2 . From these values it was possible to determine values for the enthalpies of formation of the alkylamino radicals , and to confirm these by electron impact studies. The latter values were found to be in agreement with those obtained from pyrolysis studies. Hydrazine has often been used as a source of amino radicals by pyrolysis flame decomposition shock tube decomposition , electrodeless discharge and microwave discharge , viz. 

The heats of formation of the radicals NHg, CH3NH and (CH3)2M have been determined by Dibeler, Franklin and Reese from electron impact measurements on hydrazine, and the methyl-substituted hydrazines. The values they obtained are A J (NH2, g) = 44 2 JH (CH3NH, g) 48 rh 2 and zlH f(CH3)2N, g] = 61 2 kcal/mole. The value for the NHg radical is close to that calculated from Szwarc s pyrolysis measurements of hydrazine. The value (HgN— NHg) — 60 4 kcal/mole, when combined with g) = 22-lkcal/mole, leads to zlH (NH2,g)... 

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