The Gas Phase Kinetics of Methylhydrazine and Related Compounds.
Special technical rept. no. 1, 1 Jun 69-1 Dec 70,
STANFORD RESEARCH INST MENLO PARK CA
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The following compounds have been pyrolyzed under very low pressure conditions VLPP Benzylamine N-methylbenzylamine N,N-dimethylbenzylamine Monomethylhydrazine Unsymmetrical dimethylhydrazine Symmetrical dimethylhydrazine and Tetramethylhydrazine. The rate constants kuni for the first order disappearance of these molecules have been determined. The kuni are not the rate constants of ultimate interest since they reflect the fact that energy transfer competes with the chemical decomposition. Use of the Rice-Ramsperger-Kassel-Marcus RRKM theory allows the determination of the rate constants associated with the purely chemical change kinfinity if the mode of decomposition is known. The mechanism of pyrolysis of the three benzylamines is shown to occur through C-N bond homolysis. The results and other evidence lead to the conclusion that MMH decomposes via molecular concealed elimination of NH3 and H2 and not by N-N bond scission. Author
- Physical Chemistry