Analysis of Reaction Products of Nitrogen Tetroxide with Hydrazines under Nonignition Conditions

Products formed by reaction of nitrogen tetroxide and hydrazine or methylhydrazines at low temperatures were collected and analyzed, using mass spectroscopy, gas chromatography and infrared absorption spectroscopy. It was found that hydrazine and nitrogen tetroxide form water, nitrogen, nitric oxide, hydrazinium nitrate, and ammonia. When monomethylhydrazine is used instead of hydrazine, the products include methylamine, dimethylamine, methanol, methylnitrosamine, dimethylnitro samine, N-methylformamide, water, methylhydrazinium nitrate, nitrogen, and dissolved oxides of carbon and nitrogen. When 1,1-dimethylhydrazine is used in place of hydrazine, the products include methylamine, dimethylamine, methanol, dimethylnitrosamine, dimethylformamide, formamide, nitrogen, water, dimethylhydrazinium nitrate, and dissolved oxides of carbon and nitrogen. Between 6Q% and 8Q% of the liquid portion of the products is dimethylnitro samine. Based on the evidence provided by these analyses, reaction mechanisms are proposed.