Ozone hydrazine reactions

The results of the study reported here show clearly that, upon release into the atmosphere, N,N-dlmethylhydrazlne (UDMH) can be rapidly converted to N-nitrosodimethylamine by its reaction with atmospheric ozone. A similar conclusion can be reached concerning nitrosamine formation from other unsymmetrically disubstituted hydrazines ... 

Although nitrosamine and nitramine formation from UDMH (and similarly substituted hydrazines) will probably be the major reaction pathway as long as the atmosphere into which the hydrazines are emitted contains some ozone (as does the "natural" troposphere), our results indicate that different products would potentially be formed if these compounds are emitted into polluted atmospheres where O3 is suppressed by high levels of NO. 

J. N. "Reactions of Hydrazines with Ozone under Simulated Atmospheric Conditions," Environ. Sci. Technol., in press, 1981. 

Tuazon, E. C., W. P. L Carter, R. Atkinson, and J. N. Pitts, Jr., The Gas-Phase Reaction of Hydrazine and Ozone A Nonphotolytic Source of OH Radicals for Measurement of Relative OH Radical Rate Constants, Int. J. Chem. Kinet., 15, 619-629 (1983a). 

This technique calls for drying the sample in a liq drying column using Linde 4A molecular sieves (water detn), and then using the near IR spectrum between 2.2 and 1.7 micrometers to determine the ratio of UDMH to diethylenetriamine] 5) H.N. Voltrauer, Hydrazine Analysis Using Chemiluminescence , SAM-76-37, Aero Chem Res Lab, Princeton, Contract F41609-76-C-0029 (1976) [A procedure is reported using the chemiluminescent reactions of ozone with monomethylhydrazine and Aero-zine-50 (UDMH/hydrazine in 50/50 wt %) to... 

Of all the reactions studied, only the synthesis of nitrogen oxides and acetylene in arcs or plasma torches and that of ozone in glow and corona discharges are of major importance. In addition, a few small-scale preparations of inorganic compounds have been developed, e.g. synthesis of hydrazine and of hydrides and halides of silicon, germanium, tin, lead, phosphorus or arsenic 3> ... 

Explosive reaction with alkenes + diiodomethane, sulfur dioxide. Reacts violently with bromine, water, nitro compounds. Ignites on contact with air, ozone, methanol, or hydrazine. Reacts violently with nonmetal halides (e.g., arsenic trichloride or phosphorus trichloride) to produce pyrophoric triethyl arsine or triethyl phosphine. To fight fire, do not use water, foam, or halogenated extinguishing agents. Use dty materials, such as graphite, sand, etc. When heated to decomposition it emits toxic fumes of ZnO. See also ZINC COMPOUNDS. 

Tuazon EC, Carter WP, Winer AM, et al. 1981. Reactions of hydrazines with ozone under simulated atmospheric conditions. Environ Sci Technol 15 823-828. 

The experiments were made with ammonia using an all-glass ozonizer the surface of the inner electrode of which was deposited with a thin film of a metal. The metals used were Pt, Pd, Ni, Au and Ag. With recirculation of the gas mixture at a pressure close to atmospheric steady-state conversions into hydrazine as high as 13.5% were attained with Pd which is an increase in the N2H4 yield by a factor of 4 (Fig. 18). The overall conversion of ammonia and the formation of N2 and H2 were almost independent of the metal coatings (Fig. 18) suggesting that hydrazine is not an intermediate in the d omposition of NH3 into Nj and Hj. Therefore, it seems that there are two independent reaction pathways the formation of hydrazine which is a surface reaction that is dependent on the state of the electrode surface... 

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