Aestus Credit - Boeing / Rocketdyne

Nitrogen tetroxide became the storable liquid propellant of choice from the late 1950's. Nitrogen tetroxide consists principally of the tetroxide in equilibrium with a small amount of nitrogen dioxide (NO2). The purified grade contains less than 0.1 per cent water. Nitrogen tetroxide (N2O4) has a characteristic reddish-brown colour in both liquid and gaseous phases. The solid tetroxide is colorless. N2O4 has an irritating, unpleasant acid-like odour. N2O4 is a very reactive, toxic oxidiser. It is non-flammable with air; however, it will inflame combustible materials. It is not sensitive to mechanical shock, heat, or detonation. Nitrogen dioxide is made by the catalytic oxidation of ammonia; steam is used as a diluent to reduce the combustion temperature. Most of the water is condensed out, and the gases are further cooled; the nitric oxide is oxidised to nitrogen dioxide, and the remainder of the water is removed as nitric acid. The gas is essentially pure nitrogen tetroxide, which is condensed in a brine-cooled liquefier. 1959 production amounted to 60,000 tonnes per year. In carload lots of one-ton cylinders, the price was $ 0.15 per kg. By 1990 NASA was paying $ 6.00 per kg due to environmental regulations.

Monomethylhydrazine (CH3NHNH2) is a storable liquid fuel that found favour in the United States for use in orbital spacecraft engines. Its advantages in comparison to UDMH are higher density and slightly higher performance. Monomethylhydrazine (MMH) is 95+ per cent pure, while the normally expected impurities are methylamine and water. MMH is a clear, water-white hygroscopic liquid which tends to turn yellow upon exposure to air. MMH is a toxic, volatile liquid which will react with carbon dioxide and oxygen. MMH has the typical sharp ammoniacal or fishy odour of amines. It is completely miscible in all proportions with hydrazine, water, and low molecular-weight alcohols. MMH is not sensitive to impact or friction; it is more stable than hydrazine on mild heating and similar to hydrazine in sensitivity to catalytic oxidation.

Monomethylhydrazine may be produced by a modified Raschig process; methylamine is substituted for ammonia in the reaction with chloramine. In general, substituted hydrazines may be prepared by the reaction of an alkylsulfate or halide with hydrazine. In 1959 the price for MMH was $ 15 per kg. It was projected that this would be reduced to $ 2.00 per kg in mass production. By 1990 NASA was actually paying $ 17.00 per kg due to stringent environmental protection regulations. By 2006 this had skyrocketed to $170.00 per kg.