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.
Hydrazine (N2H4) found early use as a fuel, but it was quickly replaced by UDMH. It is still used as a monopropellant for satellite station-keeping motors. Hydrazine marketed for rocket propellant contains a minimum of 97 per cent N2H4, the other constituent being primarily water. Hydrazine is a clear, water-white, hygroscopic liquid. The solid is white. Hydrazine a toxic, flammable caustic liquid and a strong reducing agent. Its odour is similar that of ammonia, though less strong. It is slightly soluble in ammonia and methyl-amine. It is soluble in water, methanol, ethanol, UDMH, and ethylenediamine. Hydrazine is manufactured by the Raschig process, which involves the oxidation of ammonia to chloramine, either indirectly with aqueous sodium hypochlorite or directly with chlorine, and subsequent reaction of chloramine with excess ammonia. Raw materials include caustic, ammonia, and chlorine; these are high-tonnage, heavy chemicals. The cost of anhydrous hydrazine in drum quantities in 1959 was $ 7.00 per kg. The projected price, based on large-scale commercial production, was expected to be $ 1.00 per kg. Due to environmental regulations, by 1990 NASA was paying $ 17.00 per kg.