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.
In January 1953 Rocketdyne commenced the REAP program to develop a number of improvements to the engines being developed for the Navaho and Atlas missiles. Among these was development of a special grade of kerosene suitable for rocket engines. Prior to that any number of rocket propellants derived from petroleum had been used. Goddard had begun with gasoline, and there were experimental engines powered by kerosene, diesel oil, paint thinner, or jet fuel kerosene JP-4 or JP-5. The wide variance in physical properties among fuels of the same class led to the identification of narrow-range petroleum fractions, embodied in 1954 in the standard US kerosene rocket fuel RP-1, covered by Military Specification MIL-R-25576. In Russia, similar specifications were developed for kerosene under the specifications T-1 and RG-1. The Russians also developed a compound of unknown formulation in the 1980's known as 'Sintin', or synthetic kerosene. Rocket propellant RP-1 is a straight-run kerosene fraction, which is subjected to further treatment, i.e., acid washing, sulphur dioxide extraction. Thus, unsaturated substances which polymerise in storage are removed, as are sulphur-containing hydrocarbons. Furthermore, in order to meet specification requirements of density, heat of combustion, and aromatic content, the kerosene must be obtained from crudes with a high naphthene content. RP-1 is an excellent solvent for many organic materials. The flash point is above 43 deg C. Above that temperature RP-1 will form explosive mixtures with air. The temperature range for explosive mixtures (rich limit) is 79 to 85 deg C. RP-1 is not so toxic as the JP series of fuels because of its lower aromatic content. In the United States, suitable kerosene fractions in 1960 were limited almost exclusively to the West Coast. The estimated 1956 United States production was 7700 tonnes, and the price was $0.05 per kg. By the 1980's it was typically $ 0.20 per kg. Russian formulations have typical densities of 0.82 to 0.85 g/cc, and even higher densities were achieved in the N1 and Soyuz 11A511U rockets by superchilling the fuel prior to loading.