nitrogen fixation

nitrogen fixation, any natural or industrial process that causes free nitrogen (N₂), which is a relatively inert gas plentiful in air, to combine chemically with other elements to form more-reactive nitrogen compounds such as ammonia, nitrates, or nitrites.

Under ordinary conditions, nitrogen does not react with other elements. Yet nitrogenous compounds are found in all fertile soils, in all living things, in many foodstuffs, in coal, and in such naturally occurring chemicals as sodium nitrate (saltpetre) and ammonia. Nitrogen is also found in the nucleus of every living cell as one of the chemical components of DNA.

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How the Nitrogen Cycle Works

Nitrogen fixation in nature

Nitrogen is fixed, or combined, in nature as nitric oxide by lightning and ultraviolet rays, but more significant amounts of nitrogen are fixed as ammonia, nitrites, and nitrates by soil microorganisms. More than 90 percent of all nitrogen fixation is effected by them. Two kinds of nitrogen-fixing microorganisms are recognized: free-living (nonsymbiotic) bacteria, including the cyanobacteria (or blue-green algae) Anabaena and Nostoc and genera such as Azotobacter, Beijerinckia, and Clostridium; and mutualistic (symbiotic) bacteria such as Rhizobium, associated with leguminous plants, and various Azospirillum species, associated with cereal grasses.

The symbiotic nitrogen-fixing bacteria invade the root hairs of host plants, where they multiply and stimulate the formation of root nodules, enlargements of plant cells and bacteria in intimate association. Within the nodules, the bacteria convert free nitrogen to ammonia, which the host plant utilizes for its development. To ensure sufficient nodule formation and optimum growth of legumes (e.g., alfalfa, beans, clovers, peas, and soybeans), seeds are usually inoculated with commercial cultures of appropriate Rhizobium species, especially in soils poor or lacking in the required bacterium. (See also nitrogen cycle.)

Industrial nitrogen fixation

Nitrogenous materials have long been used in agriculture as fertilizers, and in the course of the 19th century the importance of fixed nitrogen to growing plants was increasingly understood. Accordingly, ammonia released in making coke from coal was recovered and utilized as a fertilizer, as were deposits of sodium nitrate (saltpetre) from Chile. Wherever intensive agriculture was practiced, there arose a demand for nitrogen compounds to supplement the natural supply in the soil. At the same time, the increasing quantity of Chile saltpetre used to make gunpowder led to a worldwide search for natural deposits of this nitrogen compound. By the end of the 19th century it was clear that recoveries from the coal-carbonizing industry and the importation of Chilean nitrates could not meet future demands. Moreover, it was realized that, in the event of a major war, a nation cut off from the Chilean supply would soon be unable to manufacture munitions in adequate amounts.

During the first decade of the 20th century, intensive research efforts culminated in the development of several commercial nitrogen-fixation processes. The three most-productive approaches were the direct combination of nitrogen with oxygen, the reaction of nitrogen with calcium carbide, and the direct combination of nitrogen with hydrogen. In the first approach, air or any other uncombined mixture of oxygen and nitrogen is heated to a very high temperature, and a small portion of the mixture reacts to form the gas nitric oxide. The nitric oxide is then chemically converted to nitrates for use as fertilizers. By 1902 electric generators were in use at Niagara Falls, New York, to combine nitrogen and oxygen in the high temperatures of an electric arc. This venture failed commercially, but in 1904 Christian Birkeland and Samuel Eyde of Norway used an arc method in a small plant that was the forerunner of several larger, commercially successful plants that were built in Norway and other countries.

The arc process, however, was costly and inherently inefficient in its use of energy, and it was soon abandoned for better processes. One such method used the reaction of nitrogen with calcium carbide at high temperatures to form calcium cyanamide, which hydrolyzes to ammonia and urea. The cyanamide process was utilized on a large scale by several countries before and during World War I, but it too was energy-intensive, and by 1918 the Haber-Bosch process had rendered it obsolete.

The Haber-Bosch process directly synthesizes ammonia from nitrogen and hydrogen and is the most economical nitrogen-fixation process known. About 1909 the German chemist Fritz Haber ascertained that nitrogen from the air could be combined with hydrogen under extremely high pressures and moderately high temperatures in the presence of an active catalyst to yield an extremely high proportion of ammonia, which is the starting point for the production of a wide range of nitrogen compounds. This process, made commercially feasible by Carl Bosch, came to be called the Haber-Bosch process or the synthetic ammonia process. Germany’s successful reliance on this process during World War I led to a rapid expansion of the industry and the construction of similar plants in many other countries after the war. The Haber-Bosch method is now one of the largest and most-basic processes of the chemical industry throughout the world.