Nitrogen

Nitrogen is a chemical element which has the symbol N and atomic number 7. Elemental nitrogen is a colorless, odorless, tasteless and mostly inert diatomic gas at standard conditions, constituting 78.1% by volume of Earth’s atmosphere. Nitrogen is a constituent element of amino acids and therefore of all living organisms. Many industrially important compounds, such as ammonia, nitric acid, and cyanides, contain nitrogen.

Properties

Nitrogen is a nonmetal, with an electronegativity of 3.0. It has five electrons in its outer shell and is therefore trivalent in most compounds. The triple bond in molecular nitrogen (N₂) is one of the strongest in nature. The resulting difficulty of converting (N₂) into other compounds, and the ease (and associated high energy release) of converting nitrogen compounds into elemental N₂, have dominated the role of nitrogen in both nature and human economic activities.

At atmospheric pressure molecular nitrogen condenses (liquifies) at 77 K (?195.8 °C) and freezes at 63 K (?210.0 °C) into the beta hexagonal close-packed crystal allotropic form. Below 35.4 K (?237.6 °C) nitrogen assumes the alpha cubic crystal allotropic form. Liquid nitrogen, a fluid resembling water, but with 80.8% of the density, is a common cryogen.

Unstable allotropes of nitrogen consisting of more than two nitrogen atoms have been produced in the laboratory, like N₃ and N₄. Under extremely high pressures (1.1 million atm) and high temperatures (2000 K), as produced under diamond anvil conditions, nitrogen polymerizes into the single bonded diamond crystal structure, an allotrope nicknamed “nitrogen diamond.”

Occurrence

Nitrogen is the largest single component of the Earth’s atmosphere (78.082% by volume of dry air, 75.3% by weight in dry air).

¹⁴N is created by fusion processes in stars, and is estimated to be the 7th most abundant chemical element (by mass) in our universe.

Molecular nitrogen and nitrogen compounds have been detected in interstellar space by astronomers using the Far Ultraviolet Spectroscopic Explorer. Molecular nitrogen is a major constituent of the Saturnian moon Titan’s thick atmosphere, and occurs in trace amounts in other planetary atmospheres.

Nitrogen is present in all living organisms in proteins, nucleic acids and other molecules. It is a large component of animal waste (for example, guano), usually in the form of urea, uric acid, ammonium compounds and derivatives of these nitrogenous products, which are essential nutrients for all plants that are unable to fix atmospheric nitrogen.

Isotopes

There are two stable isotopes of nitrogen: ¹⁴N and ¹⁵N. By far the most common is ¹⁴N (99.634%), which is produced in the CNO cycle in stars and the remaining is ¹⁵N. Of the ten isotopes produced synthetically, ¹³N has a half life of ten minutes and the remaining isotopes have half lives on the order of seconds or less. Biologically-mediated reactions (e.g., assimilation, nitrification, and denitrification) strongly control nitrogen dynamics in the soil. These reactions typically result in ¹⁵N enrichment of the substrate and depletion of the product.

0.73% of the molecular nitrogen in Earth’s atmosphere is comprised of the isotopologue ¹⁴N¹⁵N and almost all the rest is ¹⁴N₂.

Electromagnetic spectrum

Molecular nitrogen (¹⁴N₂) is largely transparent to infrared and visible radiation because it is a homonuclear molecule and thus has no dipole moment to couple to electromagnetic radiation at these wavelengths. Significant absorption occurs at extreme ultraviolet wavelengths, beginning around 100 nanometers. This is associated with electronic transitions in the molecule to states in which charge is not distributed evenly between nitrogen atoms. Nitrogen absorption leads to significant absorption of ultraviolet radiation in the Earth’s upper atmosphere as well as in the atmospheres of other planetary bodies. For similar reasons, pure molecular nitrogen lasers typically emit light in the ultraviolet range.

Nitrogen also makes a contribution to visible air glow from the Earth’s upper atmosphere, through electron impact excitation followed by emission. This visible blue air glow (seen in the polar aurora and in the re-entry glow of returning spacecraft) typically results not from molecular nitrogen, but rather from free nitrogen atoms combining with oxygen to form nitric oxide (NO).

Biological role

Nitrogen is an essential part of amino acids and nucleic acids, both of which are essential to all life on Earth.

Molecular nitrogen in the atmosphere cannot be used directly by either plants or animals, and needs to be converted into nitrogen compounds, or “fixed,” in order to be used by life. Precipitation often contains substantial quantities of ammonium and nitrate, both thought to be a result of nitrogen fixation by lightning and other atmospheric electric phenomena. However, because ammonium is preferentially retained by the forest canopy relative to atmospheric nitrate, most of the fixed nitrogen that reaches the soil surface under trees is in the form of nitrate. Soil nitrate is preferentially assimilated by tree roots relative to soil ammonium.

Specific bacteria (e.g. Rhizobium trifolium) possess enzymes which can fix atmospheric nitrogen (see nitrogen fixation) into a form (ammonium ion) which is chemically useful to higher organisms. This process requires a large amount of energy and anoxic conditions. Such bacteria may be free in the soil (e.g. Azotobacter) but normally exist in a symbiotic relationship in the root nodules of leguminous plants (e.g. clover, Trifolium species, or the soya bean plant, Glycine max). Nitrogen-fixing bacteria can be symbiotic with a number of unrelated plant species. Common examples are legumes, alders (Alnus) spp., lichens, Casuarina, Myrica, liverworts, and Gunnera.

As part of the symbiotic relationship, the plant subsequently converts the ammonium ion to nitrogen oxides and amino acids to form proteins and other biologically useful molecules, such as alkaloids. In return for the usable (fixed) nitrogen, the plant secretes sugars to the symbiotic bacteria.

Some plants are able to assimilate nitrogen directly in the form of nitrates which may be present in soil from natural mineral deposits, artificial fertilizers, animal waste, or organic decay (as the product of bacteria, but not bacteria specifically associated with the plant). Nitrates absorbed in this fashion are converted to nitrites by the enzyme nitrate reductase, and then converted to ammonia by another enzyme called nitrite reductase.

Nitrogen compounds are basic building blocks in animal biology. Animals use nitrogen-containing amino acids from plant sources, as starting materials for all nitrogen-compound animal biochemistry, including the manufacture of proteins and nucleic acids. Some plant-feeding insects are so dependent on nitrogen in their diet, that varying the amount of nitrogen fertilizer applied to a plant can affect the rate of reproduction of the insects feeding on it.

Soluble nitrate is an important limiting factor in the growth of certain bacteria in ocean waters. In many places in the world, artificial fertilizers applied to crop-lands to increase yields result in run-off delivery of soluble nitrogen to oceans at river mouths. This process can result in eutrophication of the water, as nitrogen-driven bacterial growth depletes water oxygen to the point that all higher organisms die. Well-known “dead zone” areas in the U.S. Gulf Coast and the Black Sea are due to this important polluting process.

Many saltwater fish manufacture large amounts of trimethylamine oxide to protect them from the high osmotic effects of their environment (conversion of this compound to dimethylamine is responsible for the early odor in unfresh saltwater fish: PMID 15186102). In animals, the free radical molecule nitric oxide (NO), which is derived from an amino acid, serves as an important regulatory molecule for circulation.

Animal metabolism of NO results in production of nitrite. Animal metabolism of nitrogen in proteins generally results in excretion of urea, while animal metabolism of nucleic acids results in excretion of urea and uric acid. The characteristic odor of animal flesh decay is caused by nitrogen-containing long-chain amines, such as putrescine and cadaverine.

Decay of organisms and their waste products may produce small amounts of nitrate, but most decay eventually returns nitrogen content to the atmosphere, as molecular nitrogen.