Nitrogen is a chemical element with symbol N and atomic number 7.

It was first d
iscovered and isolated by Scottish physician Daniel Rutherford in 1772. Although
Carl Wilhelm Scheele and Henry Cavendish had independently done so at about the
same time, Rutherford is generally accorded the credit because his work was pub
lished first. The name nitrogen was suggested by Jean-Antoine-Claude Chaptal in
1790, when it was found that nitrogen was present in nitric acid and nitrates; t
his name derives from the Greek roots ??t??? "nitre" and -?e???? "to form". Anto
ine Lavoisier suggested instead the name azote, from the Greek ???t???? "no life
", as it is an asphyxiant gas; his name is instead used in many languages, such
as French, Russian, and Turkish, and appears in the English names of some nitrog
en compounds such as hydrazine, azides and azo compounds.
Nitrogen is the lightest member of group 15 of the periodic table, often called
the pnictogens. The name comes from the Greek p???e?? "to choke", directly refer
encing nitrogen's asphyxiating properties. It is a common element in the univers
e, estimated at about seventh in total abundance in the Milky Way and the Solar
System. At standard temperature and pressure, two atoms of the element bind to f
orm dinitrogen, a colourless and odorless diatomic gas with the formula N2. Dini
trogen forms about 78% of Earth's atmosphere, making it the most abundant uncomb
ined element. Nitrogen occurs in all organisms, primarily in amino acids (and th
us proteins), in the nucleic acids (DNA and RNA) and in the energy transfer mole
cule adenosine triphosphate. The human body contains about 3% nitrogen by mass,
the fourth most abundant element in the body after oxygen, carbon, and hydrogen.
The nitrogen cycle describes movement of the element from the air, into the bio
sphere and organic compounds, then back into the atmosphere.
Many industrially important compounds, such as ammonia, nitric acid, organic nit
rates (propellants and explosives), and cyanides, contain nitrogen. The extremel
y strong triple bond in elemental nitrogen (N=N), the second strongest bond in a
ny diatomic molecule, dominates nitrogen chemistry. This causes difficulty for b
oth organisms and industry in converting N2 into useful compounds, but at the sa
me time means that burning, exploding, or decomposing nitrogen compounds to form
nitrogen gas releases large amounts of often useful energy. Synthetically produ
ced ammonia and nitrates are key industrial fertilisers, and fertiliser nitrates
are key pollutants in the eutrophication of water systems.
Apart from its use in fertilisers and energy-stores, nitrogen is a constituent o
f organic compounds as diverse as Kevlar used in high-strength fabric and cyanoa
crylate used in superglue. Nitrogen is a constituent of every major pharmacologi
cal drug class, including antibiotics. Many drugs are mimics or prodrugs of natu
ral nitrogen-containing signal molecules: for example, the organic nitrates nitr
oglycerin and nitroprusside control blood pressure by metabolizing into nitric o
xide. Many notable nitrogen-containing drugs, such as the natural caffeine and m
orphine or the synthetic amphetamines, act on receptors of animal neurotransmitt
ers.
Contents [hide]
1 History
2 Properties
2.1 Atomic
2.2 Isotopes
3 Chemistry and compounds
3.1 Allotropes
3.2 Dinitrogen complexes
3.3 Nitrides, azides, and nitrido complexes
3.4 Hydrides
3.5 Halides and oxohalides
3.6 Oxides
3.7 Oxoacids, oxoanions, and oxoacid salts
3.8 Organic nitrogen compounds
4 Occurrence
5 Production
6 Applications
6.1 Gas
6.2 Liquid
7 Safety
7.1 Gas
7.2 Liquid
8 See also
9 References
10 Bibliography
11 External links
History
Daniel Rutherford, discoverer of nitrogen
Nitrogen compounds have a very long history, ammonium chloride having been known
to Herodotus. They were well known by the Middle Ages. Alchemists knew nitric a
cid as aqua fortis (strong water), as well as other nitrogen compounds such as a
mmonium salts and nitrate salts. The mixture of nitric and hydrochloric acids wa
s known as aqua regia (royal water), celebrated for its ability to dissolve gold
, the king of metals.[3]
The discovery of nitrogen is attributed to the Scottish physician Daniel Rutherf
ord in 1772, who called it noxious air.[4][5] Though he did not recognise it as
an entirely different chemical substance, he clearly distinguished it from Josep
h Black's "fixed air", or carbon dioxide.[6] The fact that there was a component
of air that does not support combustion was clear to Rutherford, although he wa
s not aware that it was an element. Nitrogen was also studied at about the same
time by Carl Wilhelm Scheele,[7] Henry Cavendish,[8] and Joseph Priestley,[9] wh
o referred to it as burnt air or phlogisticated air. Nitrogen gas was inert enou
gh that Antoine Lavoisier referred to it as "mephitic air" or azote, from the Gr
eek word ???t???? (azotikos), "no life".[10] In an atmosphere of pure nitrogen,
animals died and flames were extinguished. Though Lavoisier's name was not accep
ted in English, since it was pointed out that almost all gases (indeed, with the
sole exception of oxygen) are mephitic, it is used in many languages (French, I
talian, Portuguese, Polish, Russian, Albanian, Turkish, etc.; the German Stickst
off similarly refers to the same characteristic, viz. sticken "to choke or suffo
cate") and still remains in English in the common names of many nitrogen compoun
ds, such as hydrazine and compounds of the azide ion. Finally, it led to the nam
e "pnictogens" for the group headed by nitrogen, from the Greek p???e?? "to chok
e".[3]
The English word nitrogen (1794) entered the language from the French nitrogne, c
oined in 1790 by French chemist Jean-Antoine Chaptal (1756 1832),[11] from the Fre
nch nitre (potassium nitrate, also called saltpeter) and the French -gne, "produc
ing", from the Greek -?e??? (-genes, "producer, begetter"). Chaptal's meaning wa
s that nitrogen is the essential part of nitric acid, which in turn was produced
from niter. In earlier times, niter had been confused with Egyptian "natron" (s
odium carbonate) called ??t??? (nitron) in Greek which, despite the name, contai
ned no nitrate.[12]
The earliest military, industrial, and agricultural applications of nitrogen com
pounds used saltpeter (sodium nitrate or potassium nitrate), most notably in gun
powder, and later as fertiliser. In 1910, Lord Rayleigh discovered that an elect
rical discharge in nitrogen gas produced "active nitrogen", a monatomic allotrop
e of nitrogen.[13] The "whirling cloud of brilliant yellow light" produced by hi
s apparatus reacted with mercury to produce explosive mercury nitride.[14]
For a long time, sources of nitrogen compounds were limited. Natural sources ori
ginated either from biology or deposits of nitrates produced by atmospheric reac
tions. Nitrogen fixation by industrial processes like the Frank Caro process (1895 1
899) and Haber Bosch process (1908 1913) eased this shortage of nitrogen compounds,
to the extent that half of global food production (see Applications) now relies
on synthetic nitrogen fertilisers.[15] At the same time, use of the Ostwald proc
ess (1902) to produce nitrates from industrial nitrogen fixation allowed the lar
ge-scale industrial production of nitrates as feedstock in the manufacture of ex
plosives in the World Wars of the 20th century.[16][17]
Properties
Atomic
The shapes of the five orbitals occupied in nitrogen. The two colours show the p
hase or sign of the wave function in each region. From left to right: 1s, 2s (cu
taway to show internal structure), 2px, 2py, 2pz.
A nitrogen atom has seven electrons. In the ground state, they are arranged in t
he electron configuration 1s2
2s2
2p1
x2p1
y2p1
z. It therefore has five valence electrons in the 2s and 2p orbitals, three of w
hich (the p-electrons) are unpaired. It has one of the highest electronegativiti
es among the elements (3.04 on the Pauling scale), exceeded only by chlorine (3.
16), oxygen (3.44), and fluorine (3.98).[18] Following periodic trends, its sing
le-bond covalent radius of 71 pm is smaller than those of boron (84 pm) and carb
on (76 pm), while it is larger than those of oxygen (66 pm) and fluorine (57 pm)
. The nitride anion, N3-, is much larger at 146 pm, similar to that of the oxide
(O2-: 140 pm) and fluoride (F-: 133 pm) anions.[18] The first three ionisation
energies of nitrogen are 1.402, 2.856, and 4.577 MJmol-1, and the sum of the four
th and fifth is 16.920 MJmol-1. Due to these very high figures, nitrogen has no s
imple cationic chemistry.[19]
The lack of radial nodes in the 2p subshell is directly responsible for many of
the anomalous properties of the first row of the p-block, especially in nitrogen
, oxygen, and fluorine. The 2p subshell is very small and has a very similar rad
ius to the 2s shell, facilitating orbital hybridisation. It also results in very
large electrostatic forces of attraction between the nucleus and the valence el
ectrons in the 2s and 2p shells, resulting in very high electronegativities. Hyp
ervalency is almost unknown in these elements for the same reason, because the h
igh electronegativity makes it difficult for a small nitrogen atom to be a centr
al atom in an electron-rich three-center four-electron bond since it would tend
to attract the electrons strongly to itself. Thus, despite nitrogen's position a
t the head of group 15 in the periodic table, its chemistry shows huge differenc
es from that of its heavier congeners phosphorus, arsenic, antimony, and bismuth
.[20]
Nitrogen may be usefully compared to its horizontal neighbours carbon and oxygen
as well as its vertical neighbours in the pnictogen column (phosphorus, arsenic
, antimony, and bismuth). Although each period 2 element from lithium to nitroge
n shows some similarities to the period 3 element in the next group from magnesi
um to sulfur (known as the diagonal relationships), their degree drops off quite
abruptly past the boron silicon pair, so that the similarities of nitrogen to sul
fur are mostly limited to sulfur nitride ring compounds when both elements are t
he only ones present. Nitrogen resembles oxygen far more than it does carbon wit
h its high electronegativity and concomitant capability for hydrogen bonding and
the ability to form coordination complexes by donating its lone pairs of electr
ons. It does not share carbon's proclivity for catenation, with the longest chai
n of nitrogen yet discovered being composed of only eight nitrogen atoms (PhN=N N(
Ph) N=N N(Ph) N=NPh). One property nitrogen does share with both its horizontal neighb
ours is its preferentially forming multiple bonds, typically with carbon, nitrog
en, or oxygen atoms, through pp pp interactions. This is not possible for its vert
ical neighbours; thus, the nitrogen oxides, nitrites, nitrates, nitro-, nitroso-
, azo-, and diazo-compounds, azides, cyanates, thiocyanates, and imino-derivativ
es find no echo with phosphorus, arsenic, antimony, or bismuth. By the same toke
n, however, the complexity of the phosphorus oxoacids finds no echo with nitroge
n.[21]
Isotopes
Main article: Isotopes of nitrogen
Table of nuclides (Segr chart) from carbon to fluorine (including nitrogen). Oran
ge indicates proton emission (nuclides outside the proton drip line); pink for p
ositron emission (inverse beta decay); black for stable nuclides; blue for elect
ron emission (beta decay); and violet for neutron emission (nuclides outside the
neutron drip line). Proton number increases going up the vertical axis and neut
ron number going to the right on the horizontal axis.
Nitrogen has two stable isotopes: 14N and 15N. The first is much more common, ma
king up 99.634% of natural nitrogen, and the second (which is slightly heavier)
makes up the remaining 0.366%. This leads to an atomic weight of around 14.007 u
.[18] Both of these stable isotopes are produced in the CNO cycle in stars, but
14N is more common as its neutron capture is the rate-limiting step. 14N is one
of the five stable odd odd nuclides (a nuclide having an odd number of protons and
neutrons); the other four are 2H, 6Li, 10B, and 180mTa.[22]
The relative abundance of 14N and 15N is practically constant in the atmosphere
but can vary elsewhere, due to natural isotopic fractionation from biological re
dox reactions and the evaporation of natural ammonia or nitric acid.[23] Biologi
cally mediated reactions (e.g., assimilation, nitrification, and denitrification
) strongly control nitrogen dynamics in the soil. These reactions typically resu
lt in 15N enrichment of the substrate and depletion of the product.[24]
The heavy isotope 15N was first discovered by S. M. Naud in 1929, soon after heav
y isotopes of the neighbouring elements oxygen and carbon were discovered.[25] I
t presents one of the lowest thermal neutron capture cross-sections of all isoto
pes.[26] It is frequently used in nuclear magnetic resonance (NMR) spectroscopy
to determine the structures of nitrogen-containing molecules, due to its fractio
nal nuclear spin of one-half, which offers advantages for NMR such as narrower l
ine width. 14N, though also theoretically usable, has an integer nuclear spin of
one and thus has a quadrupole moment that leads to wider and less useful spectr
a.[18] 15N NMR nevertheless has complications not encountered in the more 1H and
13C NMR spectroscopy. The low natural abundance of 15N (0.36%) significantly re
duces sensitivity, a problem which is only exacerbated by its low gyromagnetic r
atio, (only 10.14% that of 1H). As a result, the signal-to-noise ratio for 1H is
about 300 times as much as that for 15N at the same magnetic field strength.[27
] This may be somewhat alleviated by isotopic enrichment of 15N by chemical exch
ange or fractional distillation. 15N-enriched compounds have the advantage that
under standard conditions, they do not undergo chemical exchange of their nitrog
en atoms with atmospheric nitrogen, unlike compounds with labelled hydrogen, car
bon, and oxygen isotopes that must be kept away from the atmosphere.[18] The 15N
:14N ratio is commonly used in stable isotope analysis in the fields of geochemi
stry, hydrology, paleoclimatology and paleoceanography, where it is called d15N.
[28]
Of the ten other isotopes produced synthetically, ranging from 12N to 23N, 13N h
as a half-life of ten minutes and the remaining isotopes have half-lives on the
order of seconds (16N and 17N) or even milliseconds. No other nitrogen isotopes
are possible as they would fall outside the nuclear drip lines, leaking out a pr
oton or neutron.[29] Given the half-life difference, 13N is the most important n
itrogen radioisotope, being relatively long-lived enough to use in positron emis
sion tomography (PET), although its half-life is still short and thus it must be
produced at the venue of the PET, for example in a cyclotron via proton bombard
ment of 16O producing 13N and an alpha particle.[30]
The radioisotope 16N is the dominant radionuclide in the coolant of pressurised
water reactors or boiling water reactors during normal operation, and thus it is
a sensitive and immediate indicator of leaks from the primary coolant system to
the secondary steam cycle, and is the primary means of detection for such leaks
. It is produced from 16O (in water) via an (n,p) reaction in which the 16O atom
captures a neutron and expels a proton. It has a short half-life of about 7.1 s
,[29] but during its decay back to 16O produces high-energy gamma radiation (5 t
o 7 MeV).[29][31] Because of this, access to the primary coolant piping in a pre
ssurised water reactor must be restricted during reactor power operation.[31]
Chemistry and compounds
Allotropes
Molecular orbital diagram of dinitrogen molecule, N2. There are five bonding orb
itals and two antibonding orbitals (marked with an asterisk), giving a total bon
d order of three.
Atomic nitrogen, also known as active nitrogen, is highly reactive, being a trir
adical with three unpaired electrons. Free nitrogen atoms easily react with most
elements to form nitrides, and even when two free nitrogen atoms collide to pro
duce an excited N2 molecule, they may release so much energy on collision with e
ven such stable molecules as carbon dioxide and water to cause homolytic fission
into radicals such as CO and O or OH and H. Atomic nitrogen is prepared by pass
ing an electric discharge through nitrogen gas at 0.1 2 mmHg, which produces atomi
c nitrogen along with a peach-yellow emission that fades slowly as an afterglow
for several minutes even after the discharge terminates.[21]
Given the great reactivity of atomic nitrogen, elemental nitrogen usually occurs
as molecular N2, dinitrogen. This molecule is a colourless, odourless, and tast
eless diamagnetic gas at standard conditions: it melts at -210 C and boils at -19
6 C.[21] Dinitrogen is mostly unreactive at room temperature, but it will neverth
eless react with lithium metal and some transition metal complexes. This is due
to its bonding, which is unique among the diatomic elements at standard conditio
ns in that it has an N=N triple bond. Triple bonds have short bond lengths (in t
his case, 109.76 pm) and high dissociation energies (in this case, 945.41 kJ/mol
), and are thus very strong, explaining dinitrogen's chemical inertness.[21]
There are some theoretical indications that other nitrogen oligomers and polymer
s may be possible. If they could be synthesised, they may have potential applica
tions as materials with a very high energy density, that could be used as powerf
ul propellants or explosives.[32] This is because they should all decompose to d
initrogen, whose N=N triple bond (bond energy 946 kJmol-1) is much stronger than
those of the N=N double bond (418 kJmol-1) or the N N single bond (160 kJmol-1): ind
eed, the triple bond has more than thrice the energy of the single bond. (The op
posite is true for the heavier pnictogens, which prefer polyatomic allotropes.)[
33] A great disadvantage is that most neutral polynitrogens are not expected to
have a large barrier towards decomposition, and that the few exceptions would be
even more challenging to synthesise than the long-sought but still unknown tetr
ahedrane. This stands in contrast to the well-characterised cationic and anionic
polynitrogens azide (N-
3), pentazenium (N+
5), and pentazolide (cyclic aromatic N-
5).[32] Under extremely high pressures (1.1 million atm) and high temperatures (
2000 K), as produced in a diamond anvil cell, nitrogen polymerises into the sing
le-bonded cubic gauche crystal structure. This structure is similar to that of d
iamond, and both have extremely strong covalent bonds, resulting in its nickname
"nitrogen diamond".[34]
At atmospheric pressure, molecular nitrogen condenses (liquefies) at 77 K (-195.
79 C) and freezes at 63 K (-210.01 C)[35] into the beta hexagonal close-packed cry
stal allotropic form. Below 35.4 K (-237.6 C) nitrogen assumes the cubic crystal
allotropic form (called the alpha phase).[36] Liquid nitrogen, a colourless flui
d resembling water in appearance, but with 80.8% of the density (the density of
liquid nitrogen at its boiling point is 0.808 g/mL), is a common cryogen.[37] So
lid nitrogen has many crystalline modifications. It forms a significant dynamic
surface coverage on Pluto[38] and outer moons of the Solar System such as Triton
.[39] Even at the low temperatures of solid nitrogen it is fairly volatile and c
an sublime to form an atmosphere, or condense back into nitrogen frost. It is ve
ry weak and flows in the form of glaciers and on Triton geysers of nitrogen gas
come from the polar ice cap region.[40]
Dinitrogen complexes
Main article: Dinitrogen complex
Structure of [Ru(NH3)5(N2)]2+ (pentaamine(dinitrogen)ruthenium(II)), the first d
initrogen complex to be discovered
The first example of a dinitrogen complex to be discovered was [Ru(NH3)5(N2)]2+
(see figure at right), and soon many other such complexes were discovered. These
complexes, in which a nitrogen molecule donates at least one lone pair of elect
rons to a central metal cation, illustrate how N2 might bind to the metal(s) in
nitrogenase and the catalyst for the Haber process: these processes involving di
nitrogen activation are vitally important in biology and in the production of fe
rtilisers.[41][42]
Dinitrogen is able to coordinate to metals in five different ways. The more well
-characterised ways are the end-on M?N=N (?1) and M?N=N?M (, bis-?1), in which th
e lone pairs on the nitrogen atoms are donated to the metal cation. The less wel
l-characterised ways involve dinitrogen donating electron pairs from the triple
bond, either as a bridging ligand to two metal cations (, bis-?2) or to just one
(?2). The fifth and unique method involves triple-coordination as a bridging lig
and, donating all three electron pairs from the triple bond (3-N2). A few complex
es feature multiple N2 ligands and some feature N2 bonded in multiple ways. Sinc
e N2 is isoelectronic with carbon monoxide (CO) and acetylene (C2H2), the bondin
g in dinitrogen complexes is closely allied to that in carbonyl compounds, altho
ugh N2 is a weaker s-donor and p-acceptor than CO. Theoretical studies show that
s donation is a more important factor allowing the formation of the M N bond than
p back-donation, which mostly only weakens the N N bond, and end-on (?1) donation
is more readily accomplished than side-on (?2) donation.[21]
Today, dinitrogen complexes are known for almost all the transition metals, acco
unting for several hundred compounds. They are normally prepared by three method
s:[21]
Replacing labile ligands such as H2O, H-, or CO directly by nitrogen: these are
often reversible reactions that proceed at mild conditions.
Reducing metal complexes in the presence of a suitable coligand in excess under
nitrogen gas. A common choice include replacing chloride ligands by dimethylphen
ylphosphine (PMe2Ph) to make up for the smaller number of nitrogen ligands attac
hed than the original chlorine ligands.
Converting a ligand with N N bonds, such as hydrazine or azide, directly into a di
nitrogen ligand.
Occasionally the N=N bond may be formed directly within a metal complex, for exa
mple by directly reacting coordinated ammonia (NH3) with nitrous acid (HNO2), bu
t this is not generally applicable. Most dinitrogen complexes have colours withi
n the range white-yellow-orange-red-brown; a few exceptions are known, such as t
he blue [{Ti(?5-C5H5)2}2-(N2)].[21]
Nitrides, azides, and nitrido complexes
Nitrogen bonds to almost all the elements in the periodic table except the first
three noble gases, helium, neon, and argon, and some of the very short-lived el
ements after bismuth, creating an immense variety of binary compounds with varyi
ng properties and applications.[21] Many binary compounds are known: with the ex
ception of the nitrogen hydrides, oxides, and fluorides, these are typically cal
le