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Iron - Wikipedia

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From Wikipedia, the free encyclopedia

Iron is a chemical element with symbol Fe (from La n: ferrum) and atomic

number 26. It is a metal in the rst transi on series. It is by mass the most
common element on Earth, forming much of Earth's outer and inner core.
It is the fourth most common element in the Earth's crust. Its abundance
in rocky planets like Earth is due to its abundant produc on by fusion in
high-mass stars, where it is the last element to be produced with release
of energy before the violent collapse of a supernova, which scaIers the
iron into space.
Like the other group 8 elements, ruthenium and osmium, iron exists in a
wide range of oxida on states, 2 to +6, although +2 and +3 are the most
common. Elemental iron occurs in meteoroids and other low oxygen
environments, but is reac ve to oxygen and water. Fresh iron surfaces
appear lustrous silvery-gray, but oxidize in normal air to give hydrated iron
oxides, commonly known as rust. Unlike the metals that form passiva ng
oxide layers, iron oxides occupy more volume than the metal and thus
ake o, exposing fresh surfaces for corrosion.
Iron metal has been used since ancient mes, although copper alloys,
which have lower mel ng temperatures, were used even earlier in human
history. Pure iron is rela vely soN, but is unobtainable by smel ng
because it is signicantly hardened and strengthened by impuri es, in
par cular carbon, from the smel ng process. A certain propor on of
carbon (between 0.002% and 2.1%) produces steel, which may be up to
1000 mes harder than pure iron. Crude iron metal is produced in blast
furnaces, where ore is reduced by coke to pig iron, which has a high
carbon content. Further renement with oxygen reduces the carbon
content to the correct propor on to make steel. Steels and iron alloys
formed with other metals (alloy steels) are by far the most common
industrial metals because they have a great range of desirable proper es
and iron-bearing rock is abundant.
Iron chemical compounds have many uses. Iron oxide mixed with
aluminium powder can be ignited to create a thermite reac on, used in
welding and purifying ores. Iron forms binary compounds with the
halogens and the chalcogens. Among its organometallic compounds is
ferrocene, the rst sandwich compound discovered.
Iron plays an important role in biology, forming complexes with molecular
oxygen in hemoglobin and myoglobin; these two compounds are common
oxygen transport proteins in vertebrates. Iron is also the metal at the
ac ve site of many important redox enzymes dealing with cellular
respira on and oxida on and reduc on in plants and animals. A human
male of average height has about 4 grams of iron in his body, a female
about 3.5 grams. This iron is distributed throughout the body in
hemoglobin, ssues, muscles, bone marrow, blood proteins, enzymes,
ferri n, hemosiderin, and transport in plasma.[4]

1 Characteris cs
1.1 Mechanical proper es
1.2 Phase diagram and allotropes
1.3 Isotopes
1.4 Occurrence
2 Chemistry and compounds



Spectral lines of iron

General proper es
Name, symbol

iron, Fe

Pronuncia on



lustrous metallic with a grayish nge

Iron in the periodic table


manganese iron cobalt

Atomic number (Z)


Group, block

group 8, d-block


period 4
transi on metal

Element category
Standard atomic
weight () (Ar)


congura on

[Ar] 3d6 4s2

2, 8, 14, 2

per shell

Physical proper es


Mel ng point

1811 K (1538 C, 2800 F)

Boiling point

3134 K (2862 C, 5182 F)

Density near r.t.

7.874 g/cm3

when liquid,
at m.p.

6.98 g/cm3

Heat of fusion

13.81 kJ/mol

Heat of
vaporiza on

340 kJ/mol

Molar heat

25.10 J/(molK)
Vapor pressure

P (Pa)

at T (K) 1728




10 k





100 k

Atomic proper es
Oxida on states

4, 2, 1, +1,[2] +2, +3, +4, +5,[3] +6

(an amphoteric oxide)

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2.1 Binary compounds

2.2 Solu on chemistry
2.3 Coordina on compounds
2.4 Organometallic compounds
3 History
3.1 Wrought iron
3.2 Cast iron
3.3 Steel
3.4 Founda ons of modern chemistry
4 Etymology
5 Symbolic role
6 Produc on of metallic iron
6.1 Industrial routes
6.1.1 Blast furnace processing
6.1.2 Direct iron reduc on
6.1.3 Further processes
7 Applica ons
7.1 Metallurgical
7.2 Iron compounds
8 Biological and pathological role
8.1 Biochemistry
8.2 Health and diet
8.3 Excess
8.4 Deciency
9 See also
10 References
11 Bibliography
12 Further reading
13 External links

Characteris cs
Mechanical proper es


Electronega vity

Pauling scale: 1.83

Ioniza on

1st: 762.5 kJ/mol

2nd: 1561.9 kJ/mol
3rd: 2957 kJ/mol

Atomic radius

empirical: 126 pm

Covalent radius

Low spin: 1323 pm

High spin: 1526 pm

Crystal structure

body-centered cubic (bcc)

a=286.65 pm

Crystal structure

face-centered cubic (fcc)

between 11851667 K

Speed of sound
thin rod

5120 m/s (at r.t.) (electroly c)


11.8 m/(mK) (at 25 C)

conduc vity

80.4 W/(mK)

resis vity

96.1 nm (at 20 C)

Curie point

1043 K

Magne c ordering

ferromagne c

Young's modulus

211 GPa

Shear modulus

82 GPa

Bulk modulus

170 GPa

Poisson ra o


Mohs hardness

Vickers hardness

608 MPa

Brinell hardness

2001180 MPa

The mechanical proper es of CAS Number

iron and its alloys can be
evaluated using a variety of
before 5000 BC
tests, including the Brinell
test, Rockwell test and the
Most stable isotopes of iron
Vickers hardness test. The
Iron whiskers
data on iron is so consistent
that it is oNen used to
5.85% is stable with 28 neutrons
Ausformed (hardened)
2930 8501200 calibrate measurements or
2.73 y
to compare tests.[6][7]
Martensi c steel
2070 600
91.75% is stable with 30 neutrons
However, the mechanical
Baini c steel
1380 400
proper es of iron are
2.12% is stable with 31 neutrons
Pearli c steel
1200 350
0.28% is stable with 32 neutrons
sample's purity: pure, single
Cold-worked iron
690 200
44.6 d 1.565
crystals of iron are actually
Small-grain iron
340 100
soNer than aluminium,[5]
2.6106 y 3.978
and the purest industrially
Carbon-containing iron 140 40
produced iron (99.99%) has a
Pure, single-crystal iron 10
hardness of 2030 Brinell.[8] An increase in the carbon content will cause a
signicant increase in the hardness and tensile strength of iron. Maximum hardness
of 65 Rc is achieved with a 0.6% carbon content, although the alloy has low tensile strength.[9] Because of the soNness of iron, it is
much easier to work with than its heavier congeners ruthenium and osmium.[10]
Characteris c values of tensile strength
(TS) and Brinell hardness (BH) of dierent
forms of iron.[5][6]
(MPa) (Brinell)

Because of its signicance for planetary cores, the physical proper es of iron at high pressures and temperatures have also been
studied extensively. The form of iron that is stable under standard condi ons can be subjected to pressures up to ca. 15 GPa
before transforming into a high-pressure form, as described in the next sec on.

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Phase diagram and allotropes

Iron represents an example of allotropy in a metal. There are at least four allotropic
forms of iron, known as , , , and ; at very high pressures and temperatures, some
controversial experimental evidence exists for a stable phase.[11]
As molten iron cools past its freezing point of
1538 C, it crystallizes into its allotrope,
which has a body-centered cubic (bcc) crystal
structure. As it cools further to 1394 C, it
changes to its -iron allotrope, a
Molar volume vs. pressure for iron at
face-centered cubic (fcc) crystal structure, or
room temperature
austenite. At 912 C and below, the crystal
structure again becomes the bcc -iron
allotrope, or ferrite. Finally, at 770 C (the Curie point, Tc) iron's magne c ordering
changes from paramagne c to ferromagne c. As the iron passes through the Curie
temperature there is no change in crystalline structure, but there is a change in
"domain structure", where each domain contains iron atoms with a par cular
Low-pressure phase diagram of pure iron
electronic spin. In unmagne zed iron, all the electronic spins of the atoms within one
domain have the same axis orienta on; however, the electrons of neighboring domains
have other orienta ons with the result of mutual cancella on and no magne c eld. In magne zed iron, the electronic spins of
the domains are aligned and the magne c eects are reinforced. Although each domain contains billions of atoms, they are very
small, about 10 micrometres across.[12] This happens because the two unpaired electrons on each iron atom are in the dz2 and dx2
y2 orbitals, which do not point directly at the nearest neighbors in the body-centered cubic ladce and therefore do not
par cipate in metallic bonding; thus, they can interact magne cally with each other so that their spins align.[13]
At pressures above approximately 10 GPa and temperatures of a few hundred kelvin or less, -iron changes into a hexagonal
close-packed (hcp) structure, which is also known as -iron; the higher-temperature -phase also changes into -iron, but does so
at higher pressure. The -phase, if it exists, would appear at pressures of at least 50 GPa and temperatures of at least 1500 K and
have an orthorhombic or a double hcp structure.[11] These high-pressure phases of iron are important as endmember models for
the solid parts of planetary cores. The inner core of the Earth is generally presumed to be an iron-nickel alloy with (or )
structure.[14] Somewhat confusingly, the term "-iron" is some mes also used to refer to -iron above its Curie point, when it
changes from being ferromagne c to paramagne c, even though its crystal structure has not changed.[13]
The mel ng point of iron is experimentally well dened for pressures less than 50 GPa. For greater pressures, studies put the
--liquid triple point at pressures that dier by tens of gigapascals and 1000 K in the mel ng point. Generally speaking,
molecular dynamics computer simula ons of iron mel ng and shock wave experiments suggest higher mel ng points and a much
steeper slope of the mel ng curve than sta c experiments carried out in diamond anvil cells.[15] The mel ng and boiling points of
iron, along with its enthalpy of atomiza on, are lower than those of the earlier 3d elements from scandium to chromium,
showing the lessened contribu on of the 3d electrons to metallic bonding as they are aIracted more and more into the inert core
by the nucleus;[16] however, they are higher than the values for the previous element manganese because that element has a
half-lled 3d subshell and consequently its d-electrons are not easily delocalized. This same trend appears for ruthenium but not

Naturally occurring iron consists of four stable isotopes: 5.845% of 54Fe, 91.754% of 56Fe, 2.119% of 57Fe and 0.282% of 58Fe. Of
these stable isotopes, only 57Fe has a nuclear spin (12). The nuclide 54Fe theore cally can undergo double electron capture to
54 Cr, but the process has never been observed and only a lower limit on the half-life of 3.11022 years has been established.[17]
60 Fe is an ex

nct radionuclide of long half-life (2.6 million years).[18] It is not found on Earth, but its ul mate decay product is its
granddaughter, the stable nuclide 60Ni.[17] Much of the past work on isotopic composi on of iron has focused on the
nucleosynthesis of 60Fe through studies of meteorites and ore forma on. In the last decade, advances in mass spectrometry have
allowed the detec on and quan ca on of minute, naturally occurring varia ons in the ra os of the stable isotopes of iron.
Much of this work is driven by the Earth and planetary science communi es, although applica ons to biological and industrial
systems are emerging.[19]
In phases of the meteorites Semarkona and Chervony Kut, a correla on between the concentra on of 60Ni, the granddaughter of
60 Fe, and the abundance of the stable iron isotopes provided evidence for the existence of 60 Fe at the me of forma on of the
Solar System. Possibly the energy released by the decay of 60Fe, along with that released by 26Al, contributed to the remel ng
and dieren a on of asteroids aNer their forma on 4.6 billion years ago. The abundance of 60Ni present in extraterrestrial
material may bring further insight into the origin and early history of the Solar System.[20]

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The most abundant iron isotope 56Fe is of par cular interest to nuclear scien sts because it represents the most common
endpoint of nucleosynthesis.[21] Since 56Ni (14 alpha par cles) is easily produced from lighter nuclei in the alpha process in
nuclear reac ons in supernovae (see silicon burning process), it is the endpoint of fusion chains inside extremely massive stars,
since addi on of another alpha par cle, resul ng in 60Zn, requires a great deal more energy. This 56Ni, which has a half-life of
about 6 days, is created in quan ty in these stars, but soon decays by two successive positron emissions within supernova decay
products in the supernova remnant gas cloud, rst to radioac ve 56Co, and then to stable 56Fe. As such, iron is the most
abundant element in the core of red giants, and is the most abundant metal in iron meteorites and in the dense metal cores of
planets such as Earth.[22] It is also very common in the universe, rela ve to other stable metals of approximately the same atomic
weight.[22][23] Iron is the sixth most abundant element in the Universe, and the most common refractory element.[24]
Although a further ny energy gain could be extracted by synthesizing 62Ni, which has a marginally higher binding energy than
ons in stars are unsuitable for this process. Element produc on in supernovas and distribu on on Earth greatly favor
iron over nickel, and in any case, 56Fe s ll has a lower mass per nucleon than 62Ni due to its higher frac on of lighter protons.[25]
Hence, elements heavier than iron require a supernova for their forma on, involving rapid neutron capture by star ng 56Fe
56 Fe, condi

In the far future of the universe, assuming that proton decay does not occur, cold fusion occurring via quantum tunnelling would
cause the light nuclei in ordinary maIer to fuse into 56Fe nuclei. Fission and alpha-par cle emission would then make heavy
nuclei decay into iron, conver ng all stellar-mass objects to cold spheres of pure iron.[26]

Metallic or na ve iron is rarely found on the surface of the Earth because it tends to
oxidize, but its oxides are pervasive and represent the primary ores. While it makes up
about 5% of the Earth's crust, both the Earth's inner and outer core are believed to consist
largely of an iron-nickel alloy cons tu ng 35% of the mass of the Earth as a whole. Iron is
consequently the most abundant element on Earth, but only the fourth most abundant
element in the Earth's crust, aNer oxygen, silicon, and aluminium.[27][28] Most of the iron
in the crust is found combined with oxygen as iron oxide minerals such as hema te
(Fe2O3), magne te (Fe3O4), and siderite (FeCO3). Many igneous rocks also contain the
sulde minerals pyrrho te and pentlandite.[29][30]
Ferropericlase (Mg,Fe)O, a solid solu on of periclase (MgO) and ws te (FeO), makes up
about 20% of the volume of the lower mantle of the Earth, which makes it the second
most abundant mineral phase in that region aNer silicate perovskite (Mg,Fe)SiO3; it also is
the major host for iron in the lower mantle.[31] At the boIom of the transi on zone of the
mantle, the reac on -(Mg,Fe)2[SiO4] (Mg,Fe)[SiO3] + (Mg,Fe)O transforms -olivine
into a mixture of perovskite and ferropericlase and vice versa. In the literature, this
mineral phase of the lower mantle is also oNen called magnesiows te.[32] Silicate
perovskite may form up to 93% of the lower mantle,[33] and the magnesium iron form,
(Mg,Fe)SiO3, is considered to be the most abundant mineral in the Earth, making up 38%
of its volume.[34]

Iron meteorites, similar in

composi on to the Earth's inner- and
outer core

Ochre path in the Roussillon

Large deposits of iron are found in banded iron forma ons. These geological forma ons
are a type of rock consis ng of repeated thin layers of iron oxides alterna ng with bands of iron-poor shale and chert. The
banded iron forma ons were laid down in the me between 3,700 million years ago and 1,800 million years ago.[35][36]
The men oned iron compounds have been used as pigments (compare ochre) since historical me and contribute as well to the
color of various geological forma ons, e.g. the Bundsandstein (Bri sh Bunter, colored sandstein).[37] In the case of the
Eisensandstein (a jurassic 'iron sandstone', e.g. from Donzdorf) in Germany[38] and Bath stone in the UK, iron pigments contribute
to the yellowish color of large amounts of historical buildings and sculptures.[39] The proverbial red color of the surface of Mars is
derived from an iron oxide-rich regolith.[40]
Signicant amounts of iron occur in the iron sulde mineral pyrite (FeS2), but it is dicult to extract iron from it and it is therefore
not used. In fact, iron is so common that produc on generally focuses only on ores with very high quan es of it. During
weathering, iron tends to leach from sulde deposits as the sulfate and from silicate deposits as the bicarbonate. Both of these
are oxidized in aqueous solu on and precipitate in even mildly elevated pH as iron(III) oxide.[41]
About 1 in 20 meteorites consist of the unique iron-nickel minerals taenite (3580% iron) and kamacite (9095% iron). Although
rare, iron meteorites are the main form of natural metallic iron on the Earth's surface.[42] According to the Interna onal Resource
Panel's Metal Stocks in Society report, the global stock of iron in use in society is 2200 kg per capita. Much of this is in
more-developed countries (700014000 kg per capita) rather than less-developed countries (2000 kg per capita).[43]

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Chemistry and compounds

Iron shows the characteris c chemical proper es of the
transi on metals, namely the ability to form variable oxida on
states diering by steps of one and a very large coordina on
and organometallic chemistry: indeed, it was the discovery of an
iron compound, ferrocene, that revolu onalized the laIer eld
in the 1950s.[44] Iron is some mes considered as a prototype for
the en re block of transi on metals, due to its abundance and
the immense role it has played in the technological progress of
humanity.[45] Its 26 electrons are arranged in the congura on
[Ar]3d64s2, of which the 3d and 4s electrons are rela vely close
in energy, and thus it can lose a variable number of electrons
and there is no clear point where further ioniza on becomes

Oxida on

Representa ve compound

2 (d10)

Disodium tetracarbonylferrate (Collman's reagent)

1 (d9)


0 (d8)

Iron pentacarbonyl

1 (d7)

Cyclopentadienyliron dicarbonyl dimer ("Fp2")

2 (d6)

Ferrous sulfate, ferrocene

3 (d5)

Ferric chloride, ferrocenium tetrauoroborate

4 (d4)


5 (d3)


Iron forms compounds mainly in the +2 and +3 oxida on states.

Potassium ferrate
6 (d2)
Tradi onally, iron(II) compounds are called ferrous, and iron(III)
compounds ferric. Iron also occurs in higher oxida on states, an
example being the purple potassium ferrate (K2FeO4) which contains iron in its +6 oxida on state, although this is very easily
reduced. Iron(IV) is a common intermediate in many biochemical oxida on reac ons.[46][47] Numerous organometallic
compounds contain formal oxida on states of +1, 0, 1, or even 2. The oxida on states and other bonding proper es are oNen
assessed using the technique of Mssbauer spectroscopy.[48] There are also many mixed valence compounds that contain both
iron(II) and iron(III) centers, such as magne te and Prussian blue (Fe4(Fe[CN]6)3).[47] The laIer is used as the tradi onal "blue" in
Iron is the rst of the transi on metals that cannot reach its group oxida on state of +8, although its heavier congeners
ruthenium and osmium can, with ruthenium having more diculty than osmium.[13] Ruthenium exhibits an aqueous ca onic
chemistry in its low oxida on states similar to that of iron, but osmium does not, favoring high oxida on states in which it forms
anionic complexes.[13] In fact, in this second half of the 3d transi on series, ver cal similari es down the groups compete with
the horizontal similari es of iron with its neighbors cobalt and nickel in the periodic table, which are also ferromagne c at room
temperature and share similar chemistry. As such, iron, cobalt, and nickel are some mes grouped together as the iron triad.[45]
The iron compounds produced on the largest scale in industry are iron(II) sulfate
(FeSO47H2O) and iron(III) chloride (FeCl3). The former is one of the most readily available
sources of iron(II), but is less stable to aerial oxida on than Mohr's salt
((NH4)2Fe(SO4)26H2O). Iron(II) compounds tend to be oxidized to iron(III) compounds in
the air.[47]
Unlike many other metals, iron does not form amalgams with mercury. As a result, mercury
is traded in standardized 76 pound asks (34 kg) made of iron.[50]
Iron is by far the most reac ve element in its group; it is pyrophoric when nely divided
and dissolves easily in dilute acids, giving Fe2+. However, it does not react with
concentrated nitric acid and other oxidizing acids due to the forma on of an impervious
oxide layer, which can nevertheless react with hydrochloric acid.[13]

Hydrated iron(III) chloride, also

known as ferric chloride

Binary compounds
Iron reacts with oxygen in the air to form various oxide and hydroxide compounds; the most common are iron(II,III) oxide (Fe3O4),
and iron(III) oxide (Fe2O3). Iron(II) oxide also exists, though it is unstable at room temperature. Despite their names, they are
actually all non-stoichiometric compounds whose composi ons may vary.[51] These oxides are the principal ores for the
produc on of iron (see bloomery and blast furnace). They are also used in the produc on of ferrites, useful magne c storage
media in computers, and pigments. The best known sulde is iron pyrite (FeS2), also known as fool's gold owing to its golden
luster.[47] It is not an iron(IV) compound, but is actually an iron(II) polysulde containing Fe2+ and S2
2 ions in a distorted sodium
chloride structure.[51]
The binary ferrous and ferric halides are well-known, with the excep on of ferric iodide. The ferrous halides typically arise from
trea ng iron metal with the corresponding hydrohalic acid to give the corresponding hydrated salts.[47]
Fe + 2 HX FeX2 + H2 (X = F, Cl, Br, I)

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Iron reacts with uorine, chlorine, and bromine to give the corresponding ferric halides,
ferric chloride being the most common.[52]
2 Fe + 3 X2 2 FeX3 (X = F, Cl, Br)
Ferric iodide is an excep on, being thermodynamically unstable due to the oxidizing
power of Fe3+ and the high reducing power of I:[52]
2 I + 2 Fe3+ I2 + 2 Fe2+ (E0 = +0.23 V)
Nevertheless, milligram amounts of ferric iodide, a black solid, may s ll be prepared
through the reac on of iron pentacarbonyl with iodine and carbon monoxide in the
presence of hexane and light at the temperature of 20 C, making sure that the system is
well sealed o from air and water.[52]

Pourbaix diagram of iron

Solu on chemistry
The standard reduc on poten als in acidic aqueous solu on for some common iron ions are given below:[13]
Fe2+ + 2 e


E0 = 0.447 V

Fe3+ + 3 e


E0 = 0.037 V

Fe3+ + 4 H O E0 = +2.20 V
4 +8H +3e

The red-purple tetrahedral ferrate(VI) anion is such a strong oxidizing agent that it oxidizes nitrogen and
ammonia at room temperature, and even water itself in acidic or neutral solu ons:[52]

4 FeO2
4 + 10 H2O 4 Fe + 20 OH + 3 O2
The Fe3+ ion has a large simple ca onic chemistry, although the pale-violet hexaquo ion [Fe(H2O)6]3+ is very
readily hydrolyzed when pH increases above 0 as follows:[53]

[Fe(H2O)5(OH)]2+ + H+

K = 103.05 mol dm3

[Fe(H2O)5(OH)]2+ [Fe(H2O)4(OH)2]+ + H+

K = 103.26 mol dm3

2 [Fe(H2O)6]3+

Comparison of
colors of
solu ons of
ferrate (leN) and


[Fe(H2O)4(OH)]2 + 2 H+ + 2 H2O K = 102.91 mol dm3

As pH rises above 0 the above yellow hydrolyzed species form

and as it rises above 23, reddish-brown hydrous iron(III)
oxide precipitates out of solu on. Although Fe3+ has an d5
congura on, its absorp on spectrum is not like that of Mn2+
with its weak, spin-forbidden dd bands, because Fe3+ has
higher posi ve charge and is more polarizing, lowering the
energy of its ligand-to-metal charge transfer absorp ons.
Thus, all the above complexes are rather strongly colored,
Dark red iron(III) oxide
Blue-green iron(II) sulfate
with the single excep on of the hexaquo ion and even that
has a spectrum dominated by charge transfer in the near
ultraviolet region.
On the other hand, the pale green
iron(II) hexaquo ion [Fe(H2O)6]2+ does not undergo appreciable hydrolysis. Carbon dioxide is not evolved when carbonate anions
are added, which instead results in white iron(II) carbonate being precipitated out. In excess carbon dioxide this forms the slightly
soluble bicarbonate, which occurs commonly in groundwater, but it oxidises quickly in air to form iron(III) oxide that accounts for
the brown deposits present in a sizeable number of streams.[54]

Coordina on compounds
Many coordina on compounds of iron are known. A typical six-coordinate anion is hexachloroferrate(III), [FeCl6]3, found in the
mixed salt tetrakis(methylammonium) hexachloroferrate(III) chloride.[55][56] Complexes with mul ple bidentate ligands have
geometric isomers. For example, the trans-chlorohydridobis(bis-1,2-(diphenylphosphino)ethane)iron(II) complex is used as a
star ng material for compounds with the Fe(dppe)2 moiety.[57][58] The ferrioxalate ion with three oxalate ligands (shown at right)
displays helical chirality with its two non-superposable geometries labelled (lambda) for the leN-handed screw axis and
(delta) for the right-handed screw axis, in line with IUPAC conven ons.[53] Potassium ferrioxalate is used in chemical ac nometry

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and along with its sodium salt undergoes photoreduc on applied in old-style
photographic processes. The dihydrate of iron(II) oxalate has a polymeric
structure with co-planar oxalate ions bridging between iron centres with the
water of crystallisa on located forming the caps of each octahedron, as
illustrated below.[59]

The two enan omorphs of the ferrioxalate ion

Ball-and-s ck model of a chain in the crystal structure of iron(II) oxalate dihydrate

Prussian blue, Fe4[Fe(CN)6]3, is the most famous of the cyanide complexes of iron. Its
forma on can be used as a simple wet chemistry test to dis nguish between aqueous
solu ons of Fe2+ and Fe3+ as they react (respec vely) with potassium ferricyanide and
potassium ferrocyanide to form Prussian blue.[47]

Prussian blue

Iron(III) complexes are quite similar to those of chromium(III) with the excep on of
iron(III)'s preference for O-donor instead of N-donor ligands. The laIer tend to be rather more
unstable than iron(II) complexes and oNen dissociate in water. Many FeO complexes show intense
colors and are used as tests for phenols or enols. For example, in the ferric chloride test, used to
determine the presence of phenols, iron(III) chloride reacts with a phenol to form a deep violet
3 ArOH + FeCl3 Fe(OAr)3 + 3 HCl (Ar = aryl)
Among the halide and pseudohalide complexes, uoro complexes of iron(III) are the most stable,
with the colorless [FeF5(H2O)]2 being the most stable in aqueous solu on. Chloro complexes are less
stable and favor tetrahedral coordina on as in [FeCl4]; nally, [FeBr4] and [FeI4] reduce themselves
Blood-red posi ve
easily to iron(II). Thiocyanate is a common test for the presence of iron(III) as it forms the blood-red
thiocyanate test for
[Fe(SCN)(H2O)5]2+. Like manganese(II), most iron(III) complexes are high-spin, the excep ons being
those with ligands that are high in the spectrochemical series such as cyanide. An example of a
low-spin iron(III) complex is [Fe(CN)6]3. The cyanide ligands may easily be detached in [Fe(CN)6]3, and hence this complex is
poisonous, unlike the iron(II) complex [Fe(CN)6]4 found in Prussian blue,[53] which does not release hydrogen cyanide except
when dilute acids are added.[54] Iron shows a great variety of electronic spin states, including every possible spin quantum
number value for a d-block element from 0 (diamagne c) to 52 (5 unpaired electrons). This value is always half the number of
unpaired electrons. Complexes with zero to two unpaired electrons are considered low-spin and those with four or ve are
considered high-spin.[51]
Iron(II) complexes are less stable than iron(III) complexes but the preference for O-donor ligands is less marked, so that for
example [Fe(NH3)6]2+ is known while [Fe(NH3)6]3+ is not. They have a tendency to be oxidized to iron(III) but this can be
moderated by low pH and the specic ligands used.[54]

Organometallic compounds
Cyanide complexes are technically organometallic but more important are carbonyl complexes and sandwich and half-sandwich
compounds. The premier iron(0) compound is iron pentacarbonyl, Fe(CO)5, which is used to produce carbonyl iron powder, a
highly reac ve form of metallic iron. Thermolysis of iron pentacarbonyl gives the trinuclear cluster, triiron dodecacarbonyl.
Collman's reagent, disodium tetracarbonylferrate, is a useful reagent for organic chemistry; it contains iron in the 2 oxida on
state. Cyclopentadienyliron dicarbonyl dimer contains iron in the rare +1 oxida on state.[60]
Ferrocene was an extremely important compound in the early history of the branch of organometallic chemistry, and to this day
iron is s ll one of the most important metals in this eld.[61] It was rst synthesised in 1951 during an aIempt to prepare the
fulvalene (C10H8) by oxida ve dimeriza on of cyclopentadiene; the resultant product was found to have molecular formula
C10H10Fe and reported to exhibit "remarkable stability".[62] The discovery sparked substan al interest in the eld of
organometallic chemistry,[63][64] in part because the structure proposed by Pauson and Kealy (shown at right) was inconsistent
with then-exis ng bonding models and did not explain its unexpected stability. Consequently, the ini al challenge was to
deni vely determine the structure of ferrocene in the hope that its bonding and proper es would then be understood. The

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shockingly novel sandwich structure, [Fe(5-C5H5)2],[63] was deduced and

reported independently by three groups in 1952: Robert Burns Woodward and
Georey Wilkinson inves gated the reac vity in order to determine the
structure[65] and demonstrated that ferrocene undergoes similar reac ons to a
typical aroma c molecule (such as benzene),[66] Ernst OIo Fischer deduced the
sandwich structure and also began synthesising other metallocenes including
cobaltocene;[67] Eiland and Pepinsky provided X-ray crystallographic
conrma on of the sandwich structure.[68] Applying valence bond theory to
ferrocene by considering an Fe2+ centre and two cyclopentadienide anions
(C5H5), which are known to be aroma c according to Hckel's rule and hence
highly stable, allowed correct predic on of the geometry of the molecule. Once
molecular orbital theory was successfully applied and the Dewar-ChaIDuncanson model proposed,[69] the reasons for ferrocene's remarkable stability
became clear.[70] Ferrocene was not the rst organometallic compound known
Zeise's salt, K[PtCl3(C2H4)]H2O was reported in 1831[71][72] and Mond's
discovery of Ni(CO)4 occurred in 1888,[73] but it was ferrocene's discovery that
began organometallic chemistry as a separate area of chemistry. It was so important that Wilkinson
and Fischer shared the 1973 Nobel Prize for Chemistry "for their pioneering work, performed
independently, on the chemistry of the organometallic, so called sandwich compounds".[74]
Ferrocene itself can be used as the backbone of a ligand, e.g. 1,1'-bis(diphenylphosphino)ferrocene
(dppf). Ferrocene can itself be oxidized to the ferrocenium ca on (Fc+); the ferrocene/ferrocenium
couple is oNen used as a reference in electrochemistry.[64]
Metallocenes like ferrocene can be prepared by reac on of freshly-cracked cyclopentadiene with
iron(II) chloride and a weak base.[75] It is an aroma c substance and undergoes subs tu on
reac ons rather than addi on reac ons on the cyclopentadienyl ligands. For example,
Friedel-CraNs acyla on of ferrocene with ace c anhydride yields acetylferrocene[76] just as
acyla on of benzene yields acetophenone under similar condi ons.

Fulvalene, which Pauson

and Kealy sought to

The (incorrect) structure

for ferrocene that Pauson
and Kealy proposed

The structural
formula of

Powdered ferrocene

Iron-centered organometallic species are used as catalysts. The Knlker complex, for example, is a transfer hydrogena on catalyst
for ketones.[77]

Wrought iron
Iron belongs to the elements undoubtedly known to the ancient world.[78] It has been worked, or wrought,
for millennia. However, iron objects of great age are much rarer than objects made of gold or silver due to the
ease with which iron corrodes.[79]

The symbol for

Mars has been
used since
an quity to
represent iron.

Beads made from meteoric iron in 3500 BCE or earlier were found in Gerzah, Egypt by G. A. Wainwright.[80]
The beads contain 7.5% nickel, which is a signature of meteoric origin since iron found in the Earth's crust
generally has only minuscule nickel impuri es. Meteoric iron was highly regarded due to its origin in the
heavens and was oNen used to forge weapons and tools.[80] For example, a dagger made of meteoric iron
was found in the tomb of Tutankhamun, containing similar propor ons of iron, cobalt, and nickel to a
meteorite discovered in the area, deposited by an ancient meteor shower.[81][82][83] Items that were likely
made of iron by Egyp ans date from 3000 to 2500 BCE.[79] Meteori c iron is comparably soN and duc le and

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easily forged by cold working but may get briIle when heated because of the nickel
The rst iron produc on started in the Middle Bronze Age but it took several centuries
before iron displaced bronze. Samples of smelted iron from Asmar, Mesopotamia and Tall
Chagar Bazaar in northern Syria were made some me between 3000 and 2700 BCE.[85]
The Hidtes established an empire north-central Anatolia around 1600 BCE. They appear
to be the rst to understand the produc on of iron from its ores and regard it highly in
their society.[86] The Hidtes began to smelt iron between 1500 and 1200 BCE and the
prac ce spread to the rest of the Near East aNer their empire fell in 1180 BCE.[85] The
subsequent period is called the Iron Age.
Ar facts of smelted iron are found in India da ng from 1800 to 1200 BCE,[87] and in the
Levant from about 1500 BCE (sugges ng smel ng in Anatolia or the Caucasus).[88][89]
Alleged references (compare history of metallurgy in South Asia) to iron in the Indian
Vedas have been used for claims of a very early usage of iron in India respec vely to date
the texts as such. The rigveda term ayas (metal) probably refers to copper and bronze,
while iron or yma ayas, literally "black metal", rst is men oned in the post-rigvedic

The iron pillar of Delhi is an example

of the iron extrac on and processing
methodologies of early India.

There is some archaeological evidence of iron being smelted in Zimbabwe and southeast
Africa as early as the eighth century BCE.[91] Iron working was introduced to Greece in the
late 11th century BCE, from which it spread quickly throughout Europe.[92]
The spread of ironworking in Central and Western Europe is associated with Cel c
expansion. According to Pliny the Elder, iron use was common in the Roman era.[80] The
annual iron output of the Roman Empire is es mated at 84750 t,[93] while the similarly
populous and contemporary Han China produced around 5000 t.[94] In China, iron only
appears circa 700500 BCE.[95] Iron smel ng may have been introduced into China
through Central Asia.[96] The earliest evidence of the use of a blast furnace in China dates
to the 1st century AD,[97] and cupola furnaces were used as early as the Warring States
period (403221 BCE).[98] Usage of the blast and cupola furnace remained widespread
during the Song and Tang Dynas es.[99]

Iron harpoon head from Greenland.

The iron edge covers a narwhaltusk
harpoon using meteorite iron from
the Cape York meteorite, one of the
largest iron meteorites known.

During the Industrial Revolu on in Britain, Henry Cort began rening iron from pig iron to
wrought iron (or bar iron) using innova ve produc on systems. In 1783 he patented the
puddling process for rening iron ore. It was later improved by others, including Joseph Hall.[100]

Cast iron
Cast iron was rst produced in China during 5th century BCE,[101] but was hardly in Europe un l the medieval period.[102][103]
The earliest cast iron ar facts were discovered by archaeologists in what is now modern Luhe County, Jiangsu in China. Cast iron
was used in ancient China for warfare, agriculture, and architecture.[104] During the medieval period, means were found in
Europe of producing wrought iron from cast iron (in this context known as pig iron) using nery forges. For all these processes,
charcoal was required as fuel.[105]
Medieval blast furnaces were about 10 feet (3.0 m) tall and made of reproof brick; forced
air was usually provided by hand-operated bellows.[103] Modern blast furnaces have
grown much bigger, with hearths fourteen meters in diameter that allow them to produce
thousands of tons of iron each day, but essen ally operate in much the same way as they
did during medieval mes.[105]
In 1709, Abraham Darby I established a coke-red blast furnace to produce cast iron,
replacing charcoal, although con nuing to use blast furnaces. The ensuing availability of
inexpensive iron was one of the factors leading to the Industrial Revolu on. Toward the
end of the 18th century, cast iron began to replace wrought iron for certain purposes,
because it was cheaper. Carbon content in iron was not implicated as the reason for the
dierences in proper es of wrought iron, cast iron, and steel un l the 18th century.[85]

Coalbrookdale by Night, 1801. Blast

furnaces light the iron making town
of Coalbrookdale.

Since iron was becoming cheaper and more plen ful, it also became a major structural material following the building of the
innova ve rst iron bridge in 1778. This bridge s ll stands today as a monument to the role iron played in the Industrial
Revolu on. Following this, iron was used in rails, boats, ships, aqueducts, and buildings, as well as in iron cylinders in steam
engines.[105] Railways have been central to the forma on of modernity and ideas of progress[106] and various languages (e.g.

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French, Spanish, Italien and German) refer to railways as iron road.

Steel (with smaller carbon content than pig iron but more than wrought iron) was rst produced in an quity by using a bloomery.
Blacksmiths in Luristan in western Persia were making good steel by 1000 BCE.[85] Then improved versions, Wootz steel by India
and Damascus steel were developed around 300 BCE and 500 CE respec vely. These methods were specialized, and so steel did
not become a major commodity un l the 1850s.[107]
New methods of producing it by carburizing bars of iron in the cementa on process were devised in the 17th century. In the
Industrial Revolu on, new methods of producing bar iron without charcoal were devised and these were later applied to produce
steel. In the late 1850s, Henry Bessemer invented a new steelmaking process, involving blowing air through molten pig iron, to
produce mild steel. This made steel much more economical, thereby leading to wrought iron no longer being produced in large
quan es.[108]

Founda ons of modern chemistry

In 1774, Antoine Lavoisier used the reac on of water steam with metallic iron inside an incandescent iron tube to produce
hydrogen in his experiments leading to the demonstra on of the conserva on of mass, which was instrumental in changing
chemistry from a qualita ve science to a quan ta ve one.[109]

As iron has been in use for such a long me, it has many dierent names in dierent languages. The source of its chemical symbol
Fe is the La n word ferrum, and its descendants are the names of the element in the Romance languages (for example, French fer,
Spanish hierro, and Italian and Portuguese ferro).[110] The word ferrum itself possibly comes from the Semi c languages, via
Etruscan, from a root that also gave rise to Old English brs "brass".[111] The English word iron derives ul mately from ProtoGermanic *isarnan, which is also the source of the German name Eisen. It was most likely borrowed from Cel c *isarnon, which
ul mately comes from Proto-Indo-European *is-(e)ro- "powerful, holy" and nally *eis "strong", referencing iron's strength as a
metal.[112] Kluge relates *isarnon to illyric and lat. ira, 'wrath'[4]) The Balto-Slavic names for iron (for example, Russian
[zhelezo]) are the only ones to come directly from the Proto-Indo-European *ghelgh- "iron".[113] In many of these languages, the
word for iron may also be used to denote other objects made of iron or steel, or gura vely because of the hardness and strength
of the metal.[114] The Chinese 2 (tradi onal ; simplied ) derives from Proto-Sino-Tibetan *hliek,[115] and was borrowed
into Japanese as tetsu, which also has the na ve reading kurogane "black metal" (similar to how iron is referenced in the
English word blacksmith).[116]

Symbolic role
Iron plays a certain role in mythology and has found various usage as a metaphor and in in
folklore. The Greek poet Hesiod's Works and Days (lines 109201) lists dierent ages of
man named aNer metals like gold, silver, bronze and iron to account for successive ages of
humanity.[117] The iron age was closely related with Rome, and in Ovid's Metamorphoses
The Virtues, in despair, quit the earth ; and the depravity of man becomes
universal and complete. Hard steel succeeded then.
Ovid, Metamorphoses, Book I, Iron age, line 160
The symbolic role was important e.g. for the German Campaign of 1813. Frederick William
III commissioned then the rst Iron Cross as military decora on. Berlin iron jewellery
reached its peak produc on between 1813 and 1815, when the Prussian royal family urged
ci zens to donate gold and silver jewellery for military funding. The inscrip on Gold gab
ich fr Eisen (I gave gold for iron) was used as well in later war eorts.[118]

"Gold gab ich fr Eisen" "I gave gold

for iron". German-American brooch
from WWI.

Produc on of metallic iron

Industrial routes
The produc on of iron or steel is a process consis ng of two main stages. In the rst stage pig iron is produced in a blast furnace.
Alterna vely, it may be directly reduced. In the second stage, pig iron is converted to wrought iron, steel, or cast iron.[119]

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For a few limited purposes when it is needed, pure iron is produced in the laboratory in
small quan es by reducing the pure oxide or hydroxide with hydrogen, or forming iron
pentacarbonyl and hea ng it to 250 C so that it decomposes to form pure iron powder.[41]
Another method is electrolysis of ferrous chloride onto an iron cathode.[120]
Blast furnace processing
Industrial iron produc on starts with iron ores, principally hema te, which has a nominal
formula Fe2O3, and magne te, with the formula Fe3O4. These ores are reduced to the
metal in a carbothermic reac on, i.e. by treatment with carbon. The conversion is typically
conducted in a blast furnace at temperatures of about 2000 C. Carbon is provided in the
form of coke. The process also contains a ux such as limestone, which is used to remove
silicaceous minerals in the ore, which would otherwise clog the furnace. The coke and
limestone are fed into the top of the furnace, while a massive blast of air heated to 900 C,
about 4 tons per ton of iron,[103] is forced into the furnace at the boIom.[119]

Iron powder

In the furnace, the coke reacts with oxygen in the air blast to produce carbon
2 C + O2 2 CO
The carbon monoxide reduces the iron ore (in the chemical equa on below, hema te) to
molten iron, becoming carbon dioxide in the process:[119]
Fe2O3 + 3 CO 2 Fe + 3 CO2
Some iron in the high-temperature lower region of the furnace reacts directly with the

The ning process of smel ng iron

ore to make wrought iron from pig
iron, with the right illustra on
displaying men working a blast
furnace, from the Tiangong Kaiwu
encyclopedia, published in 1637 by
Song Yingxing.

2 Fe2O3 + 3 C 4 Fe + 3 CO2
The ux present to melt impuri es in the ore is principally limestone (calcium carbonate)
and dolomite (calcium-magnesium carbonate). Other specialized uxes are used
depending on the details of the ore. In the heat of the furnace the limestone ux
decomposes to calcium oxide (also known as quicklime):[119]
CaCO3 CaO + CO2
Then calcium oxide combines with silicon dioxide to form a liquid slag.[119]
CaO + SiO2 CaSiO3

How iron was extracted in the 19th


The slag melts in the heat of the furnace. In the boIom of the furnace, the molten slag
oats on top of the denser molten iron, and apertures in the side of the furnace are opened to run o the iron and the slag
separately. The iron, once cooled, is called pig iron, while the slag can be used as a material in road construc on or to improve
mineral-poor soils for agriculture.[103]
Direct iron reduc on
Owing to environmental concerns, alterna ve methods of processing iron have been
developed. "Direct iron reduc on" reduces iron ore to a powder called "sponge" iron or
"direct" iron that is suitable for steelmaking.[103] Two main reac ons comprise the direct
reduc on process:
Natural gas is par ally oxidized (with heat and a catalyst):[103]
2 CH4 + O2 2 CO + 4 H2

This heap of iron ore pellets will be

used in steel produc on.

These gases are then treated with iron ore in a furnace, producing solid sponge iron:[103]
Fe2O3 + CO + 2 H2 2 Fe + CO2 + 2 H2O
Silica is removed by adding a limestone ux as described above.[103]

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Further processes
Pig iron is not pure iron, but has 45% carbon dissolved in it with small amounts of other
impuri es like sulfur, magnesium, phosphorus and manganese. As the carbon is the major
impurity, the iron (pig iron) becomes briIle and hard.[119] Removing the other impuri es
results in cast iron, which is used to cast ar cles in foundries such as stoves, pipes,
radiators, lamp-posts and rails.[119]
Alterna vely pig iron may be made into steel (with up to about 2% carbon) or wrought
iron (commercially pure iron). Various processes have been used for this, including nery
forges, puddling furnaces, Bessemer converters, open hearth furnaces, basic oxygen
furnaces, and electric arc furnaces. In all cases, the objec ve is to oxidize some or all of the
carbon, together with other impuri es. On the other hand, other metals may be added to
make alloy steels.[105]

A pot of molten iron being used to

make steel

Annealing involves the hea ng of a piece of steel to 700800 C for several hours and then gradual cooling. It makes the steel
soNer and more workable.[121]

Applica ons
Iron is the most widely used of all the metals, accoun ng for
over 90% of worldwide metal produc on. Its low cost and high
strength make it indispensable in engineering applica ons
such as the construc on of machinery and machine tools,
automobiles, the hulls of large ships, and structural
components for buildings. Since pure iron is quite soN, it is
most commonly combined with alloying elements to make
Ferrite (-iron) is a fairly soN metal that can dissolve only a
small concentra on of carbon (no more than 0.021% by mass
at 910 C).[123] Austenite (-iron) is similarly soN and metallic
but can dissolve considerably more carbon (as much as 2.04%
by mass at 1146 C). This form of iron is used in the type of
stainless steel used for making cutlery, and hospital and
food-service equipment.[12]
Commercially available iron is classied based on purity and
Iron-carbon phase diagram
the abundance of addi ves. Pig iron has 3.54.5% carbon[124]
and contains varying amounts of contaminants such as sulfur,
silicon and phosphorus. Pig iron is not a saleable product, but rather an intermediate step in the produc on of cast iron and steel.
The reduc on of contaminants in pig iron that nega vely aect material proper es, such as sulfur and phosphorus, yields cast
iron containing 24% carbon, 16% silicon, and small amounts of manganese.[119] Pig iron has a mel ng point in the range of
14201470 K, which is lower than either of its two main components, and makes it the rst product to be melted when carbon
and iron are heated together.[13] Its mechanical proper es vary greatly and depend on the form the carbon takes in the alloy.[10]
"White" cast irons contain their carbon in the form of cemen te, or iron carbide (Fe3C).[10] This hard, briIle compound
dominates the mechanical proper es of white cast irons, rendering them hard, but unresistant to shock. The broken surface of a
white cast iron is full of ne facets of the broken iron-carbide, a very pale, silvery, shiny material, hence the appella on. Cooling a
mixture of iron with 0.8% carbon slowly below 723 C to room temperature results in separate, alterna ng layers of cemen te
and ferrite, which is soN and malleable and is called pearlite for its appearance. Rapid cooling, on the other hand, does not allow
me for this separa on and creates hard and briIle martensite. The steel can then be tempered by rehea ng to a temperature in
between, changing the propor ons of pearlite and martensite. The end product below 0.8% carbon content is a pearlite-ferrite
mixture, and that above 0.8% carbon content is a pearlite-cemen te mixture.[10]
In gray iron the carbon exists as separate, ne akes of graphite, and also renders the material briIle due to the sharp edged
akes of graphite that produce stress concentra on sites within the material.[125] A newer variant of gray iron, referred to as
duc le iron is specially treated with trace amounts of magnesium to alter the shape of graphite to spheroids, or nodules,
reducing the stress concentra ons and vastly increasing the toughness and strength of the material.[125]
Wrought iron contains less than 0.25% carbon but large amounts of slag that give it a brous characteris c.[124] It is a tough,

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malleable product, but not as fusible as pig iron. If honed to an edge, it loses it quickly. Wrought iron is characterized by the
presence of ne bers of slag entrapped within the metal. Wrought iron is more corrosion resistant than steel. It has been almost
completely replaced by mild steel for tradi onal "wrought iron" products and blacksmithing.
Mild steel corrodes more readily than wrought iron, but is cheaper and
more widely available. Carbon steel contains 2.0% carbon or less,[127] with
small amounts of manganese, sulfur, phosphorus, and silicon. Alloy steels
contain varying amounts of carbon as well as other metals, such as
chromium, vanadium, molybdenum, nickel, tungsten, etc. Their alloy
content raises their cost, and so they are usually only employed for
specialist uses. One common alloy steel, though, is stainless steel. Recent
developments in ferrous metallurgy have produced a growing range of
microalloyed steels, also termed 'HSLA' or high-strength, low alloy steels,
containing ny addi ons to produce high strengths and oNen spectacular
toughness at minimal cost.[127][128][129]
Apart from tradi onal applica ons, iron is also used for protec on from
ionizing radia on. Although it is lighter than another tradi onal protec on
material, lead, it is much stronger mechanically. The aIenua on of
radia on as a func on of energy is shown in the graph.[130]

Iron produc on 2009 (million tonnes)[126]

Country Iron ore Pig iron Direct iron Steel

1,114.9 549.4




























South Korea 0.1












The main disadvantage of iron and steel is that pure iron, and most of its
alloys, suer badly from rust if not protected in some way, a cost amoun ng to over 1% of
the world's economy.[131] Pain ng, galvaniza on, passiva on, plas c coa ng and bluing
are all used to protect iron from rust by excluding water and oxygen or by cathodic
protec on. The mechanism of the rus ng of iron is as follows:[131]
Cathode: 3 O2 + 6 H2O + 12 e 12 OH
Anode: 4 Fe 4 Fe2+ + 8 e; 4 Fe2+ 4 Fe3+ + 4 e
Overall: 4 Fe + 3 O2 + 6 H2O 4 Fe3+ + 12 OH 4 Fe(OH)3 or 4 FeO(OH) + 4 H2O
The electrolyte is usually iron(II) sulfate in urban areas (formed when atmospheric sulfur
dioxide aIacks iron), and salt par cles in the atmosphere in seaside areas.[131]

Photon mass aIenua on coecient

for iron.

Iron compounds
Although the dominant use of iron is in metallurgy, iron compounds are also pervasive in industry. Iron catalysts are tradi onally
used in the Haber-Bosch process for the produc on of ammonia and the Fischer-Tropsch process for conversion of carbon
monoxide to hydrocarbons for fuels and lubricants.[132] Powdered iron in an acidic solvent was used in the Bechamp reduc on
the reduc on of nitrobenzene to aniline.[133]
Iron(III) chloride nds use in water purica on and sewage treatment, in the dyeing of cloth, as a coloring agent in paints, as an
addi ve in animal feed, and as an etchant for copper in the manufacture of printed circuit boards.[134] It can also be dissolved in
alcohol to form ncture of iron, which is used as a medicine to stop bleeding in canaries.[135]
Iron(II) sulfate is used as a precursor to other iron compounds. It is also used to reduce chromate in cement. It is used to for fy
foods and treat iron deciency anemia. Iron(III) sulfate is used in seIling minute sewage par cles in tank water. Iron(II) chloride is
used as a reducing occula ng agent, in the forma on of iron complexes and magne c iron oxides, and as a reducing agent in
organic synthesis.[134]

Biological and pathological role

Iron is involved in numerous biological processes.[136][137] It is the most important transi on metal in all living organisms.[138]
Iron-proteins are found in all living organisms: archaeans, bacteria and eukaryotes, including humans. For example, the color of
blood is due to hemoglobin, an iron-containing protein. As illustrated by hemoglobin, iron is oNen bound to cofactors, such as
hemes, which are non-protein compounds, oNen involving metal ions, that are required for a protein's biological ac vity to
happen. The iron-sulfur clusters are pervasive and include nitrogenase, the enzymes responsible for biological nitrogen xa on.
The main roles of iron-containing proteins are the transport and storage of oxygen, as well as the transfer of electrons.[138]
Iron is a necessary trace element found in nearly all living organisms. Iron-containing enzymes and proteins, oNen containing
heme prosthe c groups, par cipate in many biological oxida ons and in transport. Examples of proteins found in higher
organisms include hemoglobin, cytochrome (see high-valent iron), and catalase.[139] The average adult human contains about
0.005% body weight of iron, or about four grams, of which three quarters is in hemoglobin a level that remains constant despite

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only about one milligram of iron being absorbed each day,[138] because the human body
recycles its hemoglobin for the iron content.[140]

Iron acquisi on poses a problem for aerobic organisms because ferric iron is poorly soluble
near neutral pH. Thus, these organisms have developed means to absorb iron as
complexes, some mes taking up ferrous iron before oxidising it back to ferric iron. In
par cular, bacteria have evolved very high-anity sequestering agents called
ANer uptake in human cells, iron storage is carefully regulated; iron ions are never "free".
This is because free iron ions have a high poten al for biological toxicity.[144] A major
component of this regula on is the protein transferrin, which binds iron ions absorbed
Structure of Heme b; in the protein
from the duodenum and carries it in the blood to cells.[145] Transferrin contains Fe3+ in the
addi onal ligand(s) would be
middle of a distorted octahedron, bonded to one nitrogen, three oxygens and a chela ng
aIached to Fe.
carbonate anion that traps the Fe3+ ion: it has such a high stability constant that it is very
eec ve at taking up Fe3+ ions even from the most stable complexes. At the bone marrow,
transferrin is reduced from Fe3+ and Fe2+ and stored as ferri n to be incorporated into hemoglobin.[138]
The most commonly known and studied bioinorganic iron compounds (biological iron molecules) are the heme proteins:
examples are hemoglobin, myoglobin, and cytochrome P450. These compounds par cipate in transpor ng gases, building
enzymes, and transferring electrons.[138] Metalloproteins are a group of proteins with metal ion cofactors. Some examples of iron
metalloproteins are ferri n and rubredoxin.[138] Many enzymes vital to life contain iron, such as catalase,[146] lipoxygenases,[147]
and IRE-BP.[148]
Hemoglobin is an oxygen carrier that occurs in red blood cells and contributes their color, transpor ng oxygen in the arteries from
the lungs to the muscles where it is transferred to myoglobin, which stores it un l it is needed for the metabolic oxida on of
glucose, which generates energy. Here the hemoglobin binds to carbon dioxide, produced when glucose is oxidized, which is
transported through the veins by hemoglobin (predominantly as bicarbonate anions) back to the lungs where it is exhaled.[138] In
hemoglobin, the iron is in one of four heme groups and has six possible coordina on sites; four are occupied by nitrogen atoms in
a porphyrin ring, the Nh by an imidazole nitrogen in a his dine residue of one of the protein chains aIached to the heme group,
and the sixth is reserved for the oxygen molecule it can reversibly bind to.[138] When hemoglobin is not aIached to oxygen (and
is then called deoxyhemoglobin), the Fe2+ ion at the center of the heme group (in the hydrophobic protein interior) is in a
high-spin congura on. It is thus too large to t inside the porphyrin ring, which bends instead into a dome with the Fe2+ ion
about 55 picometers above it. In this congura on, the sixth coordina on site reserved for the oxygen is blocked by another
his dine residue.[138] When deoxyhemoglobin picks up an oxygen molecule, this his dine residue moves away and returns once
the oxygen is securely aIached to form a hydrogen bond with it. This results in the Fe2+ ion switching to a low-spin congura on,
resul ng in a 20% decrease in ionic radius so that now it can t into the porphyrin ring, which becomes planar.[138] (Addi onally,
this hydrogen bonding results in the l ng of the oxygen molecule, resul ng in a FeOO bond angle of around 120 that avoids
the forma on of FeOFe or FeO2Fe bridges that would lead to electron transfer, the oxida on of Fe2+ to Fe3+, and the
destruc on of hemoglobin.) This results in a movement of all the protein chains that leads to the other subunits of hemoglobin
changing shape to a form with larger oxygen anity. Thus, when deoxyhemoglobin takes up oxygen, its anity for more oxygen
increases, and vice versa.[138] Myoglobin, on the other hand, contains only one heme group and hence this coopera ve eect
cannot occur. Thus, while hemoglobin is almost saturated with oxygen in the high par al pressures of oxygen found in the lungs,
its anity for oxygen is much lower than myoglobin in the low par al pressures of oxygen found in muscle ssue, resul ng in
oxygen transfer.[138] This is further enhanced by the concomitant Bohr eect (named aNer Chris an Bohr, the father of Niels
Bohr), in which lowered pH (as occurs when carbon dioxide is released in the muscles) further lowers the oxygen anity of
Carbon monoxide and phosphorus triuoride are poisonous to humans because they bind to hemoglobin similarly to oxygen, but
with much more strength, so that oxygen can no longer be transported throughout the body. This eect also plays a minor role in
the toxicity of cyanide, but there the major eect is by far its interference with the proper func oning of the electron transport
protein cytochrome a.[138] The cytochrome proteins also involve heme groups and are involved in the metabolic oxida on of
glucose by oxygen. The sixth coordina on site is then occupied by either another imidazole nitrogen or a methionine sulfur, so
that these proteins are largely inert to oxygen with the excep on of cytochrome a, which bonds directly to oxygen and thus is
very easily poisoned by cyanide.[138] Here, the electron transfer takes place as the iron remains in low spin but changes between
the +2 and +3 oxida on states. Since the reduc on poten al of each step is slightly greater than the previous one, the energy is
released step-by-step and can thus be stored in adenosine triphosphate. Cytochrome a is slightly dis nct, as it occurs at the
mitochondrial membrane, binds directly to oxygen, and transports protons as well as electrons, as follows:[138]

4 Cytc2+ + O2 + 8Hinside 4 Cytc3+ + 2 H2O + 4Houtside

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Although the heme proteins are the most important class of iron-containing proteins, the iron-sulfur proteins are also very
important, being involved in electron transfer, which is possible since iron can exist stably in either the +2 or +3 oxida on states.
These have one, two, four, or eight iron atoms that are each approximately tetrahedrally coordinated to four sulfur atoms;
because of this tetrahedral coordina on, they always have high-spin iron. The simplest of such compounds is rubredoxin, which
has only one iron atom coordinated to four sulfur atoms from cysteine residues in the surrounding pep de chains. Another
important class of iron-sulfur proteins is the ferredoxins, which have mul ple iron atoms. Transferrin does not belong to either of
these classes.[138]

Health and diet

Iron is pervasive, but par cularly rich sources of dietary iron include red meat, len ls, beans, poultry, sh, leaf vegetables,
watercress, tofu, chickpeas, black-eyed peas, and blackstrap molasses. Bread and breakfast cereals are some mes specically
for ed with iron. Iron in low amounts is found in molasses, te, and farina.[149][150]
Iron provided by dietary supplements is oNen found as iron(II) fumarate, although iron(II) sulfate is cheaper and is absorbed
equally well.[134] Elemental iron, or reduced iron, despite being absorbed at only one-third to two-thirds the eciency (rela ve
to iron sulfate),[151] is oNen added to foods such as breakfast cereals or enriched wheat our. Iron is most available to the body
when chelated to amino acids[152] and is also available for use as a common iron supplement. Glycine, the cheapest and most
common amino acid is most oNen used to produce iron glycinate supplements.[153] The Recommended Dietary Allowance (RDA)
for iron varies considerably depending on age, sex, and source of dietary iron: for example, heme-based iron has higher

Iron uptake is ghtly regulated by the human body, which has no regulated physiological means of excre ng iron. Only small
amounts of iron are lost daily due to mucosal and skin epithelial cell sloughing, so control of iron levels is primarily accomplished
by regula ng uptake.[155] Regula on of iron uptake is impaired in some people as a result of a gene c defect that maps to the
HLA-H gene region on chromosome 6 and leads to abnormally low levels of hepcidin, a key regulator of the entry of iron into the
circulatory system in mammals.[156] In these people, excessive iron intake can result in iron overload disorders, known medically
as hemochromatosis. Many people have an undiagnosed gene c suscep bility to iron overload, and are not aware of a family
history of the problem. For this reason, people should not take iron supplements unless they suer from iron deciency and have
consulted a doctor. Hemochromatosis is es mated to be the a cause of 0.3 to 0.8% of all metabolic diseases of Caucasians.[157]
Overdoses of ingested iron can cause excessive levels of free iron in the blood. High blood levels of free ferrous iron react with
peroxides to produce highly reac ve free radicals that can damage DNA, proteins, lipids, and other cellular components. Iron
toxicity occurs when the cell contains free iron, which generally occurs when iron levels exceed the availability of transferrin to
bind the iron. Damage to the cells of the gastrointes nal tract can also prevent them from regula ng iron absorp on, leading to
further increases in blood levels. Iron typically damages cells in the heart, liver and elsewhere, causing adverse eects that
include coma, metabolic acidosis, shock, liver failure, coagulopathy, adult respiratory distress syndrome, long-term organ
damage, and even death.[158] Humans experience iron toxicity when the iron exceeds 20 milligrams for every kilogram of body
mass; 60 milligrams per kilogram is considered a lethal dose.[159] Overconsump on of iron, oNen the result of children ea ng
large quan es of ferrous sulfate tablets intended for adult consump on, is one of the most common toxicological causes of
death in children under six.[159] The Dietary Reference Intake (DRI) sets the Tolerable Upper Intake Level (UL) for adults at
45 mg/day. For children under fourteen years old the UL is 40 mg/day.[160]
The medical management of iron toxicity is complicated, and can include use of a specic chela ng agent called deferoxamine to
bind and expel excess iron from the body.[158][161][162]

Iron deciency is the most common nutri onal deciency in the world.[163][164][165] When loss of iron is not adequately
compensated by adequate dietary iron intake, a state of latent iron deciency occurs, which over me leads to iron-deciency
anemia if leN untreated, which is characterised by an insucient number of red blood cells and an insucient amount of
hemoglobin.[166] Children, pre-menopausal women (women of child-bearing age), and people with poor diet are most
suscep ble to the disease. Most cases of iron-deciency anemia are mild, but if not treated can cause problems like fast or
irregular heartbeat, complica ons during pregnancy, and delayed growth in infants and children.[167]

See also
El Mutn in Bolivia, where 10% of the world's accessible iron ore is located.
Iron fer liza on proposed fer liza on of oceans to s mulate phytoplankton growth
List of countries by iron produc on

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Pelle sing process of crea on of iron ore pellets

Rustproof iron

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Further reading
H. R. Schubert, History of the Bri2sh Iron and Steel Industry ... to 1775 AD (Routledge, London, 1957)
R. F. Tylecote, History of Metallurgy (Ins tute of Materials, London 1992).
R. F. Tylecote, "Iron in the Industrial Revolu on" in J. Day and R. F. Tylecote, The Industrial Revolu2on in Metals (Ins tute of
Materials 1991), 20060.

External links
It's Elemental Iron (hIp://educa
Chemistry in its element podcast (hIp://
/element.asp) (MP3) from the Royal Society of Chemistry's Chemistry World: Iron
Iron (hIp:// at The Periodic Table of
Videos (University of Nodngham)
Metallurgy for the non-Metallurgist (hIps://
Iron (hIp:// by J. B. Calvert

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