Iron(III) compounds

Iron () is a chemical element with symbol Fe (from la, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, right in front of oxygen (32.1% and 30.1%, respectively), forming much of Earth's outer and inner core. It is the fourth most common element in the Earth's crust.

In its metallic state, iron is rare in the Earth's crust, limited mainly to deposition by meteorites. Iron ores, by contrast, are among the most abundant in the Earth's crust, although extracting usable metal from them requires kilns or furnaces capable of reaching or higher, about higher than that required to smelt copper. Humans started to master that process in Eurasia during the 2nd millennium BCE and the use of iron tools and weapons began to displace copper alloys, in some regions, only around 1200 BCE. That event is considered the transition from the Bronze Age to the Iron Age. In the modern world, iron alloys, such as steel, stainless steel, cast iron and special steels, are by far the most common industrial metals, because of their mechanical properties and low cost. The iron and steel industry is thus very important economically, and iron is the cheapest metal, with a price of a few dollars per kilogram or per pound (see Metal#uses).

Pristine and smooth pure iron surfaces are mirror-like silvery-gray. However, iron reacts readily with oxygen and water to give brown to black hydrated iron oxides, commonly known as rust. Unlike the oxides of some other metals that form passivating layers, rust occupies more volume than the metal and thus flakes off, exposing more fresh surfaces for corrosion. Although iron readily reacts, high purity iron, called electrolytic iron, has better corrosion resistance.

The body of an adult human contains about 4 grams (0.005% body weight) of iron, mostly in hemoglobin and myoglobin. These two proteins play essential roles in vertebrate metabolism, respectively oxygen transport by blood and oxygen storage in muscles. To maintain the necessary levels, human iron metabolism requires a minimum of iron in the diet. Iron is also the metal at the active site of many important redox enzymes dealing with cellular respiration and oxidation and reduction in plants and animals.

Chemically, the most common oxidation states of iron are iron(II) and iron(III). Iron shares many properties of other transition metals, including the other group 8 elements, ruthenium and osmium. Iron forms compounds in a wide range of oxidation states, −2 to +7. Iron also forms many coordination compounds; some of them, such as ferrocene, ferrioxalate, and Prussian blue, have substantial industrial, medical, or research applications.

Characteristics

Allotropes

At least four allotropes of iron (differing atom arrangements in the solid) are known, conventionally denoted α, γ, δ, and ε.

The first three forms are observed at ordinary pressures. As molten iron cools past its freezing point of 1538 °C, it crystallizes into its δ allotrope, which has a body-centered cubic (bcc) crystal structure. As it cools further to 1394 °C, it changes to its γ-iron allotrope, a face-centered cubic (fcc) crystal structure, or austenite. At 912 °C and below, the crystal structure again becomes the bcc α-iron allotrope.

The physical properties of iron at very high pressures and temperatures have also been studied extensively, because of their relevance to theories about the cores of the Earth and other planets. Above approximately 10 GPa and temperatures of a few hundred kelvin or less, α-iron changes into another hexagonal close-packed (hcp) structure, which is also known as ε-iron. The higher-temperature γ-phase also changes into ε-iron, but does so at higher pressure.

Some controversial experimental evidence exists for a stable β phase at pressures above 50 GPa and temperatures of at least 1500 K. It is supposed to have an orthorhombic or a double hcp structure. (Confusingly, the term "β-iron" is sometimes also used to refer to α-iron above its Curie point, when it changes from being ferromagnetic to paramagnetic, even though its crystal structure has not changed.)

The inner core of the Earth is generally presumed to consist of an iron- nickel alloy with ε (or β) structure.

Melting and boiling points

The melting and boiling points of iron, along with its enthalpy of atomization, are lower than those of the earlier 3d elements from scandium to chromium, showing the lessened contribution of the 3d electrons to metallic bonding as they are attracted more and more into the inert core by the nucleus;Greenwood and Earnshaw, p. 1116 however, they are higher than the values for the previous element manganese because that element has a half-filled 3d sub-shell and consequently its d-electrons are not easily delocalized. This same trend appears for ruthenium but not osmium.

The melting point of iron is experimentally well defined for pressures less than 50 GPa. For greater pressures, published data (as of 2007) still varies by tens of gigapascals and over a thousand kelvin.

Magnetic properties

Below its Curie point of , α-iron changes from paramagnetic to ferromagnetic: the spins of the two unpaired electrons in each atom generally align with the spins of its neighbors, creating an overall magnetic field. This happens because the orbitals of those two electrons (d_''z''² and d_{''x''² − ''y''²}) do not point toward neighboring atoms in the lattice, and therefore are not involved in metallic bonding.

In the absence of an external source of magnetic field, the atoms get spontaneously partitioned into magnetic domains, about 10 micrometers across, such that the atoms in each domain have parallel spins, but some domains have other orientations. Thus a macroscopic piece of iron will have a nearly zero overall magnetic field.

Application of an external magnetic field causes the domains that are magnetized in the same general direction to grow at the expense of adjacent ones that point in other directions, reinforcing the external field. This effect is exploited in devices that need to channel magnetic fields to fulfill design function, such as electrical transformers, magnetic recording heads, and electric motors. Impurities, lattice defects, or grain and particle boundaries can "pin" the domains in the new positions, so that the effect persists even after the external field is removed – thus turning the iron object into a (permanent) magnet.

Similar behavior is exhibited by some iron compounds, such as the ferrites including the mineral magnetite, a crystalline form of the mixed iron(II,III) oxide (although the atomic-scale mechanism, ferrimagnetism, is somewhat different). Pieces of magnetite with natural permanent magnetization ( lodestones) provided the earliest compasses for navigation. Particles of magnetite were extensively used in magnetic recording media such as core memories, magnetic tapes, floppies, and disks, until they were replaced by cobalt-based materials.

Isotopes

Iron has four stable isotopes: ⁵⁴Fe (5.845% of natural iron), ⁵⁶Fe (91.754%), ⁵⁷Fe (2.119%) and ⁵⁸Fe (0.282%). 20-30 artificial isotopes have also been created. Of these stable isotopes, only ⁵⁷Fe has a nuclear spin (−). The nuclide ⁵⁴Fe theoretically can undergo double electron capture to ⁵⁴Cr, but the process has never been observed and only a lower limit on the half-life of 3.1×10²² years has been established.

⁶⁰Fe is an extinct radionuclide of long half-life (2.6 million years). It is not found on Earth, but its ultimate decay product is its granddaughter, the stable nuclide ⁶⁰Ni. Much of the past work on isotopic composition of iron has focused on the nucleosynthesis of ⁶⁰Fe through studies of meteorites and ore formation. In the last decade, advances in mass spectrometry have allowed the detection and quantification of minute, naturally occurring variations in the ratios of the stable isotopes of iron. Much of this work is driven by the Earth and planetary science communities, although applications to biological and industrial systems are emerging.

In phases of the meteorites ''Semarkona'' and ''Chervony Kut,'' a correlation between the concentration of ⁶⁰Ni, the granddaughter of ⁶⁰Fe, and the abundance of the stable iron isotopes provided evidence for the existence of ⁶⁰Fe at the time of formation of the Solar System. Possibly the energy released by the decay of ⁶⁰Fe, along with that released by ²⁶Al, contributed to the remelting and differentiation of asteroids after their formation 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.

The most abundant iron isotope ⁵⁶Fe is of particular interest to nuclear scientists because it represents the most common endpoint of nucleosynthesis. Since ⁵⁶Ni (14 alpha particles) is easily produced from lighter nuclei in the alpha process in nuclear reactions in supernovae (see silicon burning process), it is the endpoint of fusion chains inside extremely massive stars, since addition of another alpha particle, resulting in ⁶⁰Zn, requires a great deal more energy. This ⁵⁶Ni, which has a half-life of about 6 days, is created in quantity in these stars, but soon decays by two successive positron emissions within supernova decay products in the supernova remnant gas cloud, first to radioactive 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.Greenwood and Earnshaw, p. 12 It is also very common in the universe, relative to other stable metals of approximately the same atomic weight. Iron is the sixth most abundant element in the universe, and the most common refractory element.

Although a further tiny energy gain could be extracted by synthesizing ⁶²Ni, which has a marginally higher binding energy than ⁵⁶Fe, conditions in stars are unsuitable for this process. Element production in supernovas and distribution on Earth greatly favor iron over nickel, and in any case, ⁵⁶Fe still has a lower mass per nucleon than ⁶²Ni due to its higher fraction of lighter protons. Hence, elements heavier than iron require a supernova for their formation, involving rapid neutron capture by starting ⁵⁶Fe nuclei.

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 matter to fuse into ⁵⁶Fe nuclei. Fission and alpha-particle emission would then make heavy nuclei decay into iron, converting all stellar-mass objects to cold spheres of pure iron.

Origin and occurrence in nature

Cosmogenesis

Iron's abundance in rocky planets like Earth is due to its abundant production during the runaway fusion and explosion of type Ia supernovae, which scatters the iron into space.

Metallic iron

Metallic or native iron is rarely found on the surface of the Earth because it tends to oxidize. However, both the Earth's inner and outer core, that account for 35% of the mass of the whole Earth, are believed to consist largely of an iron alloy, possibly with nickel. Electric currents in the liquid outer core are believed to be the origin of the Earth's magnetic field. The other terrestrial planets ( Mercury, Venus, and Mars) as well as the Moon are believed to have a metallic core consisting mostly of iron. The M-type asteroids are also believed to be partly or mostly made of metallic iron alloy.

The rare iron meteorites are the main form of natural metallic iron on the Earth's surface. Items made of cold-worked meteoritic iron have been found in various archaeological sites dating from a time when iron smelting had not yet been developed; and the Inuit in Greenland have been reported to use iron from the Cape York meteorite for tools and hunting weapons. About 1 in 20 meteorites consist of the unique iron-nickel minerals taenite (35–80% iron) and kamacite (90–95% iron). Native iron is also rarely found in basalts that have formed from magmas that have come into contact with carbon-rich sedimentary rocks, which have reduced the oxygen fugacity sufficiently for iron to crystallize. This is known as Telluric iron and is described from a few localities, such as Disko Island in West Greenland, Yakutia in Russia and Bühl in Germany.

Mantle minerals

Ferropericlase , a solid solution of periclase (MgO) and wüstite (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 after silicate perovskite ; it also is the major host for iron in the lower mantle. At the bottom of the transition zone of the mantle, the reaction γ- transforms γ-olivine into a mixture of silicate perovskite and ferropericlase and vice versa. In the literature, this mineral phase of the lower mantle is also often called magnesiowüstite.Ferropericlase
Mindat.org Silicate perovskite may form up to 93% of the lower mantle, and the magnesium iron form, , is considered to be the most abundant mineral in the Earth, making up 38% of its volume.

Earth's crust

While iron is the most abundant element on Earth, most of this iron is concentrated in the inner and outer cores. The fraction of iron that is in Earth's crust only amounts to about 5% of the overall mass of the crust and is thus only the fourth most abundant element in that layer (after oxygen, silicon, and aluminium).

Most of the iron in the crust is combined with various other elements to form many iron minerals. An important class is the iron oxide minerals such as hematite (Fe₂O₃), magnetite (Fe₃O₄), and siderite (FeCO₃), which are the major ores of iron. Many igneous rocks also contain the sulfide minerals pyrrhotite and pentlandite.Klein, Cornelis and Cornelius S. Hurlbut, Jr. (1985) ''Manual of Mineralogy,'' Wiley, 20th ed, pp. 278–79 During weathering, iron tends to leach from sulfide deposits as the sulfate and from silicate deposits as the bicarbonate. Both of these are oxidized in aqueous solution and precipitate in even mildly elevated pH as iron(III) oxide.Greenwood and Earnshaw, p. 1071

Large deposits of iron are banded iron formations, a type of rock consisting of repeated thin layers of iron oxides alternating with bands of iron-poor shale and chert. The banded iron formations were laid down in the time between and .

Materials containing finely ground iron(III) oxides or oxide-hydroxides, such as ochre, have been used as yellow, red, and brown pigments since pre-historical times. They contribute as well to the color of various rocks and clays, including entire geological formations like the Painted Hills in Oregon and the Buntsandstein ("colored sandstone", British Bunter). Through ''Eisensandstein'' (a jurassic 'iron sandstone', e.g. from Donzdorf in Germany) and Bath stone in the UK, iron compounds are responsible for the yellowish color of many historical buildings and sculptures. The proverbial red color of the surface of Mars is derived from an iron oxide-rich regolith.

Significant amounts of iron occur in the iron sulfide mineral pyrite (FeS₂), but it is difficult to extract iron from it and it is therefore not exploited. In fact, iron is so common that production generally focuses only on ores with very high quantities of it.

According to the International Resource Panel's Metal Stocks in Society report, the global stock of iron in use in society is 2,200 kg per capita. More-developed countries differ in this respect from less-developed countries (7,000–14,000 vs 2,000 kg per capita).

Oceans

Ocean science demonstrated the role of the iron in the ancient seas in both marine biota and climate.

Chemistry and compounds

Iron shows the characteristic chemical properties of the transition metals, namely the ability to form variable oxidation states differing by steps of one and a very large coordination and organometallic chemistry: indeed, it was the discovery of an iron compound, ferrocene, that revolutionalized the latter field in the 1950s.Greenwood and Earnshaw, p. 905 Iron is sometimes considered as a prototype for the entire block of transition metals, due to its abundance and the immense role it has played in the technological progress of humanity. Its 26 electrons are arranged in the configuration rd⁶4s², of which the 3d and 4s electrons are relatively close in energy, and thus it can lose a variable number of electrons and there is no clear point where further ionization becomes unprofitable.

Iron forms compounds mainly in the oxidation states +2 ( iron(II), "ferrous") and +3 (iron(III), "ferric"). Iron also occurs in higher oxidation states, e.g. the purple potassium ferrate (K₂FeO₄), which contains iron in its +6 oxidation state. Although iron(VIII) oxide (FeO₄) has been claimed, the report could not be reproduced and such a species from the removal of all electrons of the element beyond the preceding inert gas configuration (at least with iron in its +8 oxidation state) has been found to be improbable computationally. However, one form of anionic eO₄sup>– with iron in its +7 oxidation state, along with an iron(V)-peroxo isomer, has been detected by infrared spectroscopy at 4 K after cocondensation of laser-ablated Fe atoms with a mixture of O₂/Ar. Iron(IV) is a common intermediate in many biochemical oxidation reactions. Numerous organoiron compounds contain formal oxidation states of +1, 0, −1, or even −2. The oxidation states and other bonding properties are often assessed using the technique of Mössbauer spectroscopy. Many mixed valence compounds contain both iron(II) and iron(III) centers, such as magnetite and Prussian blue (). The latter is used as the traditional "blue" in blueprints.

Iron is the first of the transition metals that cannot reach its group oxidation state of +8, although its heavier congeners ruthenium and osmium can, with ruthenium having more difficulty than osmium. Ruthenium exhibits an aqueous cationic chemistry in its low oxidation states similar to that of iron, but osmium does not, favoring high oxidation states in which it forms anionic complexes. In the second half of the 3d transition series, vertical similarities down the groups compete with the horizontal similarities of iron with its neighbors cobalt and nickel in the periodic table, which are also ferromagnetic at room temperature and share similar chemistry. As such, iron, cobalt, and nickel are sometimes grouped together as the iron triad.Greenwood and Earnshaw, p. 1070

Unlike many other metals, iron does not form amalgams with mercury. As a result, mercury is traded in standardized 76 pound flasks (34 kg) made of iron.

Iron is by far the most reactive element in its group; it is pyrophoric when finely 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 formation of an impervious oxide layer, which can nevertheless react with hydrochloric acid. High purity iron, called electrolytic iron, is considered to be resistant to rust, due to its oxide layer.

Binary compounds

Oxides and hydroxides

Iron forms 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 compositions may vary. These oxides are the principal ores for the production of iron (see bloomery and blast furnace). They are also used in the production of ferrites, useful magnetic storage media in computers, and pigments. The best known sulfide is iron pyrite (FeS₂), also known as fool's gold owing to its golden luster. It is not an iron(IV) compound, but is actually an iron(II) polysulfide containing Fe²⁺ and ions in a distorted sodium chloride structure.Greenwood and Earnshaw, p. 1079

Halides

The binary ferrous and ferric halides are well-known. The ferrous halides typically arise from treating iron metal with the corresponding hydrohalic acid to give the corresponding hydrated salts.
:Fe + 2 HX → FeX₂ + H₂ (X = F, Cl, Br, I)
Iron reacts with fluorine, chlorine, and bromine to give the corresponding ferric halides, ferric chloride being the most common.
:2 Fe + 3 X₂ → 2 FeX₃ (X = F, Cl, Br)
Ferric iodide is an exception, being thermodynamically unstable due to the oxidizing power of Fe³⁺ and the high reducing power of I⁻:
:2 I⁻ + 2 Fe³⁺ → I₂ + 2 Fe²⁺ (E⁰ = +0.23 V)

Ferric iodide, a black solid, is not stable in ordinary conditions, but can be prepared through the reaction of iron pentacarbonyl with iodine and carbon monoxide in the presence of hexane and light at the temperature of −20 °C, with oxygen and water excluded. Complexes of ferric iodide with some soft bases are known to be stable compounds.

Solution chemistry

The standard reduction potentials in acidic aqueous solution for some common iron ions are given below:Greenwood and Earnshaw, pp. 1075–79

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 solutions:Greenwood and Earnshaw, pp. 1082–84
:4 + 10 → 4 + 20 + 3 O₂

The Fe³⁺ ion has a large simple cationic chemistry, although the pale-violet hexaquo ion is very readily hydrolyzed when pH increases above 0 as follows:Greenwood and Earnshaw, pp. 1088–91

As pH rises above 0 the above yellow hydrolyzed species form and as it rises above 2–3, reddish-brown hydrous iron(III) oxide precipitates out of solution. Although Fe³⁺ has a d⁵ configuration, its absorption spectrum is not like that of Mn²⁺ with its weak, spin-forbidden d–d bands, because Fe³⁺ has higher positive charge and is more polarizing, lowering the energy of its ligand-to-metal charge transfer absorptions. Thus, all the above complexes are rather strongly colored, with the single exception 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 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.Greenwood and Earnshaw, pp. 1091–97

Coordination compounds

Due to its electronic structure, iron has a very large coordination and organometallic chemistry.

Many coordination compounds of iron are known. A typical six-coordinate anion is hexachloroferrate(III), eCl₆sup>3−, found in the mixed salt tetrakis(methylammonium) hexachloroferrate(III) chloride. Complexes with multiple bidentate ligands have geometric isomers. For example, the ''trans''-chlorohydridobis(bis-1,2-(diphenylphosphino)ethane)iron(II) complex is used as a starting material for compounds with the moiety. The ferrioxalate ion with three oxalate ligands (shown at right) displays helical chirality with its two non-superposable geometries labelled ''Λ'' (lambda) for the left-handed screw axis and ''Δ'' (delta) for the right-handed screw axis, in line with IUPAC conventions. Potassium ferrioxalate is used in chemical actinometry and along with its sodium salt undergoes photoreduction 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 crystallisation located forming the caps of each octahedron, as illustrated below.

Iron(III) complexes are quite similar to those of chromium(III) with the exception of iron(III)'s preference for ''O''-donor instead of ''N''-donor ligands. The latter tend to be rather more unstable than iron(II) complexes and often dissociate in water. Many Fe–O 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 complex:

:3 ArOH + FeCl₃ → Fe(OAr)₃ + 3 HCl (Ar = aryl)

Among the halide and pseudohalide complexes, fluoro complexes of iron(III) are the most stable, with the colorless eF₅(H₂O)sup>2− being the most stable in aqueous solution. Chloro complexes are less stable and favor tetrahedral coordination as in eCl₄sup>−; eBr₄sup>− and eI₄sup>− are reduced easily to iron(II). Thiocyanate is a common test for the presence of iron(III) as it forms the blood-red e(SCN)(H₂O)₅sup>2+. Like manganese(II), most iron(III) complexes are high-spin, the exceptions being those with ligands that are high in the spectrochemical series such as cyanide. An example of a low-spin iron(III) complex is e(CN)₆sup>3−. The cyanide ligands may easily be detached in e(CN)₆sup>3−, and hence this complex is poisonous, unlike the iron(II) complex e(CN)₆sup>4− found in Prussian blue, which does not release hydrogen cyanide except when dilute acids are added. Iron shows a great variety of electronic spin states, including every possible spin quantum number value for a d-block element from 0 (diamagnetic) to (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 five are considered high-spin.

Iron(II) complexes are less stable than iron(III) complexes but the preference for ''O''-donor ligands is less marked, so that for example is known while is not. They have a tendency to be oxidized to iron(III) but this can be moderated by low pH and the specific ligands used.

Organometallic compounds

Organoiron chemistry is the study of organometallic compounds of iron, where carbon atoms are covalently bound to the metal atom. They are many and varied, including cyanide complexes, carbonyl complexes, sandwich and half-sandwich compounds.

Prussian blue or "ferric ferrocyanide", Fe₄ e(CN)₆sub>3, is an old and well-known iron-cyanide complex, extensively used as pigment and in several other applications. Its formation can be used as a simple wet chemistry test to distinguish between aqueous solutions of Fe²⁺ and Fe³⁺ as they react (respectively) with potassium ferricyanide and potassium ferrocyanide to form Prussian blue.

Another old example of an organoiron compound is iron pentacarbonyl, Fe(CO)₅, in which a neutral iron atom is bound to the carbon atoms of five carbon monoxide molecules. The compound can be used to make carbonyl iron powder, a highly reactive form of metallic iron. Thermolysis of iron pentacarbonyl gives triiron dodecacarbonyl, , a complex with a cluster of three iron atoms at its core. Collman's reagent, disodium tetracarbonylferrate, is a useful reagent for organic chemistry; it contains iron in the −2 oxidation state. Cyclopentadienyliron dicarbonyl dimer contains iron in the rare +1 oxidation state.

A landmark in this field was the discovery in 1951 of the remarkably stable sandwich compound ferrocene , by Pauson and Kealy and independently by Miller and colleagues, whose surprising molecular structure was determined only a year later by Woodward and Wilkinson and Fischer.
Ferrocene is still one of the most important tools and models in this class.Greenwood and Earnshaw, p. 1104

Iron-centered organometallic species are used as catalysts. The Knölker complex, for example, is a transfer hydrogenation catalyst for ketones.

Industrial uses

The iron compounds produced on the largest scale in industry are iron(II) sulfate (FeSO₄·7 H₂O) and iron(III) chloride (FeCl₃). The former is one of the most readily available sources of iron(II), but is less stable to aerial oxidation than Mohr's salt (). Iron(II) compounds tend to be oxidized to iron(III) compounds in the air.

History

Development of iron metallurgy

Iron is one of the elements undoubtedly known to the ancient world. It has been worked, or wrought, for millennia. However, iron artefacts of great age are much rarer than objects made of gold or silver due to the ease with which iron corrodes. The technology developed slowly, and even after the discovery of smelting it took many centuries for iron to replace bronze as the metal of choice for tools and weapons.

Meteoritic iron

Beads made from meteoric iron in 3500 BC or earlier were found in Gerzeh, Egypt by G.A. Wainwright. 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 impurities.

Meteoric iron was highly regarded due to its origin in the heavens and was often used to forge weapons and tools. For example, a dagger made of meteoric iron was found in the tomb of Tutankhamun, containing similar proportions of iron, cobalt, and nickel to a meteorite discovered in the area, deposited by an ancient meteor shower. Items that were likely made of iron by Egyptians date from 3000 to 2500 BC.

Meteoritic iron is comparably soft and ductile and easily cold forged but may get brittle when heated because of the nickel content.

Wrought iron

The first iron production 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 sometime between 3000 and 2700 BC. The Hittites established an empire in north-central Anatolia around 1600 BC. They appear to be the first to understand the production of iron from its ores and regard it highly in their society. The Hittites began to smelt iron between 1500 and 1200 BC and the practice spread to the rest of the Near East after their empire fell in 1180 BC. The subsequent period is called the Iron Age.

Artifacts of smelted iron are found in India dating from 1800 to 1200 BC, and in the Levant from about 1500 BC (suggesting smelting in Anatolia or the Caucasus). 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 respectively to date the texts as such. The rigveda term ''ayas'' (metal) refers to copper, while iron which is called as ''śyāma ayas'', literally "black copper", first is mentioned in the post-rigvedic Atharvaveda.

Some archaeological evidence suggests iron was smelted in Zimbabwe and southeast Africa as early as the eighth century BC. Iron working was introduced to Greece in the late 11th century BC, from which it spread quickly throughout Europe.

The spread of ironworking in Central and Western Europe is associated with Celtic expansion. According to Pliny the Elder, iron use was common in the Roman era. In the lands of what is now considered China, iron appears approximately 700–500 BC. Iron smelting may have been introduced into China through Central Asia.Pigott, Vincent C. (1999). ''The Archaeometallurgy of the Asian Old World''. Philadelphia: University of Pennsylvania Museum of Archaeology and Anthropology. , p. 8. The earliest evidence of the use of a blast furnace in China dates to the 1st century AD, and cupola furnaces were used as early as the Warring States period (403–221 BC).Pigott, Vincent C. (1999). ''The Archaeometallurgy of the Asian Old World''. Philadelphia: University of Pennsylvania Museum of Archaeology and Anthropology. , p. 191. Usage of the blast and cupola furnace remained widespread during the Tang and Song dynasties.

During the Industrial Revolution in Britain, Henry Cort began refining iron from pig iron to wrought iron (or bar iron) using innovative production systems. In 1783 he patented the puddling process for refining iron ore. It was later improved by others, including Joseph Hall.

Cast iron

Cast iron was first produced in China during 5th century BC, but was hardly in Europe until the medieval period. The earliest cast iron artifacts 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. During the medieval period, means were found in Europe of producing wrought iron from cast iron (in this context known as pig iron) using finery forges. For all these processes, charcoal was required as fuel.

Medieval blast furnaces were about tall and made of fireproof brick; forced air was usually provided by hand-operated bellows. 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 essentially operate in much the same way as they did during medieval times.

In 1709, Abraham Darby I established a coke-fired blast furnace to produce cast iron, replacing charcoal, although continuing to use blast furnaces. The ensuing availability of inexpensive iron was one of the factors leading to the Industrial Revolution. 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 differences in properties of wrought iron, cast iron, and steel until the 18th century.

Since iron was becoming cheaper and more plentiful, it also became a major structural material following the building of the innovative first iron bridge in 1778. This bridge still stands today as a monument to the role iron played in the Industrial Revolution. Following this, iron was used in rails, boats, ships, aqueducts, and buildings, as well as in iron cylinders in steam engines.Greenwood and Earnshaw, p. 1072 Railways have been central to the formation of modernity and ideas of progress and various languages (e.g. French, Spanish, Italian and German) refer to railways as ''iron road''.

Steel

Steel (with smaller carbon content than pig iron but more than wrought iron) was first produced in antiquity by using a bloomery. Blacksmiths in Luristan in western Persia were making good steel by 1000 BC. Then improved versions, Wootz steel by India and Damascus steel were developed around 300 BC and AD 500 respectively. These methods were specialized, and so steel did not become a major commodity until the 1850s.

New methods of producing it by carburizing bars of iron in the cementation process were devised in the 17th century. In the Industrial Revolution, 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 quantities.

Foundations of modern chemistry

In 1774, Antoine Lavoisier