Iron(III) Oxide
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Iron(III) oxide or ferric oxide is the inorganic compound with the formula Fe2O3. It is one of the three main
oxide An oxide () is a chemical compound that contains at least one oxygen atom and one other element in its chemical formula. "Oxide" itself is the dianion of oxygen, an O2– (molecular) ion. with oxygen in the oxidation state of −2. Most of the E ...
s of
iron 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 f ...
, the other two being
iron(II) oxide Iron(II) oxide or ferrous oxide is the inorganic compound with the formula FeO. Its mineral form is known as wüstite. One of several iron oxides, it is a black-colored powder that is sometimes confused with rust, the latter of which consists ...
(FeO), which is rare; and iron(II,III) oxide (Fe3O4), which also occurs naturally as the mineral
magnetite Magnetite is a mineral and one of the main iron ores, with the chemical formula Fe2+Fe3+2O4. It is one of the oxides of iron, and is ferrimagnetic; it is attracted to a magnet and can be magnetized to become a permanent magnet itself. With th ...
. As the mineral known as
hematite Hematite (), also spelled as haematite, is a common iron oxide compound with the formula, Fe2O3 and is widely found in rocks and soils. Hematite crystals belong to the rhombohedral lattice system which is designated the alpha polymorph of . ...
, Fe2O3 is the main source of iron for the steel industry. Fe2O3 is readily attacked by acids. Iron(III) oxide is often called
rust Rust is an iron oxide, a usually reddish-brown oxide formed by the reaction of iron and oxygen in the catalytic presence of water or air moisture. Rust consists of hydrous iron(III) oxides (Fe2O3·nH2O) and iron(III) oxide-hydroxide (FeO(OH ...
, and to some extent this label is useful, because rust shares several properties and has a similar composition; however, in chemistry, rust is considered an ill-defined material, described as Hydrous ferric oxide.


Structure

Fe2O3 can be obtained in various polymorphs. In the main one, α, iron adopts octahedral coordination geometry. That is, each Fe center is bound to six oxygen
ligand In coordination chemistry, a ligand is an ion or molecule ( functional group) that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's elec ...
s. In the γ polymorph, some of the Fe sit on tetrahedral sites, with four oxygen ligands.


Alpha phase

α-Fe2O3 has the
rhombohedral In geometry, a rhombohedron (also called a rhombic hexahedron or, inaccurately, a rhomboid) is a three-dimensional figure with six faces which are rhombi. It is a special case of a parallelepiped where all edges are the same length. It can be us ...
,
corundum Corundum is a crystalline form of aluminium oxide () typically containing traces of iron, titanium, vanadium and chromium. It is a rock-forming mineral. It is a naturally transparent material, but can have different colors depending on the pres ...
(α-Al2O3) structure and is the most common form. It occurs naturally as the mineral
hematite Hematite (), also spelled as haematite, is a common iron oxide compound with the formula, Fe2O3 and is widely found in rocks and soils. Hematite crystals belong to the rhombohedral lattice system which is designated the alpha polymorph of . ...
which is mined as the main
ore Ore is natural rock or sediment that contains one or more valuable minerals, typically containing metals, that can be mined, treated and sold at a profit.Encyclopædia Britannica. "Ore". Encyclopædia Britannica Online. Retrieved 7 Apr ...
of iron. It is
antiferromagnetic In materials that exhibit antiferromagnetism, the magnetic moments of atoms or molecules, usually related to the spins of electrons, align in a regular pattern with neighboring spins (on different sublattices) pointing in opposite directions. ...
below ~260 K (
Morin transition The Morin transition (also known as a spin-flop transition) is a magnetic phase transition in α-Fe2O3 hematite where the antiferromagnetic In materials that exhibit antiferromagnetism, the magnetic moments of atoms or molecules, usually rel ...
temperature), and exhibits weak
ferromagnetism Ferromagnetism is a property of certain materials (such as iron) which results in a large observed magnetic permeability, and in many cases a large magnetic coercivity allowing the material to form a permanent magnet. Ferromagnetic materials ...
between 260 K and the
Néel temperature In physics and materials science, the Curie temperature (''T''C), or Curie point, is the temperature above which certain materials lose their permanent magnetic properties, which can (in most cases) be replaced by induced magnetism. The Cur ...
, 950 K. It is easy to prepare using both
thermal decomposition Thermal decomposition, or thermolysis, is a chemical decomposition caused by heat. The decomposition temperature of a substance is the temperature at which the substance chemically decomposes. The reaction is usually endothermic as heat is re ...
and precipitation in the liquid phase. Its magnetic properties are dependent on many factors, e.g. pressure, particle size, and magnetic field intensity.


Gamma phase

γ-Fe2O3 has a cubic structure. It is metastable and converted from the alpha phase at high temperatures. It occurs naturally as the mineral
maghemite Maghemite (Fe2O3, γ-Fe2O3) is a member of the family of iron oxides. It has the same spinel ferrite structure as magnetite and is also ferrimagnetic. It is sometimes spelled as "maghaemite". ''Maghemite'' can be considered as an Fe(II)-deficie ...
. It is ferromagnetic and finds application in recording tapes, although
ultrafine particles Ultrafine particles (UFPs) are particulate matter of nanoscale size (less than 0.1 μm or 100 nm in diameter). Regulations do not exist for this size class of ambient air pollution particles, which are far smaller than the regulated PM10 and PM ...
smaller than 10 nanometers are superparamagnetic. It can be prepared by thermal dehydratation of gamma
iron(III) oxide-hydroxide Iron(III) oxide-hydroxide or ferric oxyhydroxideA. L. Mackay (1960): "β-Ferric Oxyhydroxide". ''Mineralogical Magazine'' (''Journal of the Mineralogical Society''), volume 32, issue 250, pages 545-557. is the chemical compound of iron, oxygen, ...
. Another method involves the careful oxidation of iron(II,III) oxide (Fe3O4). The ultrafine particles can be prepared by thermal decomposition of
iron(III) oxalate Ferric oxalate, also known as iron(III) oxalate, is a chemical compound composed of ferric ions and oxalate ligands; it may also be regarded as the ferric salt of oxalic acid. The anhydrous material is pale yellow; however, it may be hydrated to ...
.


Other solid phases

Several other phases have been identified or claimed. The β-phase is cubic body-centered (space group Ia3),
metastable In chemistry and physics, metastability denotes an intermediate Energy level, energetic state within a dynamical system other than the system's ground state, state of least energy. A ball resting in a hollow on a slope is a simple example of me ...
, and at temperatures above converts to alpha phase. It can be prepared by reduction of hematite by carbon,
pyrolysis The pyrolysis (or devolatilization) process is the thermal decomposition of materials at elevated temperatures, often in an inert atmosphere. It involves a change of chemical composition. The word is coined from the Greek-derived elements ''py ...
of iron(III) chloride solution, or thermal decomposition of
iron(III) sulfate Iron(III) sulfate (or ferric sulfate), is a family of inorganic compounds with the formula Fe2(SO4)3(H2O)n. A variety of hydrates are known, including the most commonly encountered form of "ferric sulfate". Solutions are used in dyeing as a morda ...
. The epsilon (ε) phase is rhombic, and shows properties intermediate between alpha and gamma, and may have useful magnetic properties applicable for purposes such as high density
recording media Data storage is the recording (storing) of information (data) in a storage medium. Handwriting, phonographic recording, magnetic tape, and optical discs are all examples of storage media. Biological molecules such as RNA and DNA are consi ...
for big data storage. Preparation of the pure epsilon phase has proven very challenging. Material with a high proportion of epsilon phase can be prepared by thermal transformation of the gamma phase. The epsilon phase is also metastable, transforming to the alpha phase at between . It can also be prepared by oxidation of iron in an
electric arc An electric arc, or arc discharge, is an electrical breakdown of a gas that produces a prolonged electrical discharge. The electric current, current through a normally Electrical conductance, nonconductive medium such as air produces a plasma (p ...
or by sol-gel precipitation from
iron(III) nitrate Iron(III) nitrate, or ferric nitrate, is the name used for a series of inorganic compounds with the formula Fe(NO3)3.(H2O)n. Most common is the nonahydrate Fe(NO3)3.(H2O)9. The hydrates are all pale colored, water-soluble paramagnetic salts. H ...
. Research has revealed epsilon iron(III) oxide in ancient Chinese Jian ceramic glazes, which may provide insight into ways to produce that form in the lab. Additionally, at high pressure an
amorphous In condensed matter physics and materials science, an amorphous solid (or non-crystalline solid, glassy solid) is a solid that lacks the long-range order that is characteristic of a crystal. Etymology The term comes from the Greek ''a'' ("wi ...
form is claimed.


Liquid phase

Molten Fe2O3 is expected to have a coordination number of close to 5 oxygen atoms about each iron atom, based on measurements of slightly oxygen deficient supercooled liquid iron oxide droplets, where supercooling circumvents the need for the high oxygen pressures required above the melting point to maintain stoichiometry.


Hydrated iron(III) oxides

Several hydrates of Iron(III) oxide exist. When alkali is added to solutions of soluble Fe(III) salts, a red-brown gelatinous precipitate forms. This is ''not'' Fe(OH)3, but Fe2O3·H2O (also written as Fe(O)OH). Several forms of the hydrated oxide of Fe(III) exist as well. The red
lepidocrocite Lepidocrocite (γ-FeO(OH)), also called esmeraldite or hydrohematite, is an iron oxide-hydroxide mineral. Lepidocrocite has an orthorhombic crystal structure, a hardness of 5, specific gravity of 4, a submetallic luster and a yellow-brown stre ...
(γ-Fe(O)OH) occurs on the outside of rusticles, and the orange
goethite Goethite (, ) is a mineral of the diaspore group, consisting of iron(III) oxide-hydroxide, specifically the "α" polymorph. It is found in soil and other low-temperature environments such as sediment. Goethite has been well known since ancient t ...
(α-Fe(O)OH) occurs internally in rusticles. When Fe2O3·H2O is heated, it loses its water of hydration. Further heating at 1670 K converts Fe2O3 to black Fe3O4 (FeIIFeIII2O4), which is known as the mineral
magnetite Magnetite is a mineral and one of the main iron ores, with the chemical formula Fe2+Fe3+2O4. It is one of the oxides of iron, and is ferrimagnetic; it is attracted to a magnet and can be magnetized to become a permanent magnet itself. With th ...
. Fe(O)OH is soluble in acids, giving . In concentrated aqueous alkali, Fe2O3 gives e(OH)6sup>3−.


Reactions

The most important reaction is its
carbothermal reduction Carbothermic reactions involve the reduction of substances, often metal oxides (O^2-), using carbon as the reducing agent. These chemical reactions are usually conducted at temperatures of several hundred degrees Celsius. Such processes are appl ...
, which gives iron used in steel-making: : Fe2O3 + 3 CO → 2 Fe + 3 CO2 Another redox reaction is the extremely exothermic
thermite Thermite () is a pyrotechnic composition of metal powder and metal oxide. When ignited by heat or chemical reaction, thermite undergoes an exothermic reduction-oxidation (redox) reaction. Most varieties are not explosive, but can create brie ...
reaction with
aluminium Aluminium (aluminum in American and Canadian English) is a chemical element with the symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately one third that of steel. I ...
. : 2 Al + Fe2O3 → 2 Fe + Al2O3 This process is used to weld thick metals such as rails of train tracks by using a ceramic container to funnel the molten iron in between two sections of rail. Thermite is also used in weapons and making small-scale cast-iron sculptures and tools. Partial reduction with hydrogen at about 400 °C produces magnetite, a black magnetic material that contains both Fe(III) and Fe(II): :3 Fe2O3 + H2 → 2 Fe3O4 + H2O Iron(III) oxide is insoluble in water but dissolves readily in strong acid, e.g. hydrochloric and
sulfuric acid Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid ( Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen and hydrogen, with the molecular formu ...
s. It also dissolves well in solutions of chelating agents such as
EDTA Ethylenediaminetetraacetic acid (EDTA) is an aminopolycarboxylic acid with the formula H2N(CH2CO2H)2sub>2. This white, water-soluble solid is widely used to bind to iron (Fe2+/Fe3+) and calcium ions (Ca2+), forming water-soluble complexes ev ...
and
oxalic acid Oxalic acid is an organic acid with the systematic name ethanedioic acid and formula . It is the simplest dicarboxylic acid. It is a white crystalline solid that forms a colorless solution in water. Its name comes from the fact that early inve ...
. Heating iron(III) oxides with other metal oxides or carbonates yields materials known as
ferrate Ferrate loosely refers to a material that can be viewed as containing anionic iron complexes. Examples include tetrachloroferrate ( eCl4sup>2−), oxyanions ( ), tetracarbonylferrate ( e(CO)4sup>2−), the organoferrates. The term ferrate derives f ...
s (ferrate (III)): : ZnO + Fe2O3 → Zn(FeO2)2


Preparation

Iron(III) oxide is a product of the oxidation of iron. It can be prepared in the laboratory by electrolyzing a solution of sodium bicarbonate, an inert electrolyte, with an iron anode: :4 Fe + 3 O2 + 2 H2O → 4 FeO(OH) The resulting hydrated iron(III) oxide, written here as FeO(OH), dehydrates around 200 °C.Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 1. p. 1661. :2 FeO(OH) → Fe2O3 + H2O


Uses


Iron industry

The overwhelming application of iron(III) oxide is as the feedstock of the steel and iron industries, e.g. the production of iron, steel, and many alloys.


Polishing

A very fine powder of ferric oxide is known as "jeweler's rouge", "red rouge", or simply rouge. It is used to put the final polish on metallic
jewelry Jewellery ( UK) or jewelry ( U.S.) consists of decorative items worn for personal adornment, such as brooches, rings, necklaces, earrings, pendants, bracelets, and cufflinks. Jewellery may be attached to the body or the clothes. From a w ...
and
lenses A lens is a transmissive optical device which focuses or disperses a light beam by means of refraction. A simple lens consists of a single piece of transparent material, while a compound lens consists of several simple lenses (''elements''), ...
, and historically as a
cosmetic Cosmetic may refer to: *Cosmetics, or make-up, substances to enhance the beauty of the human body, apart from simple cleaning *Cosmetic, an adjective describing beauty, aesthetics, or appearance, especially concerning the human body *Cosmetic, a t ...
. Rouge cuts more slowly than some modern polishes, such as
cerium(IV) oxide Cerium(IV) oxide, also known as ceric oxide, ceric dioxide, ceria, cerium oxide or cerium dioxide, is an oxide of the rare-earth metal cerium. It is a pale yellow-white powder with the chemical formula CeO2. It is an important commercial produc ...
, but is still used in optics fabrication and by jewelers for the superior finish it can produce. When polishing gold, the rouge slightly stains the gold, which contributes to the appearance of the finished piece. Rouge is sold as a powder, paste, laced on polishing cloths, or solid bar (with a
wax Waxes are a diverse class of organic compounds that are lipophilic, malleable solids near ambient temperatures. They include higher alkanes and lipids, typically with melting points above about 40 °C (104 °F), melting to giv ...
or grease binder). Other polishing compounds are also often called "rouge", even when they do not contain iron oxide. Jewelers remove the residual rouge on jewelry by use of
ultrasonic cleaning Ultrasonic cleaning is a process that uses ultrasound (usually from 20 to 40 kHz) to agitate a fluid, with a cleaning effect. Ultrasonic cleaners come in a variety of sizes, from small desktop units with an internal volume of less than , to larg ...
. Products sold as " stropping compound" are often applied to a leather strop to assist in getting a razor edge on knives, straight razors, or any other edged tool.


Pigment

Iron(III) oxide is also used as a
pigment A pigment is a colored material that is completely or nearly insoluble in water. In contrast, dyes are typically soluble, at least at some stage in their use. Generally dyes are often organic compounds whereas pigments are often inorganic compo ...
, under names "Pigment Brown 6", "Pigment Brown 7", and "Pigment Red 101". Some of them, e.g. Pigment Red 101 and Pigment Brown 6, are approved by the US
Food and Drug Administration The United States Food and Drug Administration (FDA or US FDA) is a List of United States federal agencies, federal agency of the United States Department of Health and Human Services, Department of Health and Human Services. The FDA is respon ...
(FDA) for use in cosmetics.
Iron oxides Iron oxides are chemical compounds composed of iron and oxygen. Several iron oxides are recognized. All are black magnetic solids. Often they are non-stoichiometric. Oxyhydroxides are a related class of compounds, perhaps the best known of whi ...
are used as pigments in dental composites alongside titanium oxides. Hematite is the characteristic component of the Swedish paint color
Falu red Falu red or falun red ( ; sv, falu rödfärg, ) is a permeable red paint commonly used on wooden cottages and barns in Sweden, Finland, and Norway. History Following hundreds of years of mining in Falun, large piles of residual product were ...
.


Magnetic recording

Iron(III) oxide was the most common
magnet A magnet is a material or object that produces a magnetic field. This magnetic field is invisible but is responsible for the most notable property of a magnet: a force that pulls on other ferromagnetic materials, such as iron, steel, nicke ...
ic particle used in all types of magnetic storage and recording media, including magnetic disks (for data storage) and
magnetic tape Magnetic tape is a medium for magnetic storage made of a thin, magnetizable coating on a long, narrow strip of plastic film. It was developed in Germany in 1928, based on the earlier magnetic wire recording from Denmark. Devices that use magne ...
(used in audio and video recording as well as data storage). Its use in computer disks was superseded by cobalt alloy, enabling thinner magnetic films with higher storage density.


Photocatalysis

α-Fe2O3 has been studied as a
photoanode A "photoelectrochemical cell" is one of two distinct classes of device. The first produces electrical energy similarly to a dye-sensitized photovoltaic cell, which meets the standard definition of a photovoltaic cell. The second is a photoelec ...
for solar water oxidation. However, its efficacy is limited by a short diffusion length (2–4 nm) of photo-excited charge carriers and subsequent fast recombination, requiring a large
overpotential In electrochemistry, overpotential is the potential difference (voltage) between a half-reaction's thermodynamically determined reduction potential and the potential at which the redox event is experimentally observed. The term is directly rela ...
to drive the reaction. Research has been focused on improving the water oxidation performance of Fe2O3 using nanostructuring, surface functionalization, or by employing alternate crystal phases such as β-Fe2O3.


Medicine

Calamine Calamine, also known as calamine lotion, is a medication used to treat mild itchiness. This includes from sunburn, insect bites, poison ivy, poison oak, and other mild skin conditions. It may also help dry out skin irritation. It is applie ...
lotion, used to treat mild
itch Itch (also known as pruritus) is a sensation that causes the desire or reflex to scratch. Itch has resisted many attempts to be classified as any one type of sensory experience. Itch has many similarities to pain, and while both are unpleasant ...
iness, is chiefly composed of a combination of
zinc oxide Zinc oxide is an inorganic compound with the formula . It is a white powder that is insoluble in water. ZnO is used as an additive in numerous materials and products including cosmetics, food supplements, rubbers, plastics, ceramics, glass, cement ...
, acting as
astringent An astringent (sometimes called adstringent) is a chemical that shrinks or constricts body tissues. The word derives from the Latin ''adstringere'', which means "to bind fast". Calamine lotion, witch hazel, and yerba mansa, a Californian pla ...
, and about 0.5% iron(III) oxide, the product's active ingredient, acting as antipruritic. The red color of iron(III) oxide is also mainly responsible for the lotion's pink color.


See also

* Chalcanthum


References


External links


NIOSH Pocket Guide to Chemical Hazards
{{DEFAULTSORT:Iron(Iii) Oxide E-number additives Iron oxide pigments Iron(III) compounds Transition metal oxides Sesquioxides