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Iridium is a
chemical element A chemical element is a species of atoms that have a given number of protons in their atomic nucleus, nuclei, including the pure Chemical substance, substance consisting only of that species. Unlike chemical compounds, chemical elements canno ...
with the symbol Ir and
atomic number The atomic number or nuclear charge number (symbol ''Z'') of a chemical element is the charge number of an atomic nucleus. For ordinary nuclei, this is equal to the proton number (''n''p) or the number of protons found in the nucleus of ever ...
77. A very hard, brittle, silvery-white
transition metal In chemistry, a transition metal (or transition element) is a chemical element in the d-block of the periodic table (groups 3 to 12), though the elements of group 12 (and less often group 3) are sometimes excluded. They are the elements that can ...
of the platinum group, it is considered the second-densest naturally occurring metal (after osmium) with a density of as defined by experimental X-ray crystallography. It is one of the most
corrosion Corrosion is a natural process that converts a refined metal into a more chemically stable oxide. It is the gradual deterioration of materials (usually a metal) by chemical or electrochemical reaction with their environment. Corrosion engi ...
-resistant metals, even at temperatures as high as . However, corrosion-resistance is not quantifiable in absolute terms; although only certain molten salts and halogens are corrosive to solid iridium, finely divided iridium dust is much more reactive and can be flammable, whereas gold dust is not flammable but can be attacked by substances that iridium resists, such as aqua regia. Iridium was discovered in 1803 among insoluble impurities in natural platinum. Smithson Tennant, the primary discoverer, named it after the Greek goddess Iris, personification of the rainbow, because of the striking and diverse colors of its salts. Iridium is one of the rarest elements in Earth's crust, with annual production and consumption of only . 191Ir and 193Ir are the only two naturally occurring
isotope Isotopes are two or more types of atoms that have the same atomic number (number of protons in their nuclei) and position in the periodic table (and hence belong to the same chemical element), and that differ in nucleon numbers ( mass num ...
s of iridium, as well as the only stable isotopes; the latter is the more abundant. The dominant uses of iridium are the metal itself and its alloys, as in high-performance spark plugs, crucibles for recrystallization of semiconductors at high temperatures, and electrodes for the production of chlorine in the chloralkali process. Important compounds of iridium are chlorides and iodides in industrial catalysis. Iridium is a component of some OLEDs. Iridium is found in meteorites in much higher abundance than in the Earth's crust. For this reason, the unusually high abundance of iridium in the clay layer at the Cretaceous–Paleogene boundary gave rise to the
Alvarez hypothesis The Alvarez hypothesis posits that the mass extinction of the non-avian dinosaurs and many other living things during the Cretaceous–Paleogene extinction event was caused by the impact of a large asteroid on the Earth. Prior to 2013, it was ...
that the impact of a massive extraterrestrial object caused the extinction of dinosaurs and many other species 66 million years ago, now known to be produced by the impact that formed the Chicxulub crater. Similarly, an iridium anomaly in core samples from the
Pacific Ocean The Pacific Ocean is the largest and deepest of Earth's five oceanic divisions. It extends from the Arctic Ocean in the north to the Southern Ocean (or, depending on definition, to Antarctica) in the south, and is bounded by the conti ...
suggested the Eltanin impact of about 2.5 million years ago. It is thought that the total amount of iridium in the planet Earth is much higher than that observed in crustal rocks, but as with other platinum-group metals, the high density and tendency of iridium to bond with iron caused most iridium to descend below the crust when the planet was young and still molten.


Characteristics


Physical properties

A member of the platinum group
metal A metal (from ancient Greek, Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electrical resistivity and conductivity, e ...
s, iridium is white, resembling platinum, but with a slight yellowish cast. Because of its
hardness In materials science, hardness (antonym: softness) is a measure of the resistance to localized plastic deformation induced by either mechanical indentation or abrasion. In general, different materials differ in their hardness; for example hard ...
, brittleness, and very high
melting point The melting point (or, rarely, liquefaction point) of a substance is the temperature at which it changes state from solid to liquid. At the melting point the solid and liquid phase exist in equilibrium. The melting point of a substance depen ...
, solid iridium is difficult to machine, form, or work; thus powder metallurgy is commonly employed instead. It is the only metal to maintain good mechanical properties in air at temperatures above . It has the 10th highest boiling point among all elements and becomes a superconductor at temperatures below . Iridium's modulus of elasticity is the second-highest among the metals, being surpassed only by osmium. This, together with a high shear modulus and a very low figure for Poisson's ratio (the relationship of longitudinal to lateral strain), indicate the high degree of
stiffness Stiffness is the extent to which an object resists deformation in response to an applied force. The complementary concept is flexibility or pliability: the more flexible an object is, the less stiff it is. Calculations The stiffness, k, of a ...
and resistance to deformation that have rendered its fabrication into useful components a matter of great difficulty. Despite these limitations and iridium's high cost, a number of applications have developed where mechanical strength is an essential factor in some of the extremely severe conditions encountered in modern technology. The measured
density Density (volumetric mass density or specific mass) is the substance's mass per unit of volume. The symbol most often used for density is ''ρ'' (the lower case Greek letter rho), although the Latin letter ''D'' can also be used. Mathematicall ...
of iridium is only slightly lower (by about 0.12%) than that of osmium, the densest metal known. Some ambiguity occurred regarding which of the two elements was denser, due to the small size of the difference in density and difficulties in measuring it accurately, but, with increased accuracy in factors used for calculating density, X-ray crystallographic data yielded densities of for iridium and for osmium. Iridium is extremely brittle, to the point of being hard to weld because the heat-affected zone cracks, but it can be made more ductile by addition of small quantities of
titanium Titanium is a chemical element with the symbol Ti and atomic number 22. Found in nature only as an oxide, it can be reduced to produce a lustrous transition metal with a silver color, low density, and high strength, resistant to corrosion i ...
and zirconium (0.2% of each apparently works well).- The
Vickers hardness The Vickers hardness test was developed in 1921 by Robert L. Smith and George E. Sandland at Vickers Ltd as an alternative to the Brinell method to measure the hardness of materials. The Vickers test is often easier to use than other hardness ...
of pure platinum is 56 HV, whereas platinum with 50% of iridium can reach over 500 HV.


Chemical properties

Iridium is the most corrosion-resistant metal known: it is not attacked by acids, including aqua regia. In the presence of oxygen, it reacts with
cyanide Cyanide is a naturally occurring, rapidly acting, toxic chemical that can exist in many different forms. In chemistry, a cyanide () is a chemical compound that contains a functional group. This group, known as the cyano group, consists of ...
salts. Traditional oxidants also react, including the halogens and oxygen at higher temperatures. Iridium also reacts directly with sulfur at atmospheric pressure to yield iridium disulfide.


Isotopes

Iridium has two naturally occurring, stable
isotope Isotopes are two or more types of atoms that have the same atomic number (number of protons in their nuclei) and position in the periodic table (and hence belong to the same chemical element), and that differ in nucleon numbers ( mass num ...
s, 191Ir and 193Ir, with natural abundances of 37.3% and 62.7%, respectively. At least 37 radioisotopes have also been synthesized, ranging in mass number from 164 to 202. 192Ir, which falls between the two stable isotopes, is the most stable radioisotope, with a
half-life Half-life (symbol ) is the time required for a quantity (of substance) to reduce to half of its initial value. The term is commonly used in nuclear physics to describe how quickly unstable atoms undergo radioactive decay or how long stable ...
of 73.827 days, and finds application in
brachytherapy Brachytherapy is a form of radiation therapy where a sealed radiation source is placed inside or next to the area requiring treatment. ''Brachy'' is Greek for short. Brachytherapy is commonly used as an effective treatment for cervical, pro ...
and in industrial
radiography Radiography is an imaging technique using X-rays, gamma rays, or similar ionizing radiation and non-ionizing radiation to view the internal form of an object. Applications of radiography include medical radiography ("diagnostic" and "therapeu ...
, particularly for nondestructive testing of welds in steel in the oil and gas industries; iridium-192 sources have been involved in a number of radiological accidents. Three other isotopes have half-lives of at least a day—188Ir, 189Ir, and 190Ir. Isotopes with masses below 191 decay by some combination of β+ decay, α decay, and (rare) proton emission, with the exception of 189Ir, which decays by
electron capture Electron capture (K-electron capture, also K-capture, or L-electron capture, L-capture) is a process in which the proton-rich nucleus of an electrically neutral atom absorbs an inner atomic electron, usually from the K or L electron shells. ...
. Synthetic isotopes heavier than 191 decay by β decay, although 192Ir also has a minor electron capture decay path. All known isotopes of iridium were discovered between 1934 and 2008, with the most recent discoveries being 200–202Ir. At least 32
metastable isomers A nuclear isomer is a metastable state of an atomic nucleus, in which one or more nucleons (protons or neutrons) occupy higher energy levels than in the ground state of the same nucleus. "Metastable" describes nuclei whose excited states have h ...
have been characterized, ranging in mass number from 164 to 197. The most stable of these is 192m2Ir, which decays by isomeric transition with a half-life of 241 years, making it more stable than any of iridium's synthetic isotopes in their ground states. The least stable isomer is 190m3Ir with a half-life of only 2 μs. The isotope 191Ir was the first one of any element to be shown to present a
Mössbauer effect The Mössbauer effect, or recoilless nuclear resonance fluorescence, is a physical phenomenon discovered by Rudolf Mössbauer in 1958. It involves the resonant and recoil-free emission and absorption of gamma radiation by atomic nuclei bound in a ...
. This renders it useful for Mössbauer spectroscopy for research in physics, chemistry, biochemistry, metallurgy, and mineralogy.


Chemistry


Oxidation states

Iridium forms compounds in oxidation states between −3 and +9, but the most common oxidation states are +1, +3, and +4. Well-characterized compounds containing iridium in the +6 oxidation state include and the oxides and . iridium(VIII) oxide () was generated under matrix isolation conditions at 6 K in
argon Argon is a chemical element with the symbol Ar and atomic number 18. It is in group 18 of the periodic table and is a noble gas. Argon is the third-most abundant gas in Earth's atmosphere, at 0.934% (9340 ppmv). It is more than twice a ...
. The highest oxidation state (+9), which is also the highest recorded for ''any'' element, is found in gaseous .


Binary compounds

Iridium does not form binary
hydride In chemistry, a hydride is formally the anion of hydrogen( H−). The term is applied loosely. At one extreme, all compounds containing covalently bound H atoms are called hydrides: water (H2O) is a hydride of oxygen, ammonia is a hydride ...
s. Only one binary oxide is well-characterized: Iridium dioxide, . It is a blue black solid that adopts the fluorite structure. A sesquioxide, , has been described as a blue-black powder, which is oxidized to by . The corresponding disulfides, diselenides, sesquisulfides, and sesquiselenides are known, as well as . Binary trihalides, are known for all of the halogens. For oxidation states +4 and above, only the tetrafluoride, pentafluoride and hexafluoride are known. Iridium hexafluoride, , is a volatile yellow solid, composed of octahedral molecules. It decomposes in water and is reduced to ,. Iridium pentafluoride is also a strong oxidant, but it is a tetramer, , formed by four corner-sharing octahedra.


Complexes

The
coordination complex A coordination complex consists of a central atom or ion, which is usually metallic and is called the ''coordination centre'', and a surrounding array of bound molecules or ions, that are in turn known as '' ligands'' or complexing agents. M ...
es of iridium are extensive. Iridium in its complexes is always low-spin). Ir(III) and Ir(IV) generally form octahedral complexes. Polyhydride complexes are known for the +5 and +3 oxidation states. One example is . The ternary hydride is believed to contain both the and the 18-electron anion. Iridium also oxyanions with oxidation states +4 and +5. and can be prepared from the reaction of potassium oxide or
potassium superoxide Potassium superoxide is an inorganic compound with the formula KO2. It is a yellow paramagnetic solid that decomposes in moist air. It is a rare example of a stable salt of the superoxide anion. It is used as a scrubber, dehumidifier, and gen ...
with iridium at high temperatures. Such solids are not soluble in conventional solvents. As for many elements, the chlorides are key complexes. Hexachloroiridic (IV) acid, , and its ammonium salt are the most common iridium compounds from an industrial and preparative perspectives. They are intermediates in the purification of iridium and used as precursors for most other iridium compounds, as well as in the preparation of
anode An anode is an electrode of a polarized electrical device through which conventional current enters the device. This contrasts with a cathode, an electrode of the device through which conventional current leaves the device. A common mnemonic is ...
coatings. The ion has an intense dark brown color, and can be readily reduced to the lighter-colored and vice versa.
Iridium trichloride Iridium(III) chloride is the inorganic compound with the formula IrCl3. The anhydrous compound is relatively rare, but the related hydrate is useful for preparing other iridium compounds. The anhydrous salt is a dark green crystalline solid. More ...
, , which can be obtained in anhydrous form from direct oxidation of iridium powder by
chlorine Chlorine is a chemical element with the symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between them. Chlorine i ...
at 650 °C, or in hydrated form by dissolving in hydrochloric acid, is often used as a starting material for the synthesis of other Ir(III) compounds. Another compound used as a starting material is ammonium hexachloroiridate(III), . In the presence of air, iridium metal dissolves in molten alkali-metal cyanides to produce the (hexacyanoiridate) ion.


Organoiridium chemistry

Organoiridium compounds contain iridium–
carbon Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent—its atom making four electrons available to form covalent chemical bonds. It belongs to group 14 of the periodic table. Carbon ma ...
bonds. Early studies identified the very stable tetrairidium dodecacarbonyl, . In this compound, each of the iridium atoms is bonded to the other three, forming a tetrahedral cluster. The discovery of Vaska's complex () opened the door for oxidative addition reactions, a process fundamental to useful reactions. For example, Crabtree's catalyst, a homogeneous catalyst for
hydrogenation Hydrogenation is a chemical reaction between molecular hydrogen (H2) and another compound or element, usually in the presence of a catalyst such as nickel, palladium or platinum. The process is commonly employed to reduce or saturate organic ...
reactions. Iridium complexes played a pivotal role in the development of Carbon–hydrogen bond activation (C–H activation), which promises to allow functionalization of hydrocarbons, which are traditionally regarded as unreactive.


History


Platinum group

The discovery of iridium is intertwined with that of platinum and the other metals of the platinum group. The first European reference to platinum appears in 1557 in the writings of the Italian humanist Julius Caesar Scaliger as a description of an unknown noble metal found between Darién and Mexico, "which no fire nor any Spanish artifice has yet been able to liquefy". From their first encounters with platinum, the Spanish generally saw the metal as a kind of impurity in gold, and it was treated as such. It was often simply thrown away, and there was an official decree forbidding the adulteration of gold with platinum impurities. In 1735,
Antonio de Ulloa Antonio de Ulloa y de la Torre-Giralt, FRS, FRSA, KOS (12 January 1716 – 3 July 1795) was a Spanish naval officer, scientist, and administrator. At the age of nineteen, he joined the French Geodesic Mission to what is now the countr ...
and
Jorge Juan y Santacilia Jorge Juan y Santacilia ( Novelda, Alicante, 5 January 1713 – Madrid, 21 June 1773) was a Spanish mathematician, scientist, naval officer, and mariner. He determined that the Earth is not perfectly spherical but is oblate, i.e. flattened at th ...
saw Native Americans mining platinum while the Spaniards were travelling through Colombia and Peru for eight years. Ulloa and Juan found mines with the whitish metal nuggets and took them home to Spain. Antonio de Ulloa returned to Spain and established the first mineralogy lab in Spain and was the first to systematically study platinum, which was in 1748. His historical account of the expedition included a description of platinum as being neither separable nor calcinable. Ulloa also anticipated the discovery of platinum mines. After publishing the report in 1748, Ulloa did not continue to investigate the new metal. In 1758, he was sent to superintend mercury mining operations in Huancavelica. In 1741, Charles Wood, a British
metallurgist Metallurgy is a domain of materials science and engineering that studies the physical and chemical behavior of metallic elements, their inter-metallic compounds, and their mixtures, which are known as alloys. Metallurgy encompasses both the sc ...
, found various samples of Colombian platinum in Jamaica, which he sent to William Brownrigg for further investigation. In 1750, after studying the platinum sent to him by Wood, Brownrigg presented a detailed account of the metal to the Royal Society, stating that he had seen no mention of it in any previous accounts of known minerals. Brownrigg also made note of platinum's extremely high melting point and refractoriness toward
borax Borax is a salt (ionic compound), a hydrated borate of sodium, with chemical formula often written . It is a colorless crystalline solid, that dissolves in water to make a basic solution. It is commonly available in powder or granular form ...
. Other chemists across Europe soon began studying platinum, including
Andreas Sigismund Marggraf Andreas Sigismund Marggraf (; 3 March 1709 – 7 August 1782) was a German chemist from Berlin, then capital of the Margraviate of Brandenburg, and a pioneer of analytical chemistry. He isolated zinc in 1746 by heating calamine and carbon. Tho ...
, Torbern Bergman, Jöns Jakob Berzelius, William Lewis, and
Pierre Macquer Pierre-Joseph Macquer (9 October 1718 – 15 February 1784) was an influential French chemist. He is known for his ''Dictionnaire de chymie'' (1766). He was also involved in practical applications, to medicine and industry, such as the French de ...
. In 1752, Henrik Scheffer published a detailed scientific description of the metal, which he referred to as "white gold", including an account of how he succeeded in fusing platinum ore with the aid of
arsenic Arsenic is a chemical element with the symbol As and atomic number 33. Arsenic occurs in many minerals, usually in combination with sulfur and metals, but also as a pure elemental crystal. Arsenic is a metalloid. It has various allotropes, b ...
. Scheffer described platinum as being less pliable than gold, but with similar resistance to corrosion.


Discovery

Chemists who studied platinum dissolved it in aqua regia (a mixture of hydrochloric and
nitric acid Nitric acid is the inorganic compound with the formula . It is a highly corrosive mineral acid. The compound is colorless, but older samples tend to be yellow cast due to decomposition into oxides of nitrogen. Most commercially available ni ...
s) to create soluble salts. They always observed a small amount of a dark, insoluble residue.
Joseph Louis Proust Joseph Louis Proust (26 September 1754 – 5 July 1826) was a French chemist. He was best known for his discovery of the law of definite proportions in 1794, stating that chemical compounds always combine in constant proportions. Life Joseph L. ...
thought that the residue was
graphite Graphite () is a crystalline form of the element carbon. It consists of stacked layers of graphene. Graphite occurs naturally and is the most stable form of carbon under standard conditions. Synthetic and natural graphite are consumed on la ...
. The French chemists Victor Collet-Descotils,
Antoine François, comte de Fourcroy Antoine is a French given name (from the Latin ''Antonius'' meaning 'highly praise-worthy') that is a variant of Danton, Titouan, D'Anton and Antonin. The name is used in France, Switzerland, Belgium, Canada, West Greenland, Haiti, French Guiana ...
, and Louis Nicolas Vauquelin also observed the black residue in 1803, but did not obtain enough for further experiments. In 1803, British scientist Smithson Tennant (1761–1815) analyzed the insoluble residue and concluded that it must contain a new metal. Vauquelin treated the powder alternately with alkali and acids and obtained a volatile new oxide, which he believed to be of this new metal—which he named ''ptene'', from the Greek word ''ptēnós'', "winged". Tennant, who had the advantage of a much greater amount of residue, continued his research and identified the two previously undiscovered elements in the black residue, iridium and osmium. He obtained dark red crystals (probably of ]·''n'') by a sequence of reactions with sodium hydroxide and hydrochloric acid. He named iridium after Iris (), the Greek winged goddess of the rainbow and the messenger of the Olympian gods, because many of the salts he obtained were strongly colored. Discovery of the new elements was documented in a letter to the Royal Society on June 21, 1804.


Metalworking and applications

British scientist
John George Children John George Children FRS FRSE FLS PRES (18 May 1777 – 1 January 1852 in Halstead, Kent) was a British chemist, mineralogist and zoologist. He invented a method to extract silver from ore without the need for mercury. He was a friend of Sir ...
was the first to melt a sample of iridium in 1813 with the aid of "the greatest galvanic battery that has ever been constructed" (at that time). The first to obtain high-purity iridium was Robert Hare in 1842. He found it had a density of around and noted the metal is nearly immalleable and very hard. The first melting in appreciable quantity was done by
Henri Sainte-Claire Deville Henri is an Estonian, Finnish, French, German and Luxembourgish form of the masculine given name Henry. People with this given name ; French noblemen :'' See the ' List of rulers named Henry' for Kings of France named Henri.'' * Henri I de Mon ...
and Jules Henri Debray in 1860. They required burning more than of pure and gas for each of iridium. These extreme difficulties in melting the metal limited the possibilities for handling iridium. John Isaac Hawkins was looking to obtain a fine and hard point for fountain pen nibs, and in 1834 managed to create an iridium-pointed gold pen. In 1880, John Holland and William Lofland Dudley were able to melt iridium by adding
phosphorus Phosphorus is a chemical element with the symbol P and atomic number 15. Elemental phosphorus exists in two major forms, white phosphorus and red phosphorus, but because it is highly reactive, phosphorus is never found as a free element on Ea ...
and patented the process in the United States; British company Johnson Matthey later stated they had been using a similar process since 1837 and had already presented fused iridium at a number of World Fairs. The first use of an alloy of iridium with ruthenium in thermocouples was made by Otto Feussner in 1933. These allowed for the measurement of high temperatures in air up to . In Munich, Germany in 1957
Rudolf Mössbauer Rudolf Ludwig Mössbauer (German spelling: ''Mößbauer''; ; 31 January 1929 – 14 September 2011) was a German physicist best known for his 1957 discovery of ''recoilless nuclear resonance fluorescence'' for which he was awarded the 1961 Nobe ...
, in what has been called one of the "landmark experiments in twentieth-century physics", discovered the resonant and recoil-free emission and absorption of
gamma ray A gamma ray, also known as gamma radiation (symbol γ or \gamma), is a penetrating form of electromagnetic radiation arising from the radioactive decay of atomic nuclei. It consists of the shortest wavelength electromagnetic waves, typically ...
s by atoms in a solid metal sample containing only 191Ir. This phenomenon, known as the
Mössbauer effect The Mössbauer effect, or recoilless nuclear resonance fluorescence, is a physical phenomenon discovered by Rudolf Mössbauer in 1958. It involves the resonant and recoil-free emission and absorption of gamma radiation by atomic nuclei bound in a ...
resulted in the awarding of the
Nobel Prize in Physics ) , image = Nobel Prize.png , alt = A golden medallion with an embossed image of a bearded man facing left in profile. To the left of the man is the text "ALFR•" then "NOBEL", and on the right, the text (smaller) "NAT•" then " ...
in 1961, at the age 32, just three years after he published his discovery.


Occurrence

Along with all elements having atomic weights higher than that 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 ...
, iridium is only naturally formed by the r-process (rapid neutron capture) in supernovae and neutron star mergers. Iridium is one of the nine least abundant stable elements in Earth's crust, having an average mass fraction of 0.001  ppm in crustal rock; platinum is 10 times more abundant,
gold Gold is a chemical element with the symbol Au (from la, aurum) and atomic number 79. This makes it one of the higher atomic number elements that occur naturally. It is a bright, slightly orange-yellow, dense, soft, malleable, and ductile ...
is 40 times more abundant, and
silver Silver is a chemical element with the symbol Ag (from the Latin ', derived from the Proto-Indo-European ''h₂erǵ'': "shiny" or "white") and atomic number 47. A soft, white, lustrous transition metal, it exhibits the highest electrical ...
and mercury are 80 times more abundant. Tellurium is about as abundant as iridium. In contrast to its low abundance in crustal rock, iridium is relatively common in meteorites, with concentrations of 0.5 ppm or more. The overall concentration of iridium on Earth is thought to be much higher than what is observed in crustal rocks, but because of the density and siderophilic ("iron-loving") character of iridium, it descended below the crust and into Earth's core when the planet was still molten. Iridium is found in nature as an uncombined element or in natural
alloy An alloy is a mixture of chemical elements of which at least one is a metal. Unlike chemical compounds with metallic bases, an alloy will retain all the properties of a metal in the resulting material, such as electrical conductivity, ductili ...
s; especially the iridium–osmium alloys,
osmiridium Osmiridium and iridosmine are natural alloys of the elements osmium and iridium, with traces of other platinum-group metals. Osmiridium has been defined as containing a higher proportion of iridium, with iridosmine containing more osmium. However ...
(osmium-rich), and iridosmium (iridium-rich). In the
nickel Nickel is a chemical element with symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel is a hard and ductile transition metal. Pure nickel is chemically reactive but large pieces are slow t ...
and
copper Copper is a chemical element with the symbol Cu (from la, cuprum) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pink ...
deposits, the platinum group metals occur as sulfides (i.e. (), tellurides (i.e. PtBiTe), antimonides (PdSb), and arsenides (i.e. ). In all of these compounds, platinum is exchanged by a small amount of iridium and osmium. As with all of the platinum group metals, iridium can be found naturally in alloys with raw nickel or raw copper. A number of iridium-dominant minerals, with iridium as the species-forming element, are known. They are exceedingly rare and often represent the iridium analogues of the above-given ones. The examples are irarsite and cuproiridsite, to mention some. Within Earth's crust, iridium is found at highest concentrations in three types of geologic structure: igneous deposits (crustal intrusions from below), impact craters, and deposits reworked from one of the former structures. The largest known primary reserves are in the Bushveld igneous complex in
South Africa South Africa, officially the Republic of South Africa (RSA), is the southernmost country in Africa. It is bounded to the south by of coastline that stretch along the South Atlantic and Indian Oceans; to the north by the neighbouring coun ...
, (near the largest known impact structure, the Vredefort impact structure) though the large copper–nickel deposits near Norilsk in
Russia Russia (, , ), or the Russian Federation, is a transcontinental country spanning Eastern Europe and Northern Asia. It is the largest country in the world, with its internationally recognised territory covering , and encompassing one-ei ...
, and the Sudbury Basin (also an impact crater) in
Canada Canada is a country in North America. Its ten provinces and three territories extend from the Atlantic Ocean to the Pacific Ocean and northward into the Arctic Ocean, covering over , making it the world's second-largest country by to ...
are also significant sources of iridium. Smaller reserves are found in the United States. Iridium is also found in secondary deposits, combined with platinum and other platinum group metals in alluvial deposits. The alluvial deposits used by
pre-Columbian In the history of the Americas, the pre-Columbian era spans from the original settlement of North and South America in the Upper Paleolithic period through European colonization, which began with Christopher Columbus's voyage of 1492. Usually, ...
people in the Chocó Department of Colombia are still a source for platinum-group metals. As of 2003, world reserves have not been estimated.


Marine oceanography

Iridium is found within marine organisms,
sediment Sediment is a naturally occurring material that is broken down by processes of weathering and erosion, and is subsequently transported by the action of wind, water, or ice or by the force of gravity acting on the particles. For example, sand ...
s, and the water column. The abundance of iridium in seawater and organisms is relatively low, as it does not readily form chloride complexes. The abundance in organisms is about 20 parts per trillion, or about five orders of magnitude less than in
sedimentary rock Sedimentary rocks are types of rock that are formed by the accumulation or deposition of mineral or organic particles at Earth's surface, followed by cementation. Sedimentation is the collective name for processes that cause these particles ...
s at the Cretaceous–Paleogene (K–T) boundary. The concentration of iridium in seawater and marine sediment is sensitive to marine oxygenation, seawater temperature, and various geological and biological processes. Iridium in sediments can come from
cosmic dust Cosmic dust, also called extraterrestrial dust, star dust or space dust, is dust which exists in outer space, or has fallen on Earth. Most cosmic dust particles measure between a few molecules and 0.1 mm (100 micrometers). Larger particles are c ...
, volcanoes,
precipitation In meteorology, precipitation is any product of the condensation of atmospheric water vapor that falls under gravitational pull from clouds. The main forms of precipitation include drizzle, rain, sleet, snow, ice pellets, graupel and hail. ...
from seawater, microbial processes, or hydrothermal vents, and its abundance can be strongly indicative of the source. It tends to associate with other ferrous metals in manganese nodules. Iridium is one of the characteristic elements of extraterrestrial rocks, and, along with osmium, can be used as a tracer element for meteoritic material in sediment. For example core samples from the
Pacific Ocean The Pacific Ocean is the largest and deepest of Earth's five oceanic divisions. It extends from the Arctic Ocean in the north to the Southern Ocean (or, depending on definition, to Antarctica) in the south, and is bounded by the conti ...
with elevated iridium levels suggested the Eltanin impact of about 2.5 million years ago. Some of the mass extinctions, such as the
Cretaceous extinction The Cretaceous ( ) is a geological period that lasted from about 145 to 66 million years ago (Mya). It is the third and final period of the Mesozoic Era, as well as the longest. At around 79 million years, it is the longest geological period of ...
, can be identified by anomalously high concentrations of iridium in sediment, and these can be linked to major asteroid impacts.


Cretaceous–Paleogene boundary presence

The Cretaceous–Paleogene boundary of 66 million years ago, marking the temporal border between the
Cretaceous The Cretaceous ( ) is a geological period that lasted from about 145 to 66 million years ago (Mya). It is the third and final period of the Mesozoic Era, as well as the longest. At around 79 million years, it is the longest geological period of ...
and Paleogene periods of geological time, was identified by a thin stratum of iridium-rich clay. A team led by Luis Alvarez proposed in 1980 an extraterrestrial origin for this iridium, attributing it to an asteroid or comet impact. Their theory, known as the
Alvarez hypothesis The Alvarez hypothesis posits that the mass extinction of the non-avian dinosaurs and many other living things during the Cretaceous–Paleogene extinction event was caused by the impact of a large asteroid on the Earth. Prior to 2013, it was ...
, is now widely accepted to explain the extinction of the non-avian dinosaurs. A large buried impact crater structure with an estimated age of about 66 million years was later identified under what is now the Yucatán Peninsula (the Chicxulub crater). Dewey M. McLean and others argue that the iridium may have been of
volcanic A volcano is a rupture in the crust of a planetary-mass object, such as Earth, that allows hot lava, volcanic ash, and gases to escape from a magma chamber below the surface. On Earth, volcanoes are most often found where tectonic plat ...
origin instead, because
Earth Earth is the third planet from the Sun and the only astronomical object known to harbor life. While large volumes of water can be found throughout the Solar System, only Earth sustains liquid surface water. About 71% of Earth's sur ...
's core is rich in iridium, and active volcanoes such as
Piton de la Fournaise Piton de la Fournaise (; en, "Peak of the Furnace") is a shield volcano on the eastern side of Réunion island (a French overseas department and region) in the Indian Ocean. It is currently one of the most active volcanoes in the world, al ...
, in the island of Réunion, are still releasing iridium.


Production

Worldwide production of iridium is about . The price is high and varying (see table). Illustrative factors that affect the price include oversupply of Ir crucibles and changes in LED technology. Platinum metals occur together as dilute ores. Iridium is one of the rarer platinum metals: for every 190 tonnes of platinum obtained from ores, only 7.5 tonnes of iridium is isolated. To separate the metals, they must first be brought into
solution Solution may refer to: * Solution (chemistry), a mixture where one substance is dissolved in another * Solution (equation), in mathematics ** Numerical solution, in numerical analysis, approximate solutions within specified error bounds * Solutio ...
. Two methods for rendering Ir-containing ores soluble are (i) fusion of the solid with
sodium peroxide Sodium peroxide is an inorganic compound with the formula Na2O2. This yellowish solid is the product of sodium ignited in excess oxygen. It is a strong base. This metal peroxide exists in several hydrates and peroxyhydrates including Na2O2·2H2O ...
followed by extraction of the resulting glass in aqua regia and (ii) extraction of the solid with a mixture of
chlorine Chlorine is a chemical element with the symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between them. Chlorine i ...
with hydrochloric acid. From soluble extracts, iridium is separated by precipitating solid ammonium hexachloroiridate () or by extracting with organic amines. The first method is similar to the procedure Tennant and Wollaston used for their original separation. The second method can be planned as continuous
liquid–liquid extraction Liquid–liquid extraction (LLE), also known as solvent extraction and partitioning, is a method to separate compounds or metal complexes, based on their relative solubilities in two different immiscible liquids, usually water (polar) and an orga ...
and is therefore more suitable for industrial scale production. In either case, the product, an iridium chloride salt, is reduced with hydrogen, yielding the metal as a powder or ''
sponge Sponges, the members of the phylum Porifera (; meaning 'pore bearer'), are a basal animal clade as a sister of the diploblasts. They are multicellular organisms that have bodies full of pores and channels allowing water to circulate throu ...
'', which is amenable to powder metallurgy techniques. Iridium is also obtained commercially as a by-product from
nickel Nickel is a chemical element with symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel is a hard and ductile transition metal. Pure nickel is chemically reactive but large pieces are slow t ...
and
copper Copper is a chemical element with the symbol Cu (from la, cuprum) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pink ...
mining and processing. During electrorefining of copper and nickel, noble metals such as silver, gold and the
platinum group metal The platinum-group metals (abbreviated as the PGMs; alternatively, the platinoids, platinides, platidises, platinum group, platinum metals, platinum family or platinum-group elements (PGEs)) are six noble, precious metallic elements clustered tog ...
s as well as selenium and tellurium settle to the bottom of the cell as ''anode mud'', which forms the starting point for their extraction.


Applications

The main areas of use of iridium are electrodes for producing chlorine and other aggressive products, OLEDs, crucibles, catalysts (e.g. acetic acid), and ignition tips for spark plugs.


Ir metal and alloys

Resistance to heat and corrosion are the bases for several uses of iridium and its alloys. Owing to its high melting point, hardness, and
corrosion resistance Corrosion is a natural process that converts a refined metal into a more chemically stable oxide. It is the gradual deterioration of materials (usually a metal) by chemical or electrochemical reaction with their environment. Corrosion engin ...
, iridium is used to make crucibles. Such crucibles are used in the Czochralski process to produce oxide single-crystals (such as sapphires) for use in computer memory devices and in solid state lasers. The crystals, such as gadolinium gallium garnet and yttrium gallium garnet, are grown by melting pre-sintered charges of mixed oxides under oxidizing conditions at temperatures up to . Certain long-life aircraft engine parts are made of an iridium alloy, and an iridium–
titanium Titanium is a chemical element with the symbol Ti and atomic number 22. Found in nature only as an oxide, it can be reduced to produce a lustrous transition metal with a silver color, low density, and high strength, resistant to corrosion i ...
alloy is used for deep-water pipes because of its corrosion resistance. Iridium is used for multi-pored spinnerets, through which a plastic polymer melt is extruded to form fibers, such as rayon. Osmium–iridium is used for
compass A compass is a device that shows the cardinal directions used for navigation and geographic orientation. It commonly consists of a magnetized needle or other element, such as a compass card or compass rose, which can pivot to align itself with ...
bearings and for balances. Because of their resistance to arc erosion, iridium alloys are used by some manufacturers for electrical contacts for spark plugs, and iridium-based spark plugs are particularly used in aviation.


Catalysis

Iridium compounds are used as catalysts in the Cativa process for
carbonylation Carbonylation refers to reactions that introduce carbon monoxide into organic and inorganic substrates. Carbon monoxide is abundantly available and conveniently reactive, so it is widely used as a reactant in industrial chemistry. The term carbon ...
of methanol to produce acetic acid. Iridium complexes are often active for asymmetric hydrogenation both by traditional
hydrogenation Hydrogenation is a chemical reaction between molecular hydrogen (H2) and another compound or element, usually in the presence of a catalyst such as nickel, palladium or platinum. The process is commonly employed to reduce or saturate organic ...
. and transfer hydrogenation. This property is the basis of the industrial route to the chiral herbicide (S)-metolachlor. As practiced by Syngenta on the scale of 10,000 tons/year, the complex _[Ir(COD)Clsub>2_in_the_presence_of_Josiphos_ligands.html" ;"title="r(COD)Cl.html" ;"title=" [Ir(COD)Cl"> [Ir(COD)Clsub>2 in the presence of Josiphos ligands">r(COD)Cl.html" ;"title=" [Ir(COD)Cl"> [Ir(COD)Clsub>2 in the presence of Josiphos ligands.


Medical imaging

The radioisotope iridium-192 is one of the two most important sources of energy for use in industrial Industrial radiography#Radioisotope sources, γ-radiography for non-destructive testing of
metal A metal (from ancient Greek, Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electrical resistivity and conductivity, e ...
s. Additionally, 192Ir is used as a source of gamma radiation for the treatment of cancer using
brachytherapy Brachytherapy is a form of radiation therapy where a sealed radiation source is placed inside or next to the area requiring treatment. ''Brachy'' is Greek for short. Brachytherapy is commonly used as an effective treatment for cervical, pro ...
, a form of radiotherapy where a sealed radioactive source is placed inside or next to the area requiring treatment. Specific treatments include high-dose-rate prostate brachytherapy, biliary duct brachytherapy, and intracavitary cervix brachytherapy. iridium-192 is normally produced by neutron activation of isotop iridium-191 in natural-abundance iridium metal


Photocatalysis and OLEDs

Iridium complexes are key components of white OLEDs. Similar complexes are used in
photocatalysis In chemistry, photocatalysis is the acceleration of a photoreaction in the presence of a catalyst. In catalyzed photolysis, light is absorbed by an adsorbed substrate. In photogenerated catalysis, the photocatalytic activity depends on the a ...
.


Scientific

An alloy of 90% platinum and 10% iridium was used in 1889 to construct the International Prototype Metre and kilogram mass, kept by the
International Bureau of Weights and Measures The International Bureau of Weights and Measures (french: Bureau international des poids et mesures, BIPM) is an intergovernmental organisation, through which its 59 member-states act together on measurement standards in four areas: chemistry ...
near
Paris Paris () is the capital and most populous city of France, with an estimated population of 2,165,423 residents in 2019 in an area of more than 105 km² (41 sq mi), making it the 30th most densely populated city in the world in 2020. Si ...
. The meter bar was replaced as the definition of the fundamental unit of length in 1960 by a line in the atomic spectrum of
krypton Krypton (from grc, κρυπτός, translit=kryptos 'the hidden one') is a chemical element with the symbol Kr and atomic number 36. It is a colorless, odorless, tasteless noble gas that occurs in trace amounts in the atmosphere and is of ...
, but the kilogram prototype remained the international standard of mass until 20 May 2019, when the kilogram was redefined in terms of the Planck constant.


Historical

Iridium–osmium alloys were used in
fountain pen A fountain pen is a writing instrument which uses a metal nib (pen), nib to apply a Fountain pen ink, water-based ink to paper. It is distinguished from earlier dip pens by using an internal reservoir to hold ink, eliminating the need to repeat ...
nib tips. The first major use of iridium was in 1834 in nibs mounted on gold. Since 1944, the famous Parker 51 fountain pen was fitted with a nib tipped by a ruthenium and iridium alloy (with 3.8% iridium). The tip material in modern fountain pens is still conventionally called "iridium", although there is seldom any iridium in it; other metals such as ruthenium, osmium, and tungsten have taken its place. An iridium–platinum alloy was used for the touch holes or vent pieces of
cannon A cannon is a large- caliber gun classified as a type of artillery, which usually launches a projectile using explosive chemical propellant. Gunpowder ("black powder") was the primary propellant before the invention of smokeless powder ...
. According to a report of the Paris Exhibition of 1867, one of the pieces being exhibited by Johnson and Matthey "has been used in a Whitworth gun for more than 3000 rounds, and scarcely shows signs of wear yet. Those who know the constant trouble and expense which are occasioned by the wearing of the vent-pieces of cannon when in active service, will appreciate this important adaptation". The pigment ''iridium black'', which consists of very finely divided iridium, is used for painting porcelain an intense black; it was said that "all other porcelain black colors appear grey by the side of it".


Precautions

Iridium in bulk metallic form is not biologically important or hazardous to health due to its lack of reactivity with tissues; there are only about 20  parts per trillion of iridium in human tissue. Like most metals, finely divided iridium powder can be hazardous to handle, as it is an irritant and may ignite in air. By 2015 very little is known about the toxicity of iridium compounds, primarily because it is used so rarely that few people come in contact with it and those who do only with very small amounts. However, soluble salts, such as the iridium halides, could be hazardous due to elements other than iridium or due to iridium itself. At the same time, most iridium compounds are insoluble, which makes absorption into the body difficult. A radioisotope of iridium, , is dangerous, like other radioactive isotopes. The only reported injuries related to iridium concern accidental exposure to radiation from used in
brachytherapy Brachytherapy is a form of radiation therapy where a sealed radiation source is placed inside or next to the area requiring treatment. ''Brachy'' is Greek for short. Brachytherapy is commonly used as an effective treatment for cervical, pro ...
. High-energy gamma radiation from can increase the risk of cancer. External exposure can cause burns, radiation poisoning, and death. Ingestion of 192Ir can burn the linings of the stomach and the intestines. 192Ir, 192mIr, and 194mIr tend to deposit in the
liver The liver is a major organ only found in vertebrates which performs many essential biological functions such as detoxification of the organism, and the synthesis of proteins and biochemicals necessary for digestion and growth. In humans, it i ...
, and can pose health hazards from both gamma and beta radiation.


Notes


References


External links


Iridium
at '' The Periodic Table of Videos'' (University of Nottingham)
Iridium in Encyclopædia Britannica
{{Authority control Chemical elements Transition metals Precious metals Noble metals Impact event minerals Meteorite minerals Native element minerals Chemical elements with face-centered cubic structure