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Iridium

Iridium is a chemical element; it has the symbol Ir and atomic number 77. This very hard, brittle, silvery-white transition metal of the platinum group is considered the second-densest naturally occurring metal, with a density of 22.56 g/cm3 (0.815 lb/cu in) as defined by experimental X-ray crystallography. 191Ir and 193Ir are the only two naturally occurring isotopes of iridium, as well as the only stable isotopes; the latter is the more abundant. It is one of the most corrosion-resistant metals, even at temperatures as high as 2,000 °C (3,630 °F).

Characteristics
Physical properties A member of the platinum group metals, iridium is white, resembling platinum, but with a slight yellowish cast. Because of its hardness, brittleness, and very high melting point, solid iridium is difficult to machine, form, or work; thus powder metallurgy is commonly employed instead. 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, surpassed only by osmium. 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 and zirconium (0.2% of each apparently works well). The Vickers hardness of pure platinum is 56 HV, whereas an alloy of 50% platinum and iridium can reach over 500 HV. Chemical properties Iridium is the most corrosion-resistant metal known. 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 isotopes, 191Ir and 193Ir, with natural abundances of 37.3% and 62.7%, respectively. At least 32 metastable isomers 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, == Chemistry ==
Chemistry
Oxidation states Iridium forms compounds in oxidation states between −3 and +9, but the most common oxidation states are +1, +2, +3, and +4. Iridium(VIII) oxide () was generated under matrix isolation conditions at 6 K in argon. The highest oxidation state (+9), which is also the highest recorded for any element, is found in gaseous . Only one binary oxide is well-characterized: iridium dioxide, . It is a blue-black solid that adopts the fluorite structure. One example is (iPr = isopropyl). The ternary hydride is believed to contain both the and the 18-electron anion. Iridium also forms oxyanions with oxidation states +4 and +5. and can be prepared from the reaction of potassium oxide or potassium superoxide with iridium at high temperatures. Such solids are not soluble in conventional solvents. Just like many elements, iridium forms important chloride complexes. Hexachloroiridic (IV) acid, , and its ammonium salt are common iridium compounds from both industrial and preparative perspectives. Organoiridium chemistry is a common complex of Ir(I). Organoiridium compounds contain iridium–carbon bonds. Early studies identified the very stable tetrairidium dodecacarbonyl, . |alt=Skeletal formula presentation of a chemical transformation. The initial compounds have a C5H5 ring on their top and an iridium atom in the center, which is bonded to two hydrogen atoms and a P–PH3 group or to two C–O groups. Reaction with alkane under UV light alters those groups. 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 ==
History
Platinum group , after whom iridium was named.|alt=Photo of part of a black vase with brown picture on it: A woman with wings on her back hold an arrow with right hand and gives a jar to a man. A small deer is standing in front of the woman. 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. for platinum was made by joining the symbols of silver (moon) and gold (sun). is credited in European history with the discovery of platinum. In 1735, Antonio de Ulloa and Jorge Juan y Santacilia 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. 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. a British metallurgist, 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 refractory metal-like behaviour toward borax. Other chemists across Europe soon began studying platinum, including Andreas Sigismund Marggraf, Torbern Bergman, Jöns Jakob Berzelius, William Lewis, and by South American cultures 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. 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 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). discovered the resonant and recoil-free emission and absorption of gamma rays by atoms in a solid metal sample containing only 191Ir. This phenomenon, known as the Mössbauer effect resulted in the awarding of the Nobel Prize in Physics in 1961, at the age 32, just three years after he published his discovery. == Occurrence ==
Occurrence
Along with many elements having atomic weights higher than that of iron, iridium is only naturally formed by the r-process (rapid neutron capture) in neutron star mergers and possibly rare types of supernovae. has 4.7 ppm iridium.|alt=A large black egg-shaped boulder of porous structure standing on its top, tilted 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; gold is 4 times more abundant, platinum is 10 times more abundant, silver and mercury are 80 times more abundant. In contrast to its low abundance in crustal rock, iridium is relatively common in meteorites, with concentrations of 0.5 ppm or more. Iridium is found in nature as an uncombined element or in natural alloys, especially the iridium–osmium alloys osmiridium (osmium-rich) and iridosmium (iridium-rich). In nickel and copper deposits, the platinum group metals occur as sulfides, tellurides, antimonides, and arsenides. In all of these compounds, platinum can be exchanged with a small amount of iridium or 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, and organisms is relatively low, as it does not readily form chloride complexes. Iridium in sediments can come from cosmic dust, volcanoes, precipitation from seawater, microbial processes, or hydrothermal vents, For example, core samples from the Pacific Ocean with elevated iridium levels suggested the Eltanin impact of about 2.5 million years ago. Cretaceous–Paleogene boundary presence .|alt=A cliff with pronounced layered structure: yellow, gray, white, gray. A red arrow points between the yellow and gray layers. The Cretaceous–Paleogene boundary of 66 million years ago, marking the temporal border between the Cretaceous and Paleogene periods of geological time, was identified by a thin stratum of iridium-rich clay. Their theory, known as the Alvarez hypothesis, 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 origin instead, because Earth's core is rich in iridium, and active volcanoes such as Piton de la Fournaise, in the island of Réunion, are still releasing iridium. == Production ==
Production
Worldwide production of iridium was about in 2018. The price is high and varying (see table). Iridium reached a high of US$8000 (per troy ounce) in March 2026 (which is also the record high for iridium when adjusted for inflation). 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. Two methods for rendering Ir-containing ores soluble are (i) fusion of the solid with sodium peroxide followed by extraction of the resulting glass in aqua regia and (ii) extraction of the solid with a mixture of chlorine with hydrochloric acid. 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 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, which is amenable to powder metallurgy techniques. Iridium is also obtained commercially as a by-product from nickel and copper mining and processing. During electrorefining of copper and nickel, noble metals such as silver, gold and the platinum group metals 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 ==
Applications
Due to iridium's resistance to corrosion, it has industrial applications. The main areas of use are electrodes for producing chlorine and other corrosive products, OLEDs, crucibles, catalysts (e.g. acetic acid), and ignition tips for spark plugs. 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 . Osmium–iridium is used for compass bearings and for balances. and iridium-based spark plugs are particularly used in aviation. Catalysis Iridium compounds are used as catalysts in the Cativa process for carbonylation of methanol to produce acetic acid. Iridium complexes are often active for asymmetric hydrogenation both by traditional hydrogenation. 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)Cl]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 γ-radiography for non-destructive testing of metals. Additionally, is used as a source of gamma radiation for the treatment of cancer using brachytherapy, 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. Photocatalysis and OLEDs Iridium complexes are key components of white OLEDs. Similar complexes are used in photocatalysis. Scientific bar|alt=NIST Library US Prototype meter bar An alloy of 90% platinum and 10% iridium was used in 1889 to construct the International Prototype Meter and kilogram mass, kept by the International Bureau of Weights and Measures near Paris. 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 nib labelled Iridium Point Iridium–osmium alloys were previously used in fountain pen nib tips. The first major use of iridium was in 1834 in nibs mounted on gold. An iridium–platinum alloy was used for the touch holes or vent pieces of cannon. 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 and hazards ==
Precautions and hazards
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. Iridium is relatively non-hazardous otherwise, with the only effect of Iridium ingestion being irritation of the digestive tract. However, soluble salts, such as the iridium halides, could be hazardous due to elements other than iridium or due to iridium itself. 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, and can pose health hazards from both gamma and beta radiation. == Notes ==
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