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Iridium

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Iridium (pronounced /ɨˈrɪdɨəm/ ) ɨs the chemɨcal element wɨth atomɨc number 77, and ɨs represented by the symbol Ir. A very hard, brɨttle, sɨlvery-whɨte transɨtɨon metal of the platɨnum famɨly , ɨrɨdɨum ɨs the second densest element (after osmɨum ) and ɨs the most corrosɨon -resɨstant metal, even at temperatures as hɨgh as 2000 °C. Although only certaɨn molten salts and halogens are corrosɨve to solɨd ɨrɨdɨum, fɨnely dɨvɨded ɨrɨdɨum dust ɨs much more reactɨve and can even be ɨnflammable. The most ɨmportant ɨrɨdɨum compounds ɨn terms of use are the salts and acɨds ɨt forms wɨth chlorɨne , though ɨrɨdɨum also forms a number of organometallɨc compounds used ɨn catalysɨs and ɨn research. 191 Ir and 193 Ir are the only two naturally occurrɨng ɨsotopes of ɨrɨdɨum as well as the only stable ɨsotopes ; the latter ɨs the more abundant of the two. Irɨdɨum was dɨscovered ɨn 1803 by Smɨthson Tennant ɨn London, England, among ɨnsoluble ɨmpurɨtɨes ɨn natural platɨnum from South Amerɨca . Although ɨt ɨs one of the rarest elements ɨn the Earth's crust , wɨth annual productɨon and consumptɨon of only three tonnes , ɨt has a number of specɨalɨzed ɨndustrɨal and scɨentɨfɨc applɨcatɨons. Irɨdɨum ɨs employed when hɨgh corrosɨon resɨstance and hɨgh temperatures are needed, as ɨn spark plugs , crucɨbles for recrystallɨzatɨon of semɨconductors at hɨgh temperatures, electrodes for the productɨon of chlorɨne ɨn the chloralkalɨ process , and radɨoɨsotope thermoelectrɨc generators used ɨn unmanned spacecraft . Irɨdɨum compounds also fɨnd applɨcatɨons as catalysts for the productɨon of acetɨc acɨd . An unusually hɨgh abundance of ɨrɨdɨum ɨn a clay layer of the K–T geologɨc boundary was a crucɨal clue that led to the theory that the extɨnctɨon of dɨnosaurs and many other specɨes 65 mɨllɨon years ago was caused by the ɨmpact of a massɨve extraterrestrɨal object—the so-called Alvarez hypothesɨs . Irɨdɨum ɨs found ɨn meteorɨtes wɨth an abundance much hɨgher than ɨts average abundance ɨn the Earth's crust. It ɨs thought that the amount of ɨrɨdɨum ɨn the planet Earth ɨs much hɨgher than what ɨs observed ɨn crustal rocks, but
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Page 1: Iridium

Iridium (pronounced /ɨˈrɪdiəm/) is the chemical element with atomic number 77, and is represented by the symbol Ir. A very hard, brittle, silvery-white transition metal of the platinum family, iridium is the second densest element (after osmium) and is the most corrosion-resistant metal, even at temperatures as high as 2000 °C. Although only certain molten salts and halogens are corrosive to solid iridium, finely divided iridium dust is much more reactive and can even be inflammable. The most important iridium compounds in terms of use are the salts and acids it forms with chlorine, though iridium also forms a number of organometallic compounds used in catalysis and in research. 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 of the two.

Iridium was discovered in 1803 by Smithson Tennant in London, England, among insoluble impurities in natural platinum from South America. Although it is one of the rarest elements in the Earth's crust, with annual production and consumption of only three tonnes, it has a number of specialized industrial and scientific applications. Iridium is employed when high corrosion resistance and high temperatures are needed, as in spark plugs, crucibles for recrystallization of semiconductors at high temperatures, electrodes for the production of chlorine in the chloralkali process, and radioisotope thermoelectric generators used in unmanned spacecraft. Iridium compounds also find applications as catalysts for the production of acetic acid.

An unusually high abundance of iridium in a clay layer of the K–T geologic boundary was a crucial clue that led to the theory that the extinction of dinosaurs and many other species 65 million years ago was caused by the impact of a massive extraterrestrial object—the so-called Alvarez hypothesis. Iridium is found in meteorites with an abundance much higher than its average abundance in the Earth's crust. It is thought that the amount of iridium in the planet Earth is much higher than what is observed in crustal rocks, but because of the high density and tendency of iridium to bond with iron, most iridium descended below the crust and into the Earth's core when the planet was young and still molten.

Characteristics

Physical

1 troy ounce (31 g) of arc-melted iridium

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A member of the platinum group metals, iridium is white, resembling platinum, but with a slight yellowish cast. Due to its hardness, brittleness, and very high melting point (the tenth highest of all elements), solid iridium is difficult to machine, form, or work, and thus powder metallurgy is commonly employed instead.[2] It is the only metal to maintain good mechanical properties in air at temperatures above 1600 °C.[3] Iridium has a very high boiling point (11th among all elements) and becomes a superconductor under 0.14 K.[4]

Iridium's modulus of elasticity is the second highest among the metals, only being surpassed by osmium.[3] This, together with a high modulus of rigidity and a very low figure for Poisson's ratio (the relationship of longitudinal to lateral strain), indicate the high degree of stiffness 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.[3]

The measured density of iridium is only slightly lower (by about 0.1%) than that of osmium, the densest element known.[5][6] There had been some ambiguity regarding which of the two element was denser, due to the small size of the difference in density and difficulties in measuring it accurately,[7] but, with increased accuracy in factors used for calculating density X-ray crystallographic data yielded densities of 22.56 g/cm3 for iridium and 22.59 g/cm3 for osmium.[8]

Chemical

Iridium is the most corrosion-resistant metal known:[9] it is not attacked by any acid, by aqua regia, by any molten metals, or by silicates at high temperatures. It can, however, be attacked by some molten salts, such as sodium cyanide and potassium cyanide,[9] as well as oxygen and the halogens (particularly fluorine)[10] at higher temperatures.[11]

Compounds

Oxidation statesof iridium[note 1]

−3 [Ir(CO)3]3−

−1 [Ir(CO)3(PPh3)]−

0 Ir4(CO)12

+1 [Ir(CO)Cl(PPh3)2]+2 IrCl2

+3 IrCl3

+4 IrO2

+5 Ir4F20

+6 IrF6

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Iridium forms compounds in oxidation states between −3 to +6; the most common oxidation states are +3 and +4.[2] Well-characterized examples of the highest oxidation state are rare, but include IrF6 and two mixed oxides Sr2MgIrO6 and Sr2CaIrO6.[2][12]

Iridium dioxide, IrO2, a brown powder, is the only well-characterized oxide of iridium.[2] A sesquioxide, Ir2O3, has been described as a blue-black powder which is oxidized to IrO2

by HNO3.[10] The corresponding disulfides, diselenides, sesquisulfides and sesquiselenides are known and IrS3 has also been reported.[2] Iridium also forms iridates with oxidation states +4 and +5, such as K2IrO3 and KIrO3, which can be prepared from the reaction of potassium oxide or potassium superoxide with iridium at high temperatures.[13]

While no binary hydrides of iridium, IrxHy are known, complexes are known that contain IrH5

4− and IrH63−, where iridium has the +1 and +3 oxidation states, respectively.[14] The

ternary hydride Mg6Ir2H11 is believed to contain both the IrH54− and the 18-electron IrH4

5− anion.[15]

No monohalides or dihalides are known, whereas trihalides, IrX3, are known for all of the halogens.[2] For oxidation states +4 and above, only the tetrafluoride, pentafluoride and hexafluoride are known.[2] Iridium hexafluoride, IrF6, is a volatile and highly reactive yellow solid, composed of octahedral molecules. It decomposes in water and is reduced to IrF4, a crystalline solid, by iridium black.[2] Iridium pentafluoride has similar properties but it is actually a tetramer, Ir4F20, formed by four corner-sharing octahedra.[2]

Vaska's complex

Hexachloroiridic(IV) acid, H2IrCl6, and its ammonium salt are the most important iridium compounds from an industrial perspective.[16] They are involved in the purification of iridium and used as precursors for most other iridium compounds, as well as in the preparation of anode coatings. The [IrCl6]2− ion has an intense dark brown color, and can be readily reduced to the lighter-colored [IrCl6]3− and vice versa.[16] Iridium trichloride, IrCl3, which can be obtained in anhydrous form from direct oxidation of iridium powder by chlorine at 650 °C,[16] or in hydrated form by dissolving Ir2O3 in hydrochloric acid, is often used as a starting material for the synthesis of other Ir(III) compounds.[2] Another compound used as a starting material is ammonium hexachloroiridate(III), (NH4)3IrCl6. Iridium(III) complexes are diamagnetic (low-spin) and generally have an octahedral molecular geometry.[2]

Organoiridium compounds contain iridium–carbon bonds where the metal is usually in lower oxidation states. For example, oxidation state zero is found in tetrairidium dodecacarbonyl, Ir4(CO)12, which is the most common and stable binary carbonyl of

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iridium.[2] In this compound, each of the iridium atoms is bonded to the other three, forming a tetrahedral cluster. Some organometallic Ir(I) compounds are notable enough to be named after their discoverers. One is Vaska's complex, IrCl(CO)[P(C6H5)3]2, which has the unusual property of binding to the dioxygen molecule, O2.[17] Another one is Crabtree's catalyst, a homogeneous catalyst for hydrogenation reactions.[18] These compounds are both square planar, d8 complexes, with a total of 16 valence electrons, which accounts for their reactivity.[19]

Isotopes

Main article: Isotopes of iridium

Iridium has two naturally occurring, stable isotopes, 191Ir and 193Ir, with natural abundances of 37.3% and 62.7%, respectively.[20] At least 34 radioisotopes have also been synthesized, ranging in mass number from 164 to 199. Twenty-seven of these are lighter than the stable isotopes, while six are heavier. 192 Ir , which falls between the two stable isotopes, is the most stable radioisotope, with a half-life of 73.827 days, and finds application in brachytherapy.[21] Three other isotopes have half-lives of at least a day—188Ir, 189Ir, 190Ir.[20] One of the least stable isotopes is 165Ir with a half-life of 1 µs. Isotopes with masses below 191 decay by some combination of β + decay , α decay, and proton emission, with the exceptions of 189Ir, which decays by electron capture, and 190Ir, which decays by positron emission. Synthetic isotopes heavier than 191 decay by β − decay , although 192Ir also has a minor electron capture decay path.[20] All known isotopes of iridium were discovered between 1934 and 2001; the most recent is 171Ir.[22]

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,[20] 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.[20] The isotope 191Ir was the first one of any element to be shown to present a Mössbauer effect. This renders it useful for Mössbauer spectroscopy for research in physics, chemistry, biochemistry, metallurgy, and mineralogy.[23]

History

The discovery of iridium is intertwined with that of platinum and the other metals of the platinum group. Native platinum used by ancient Ethiopians[24] and by South American cultures[25] always contained a small amount of the other platinum group metals, including iridium. Platinum reached Europe as platina ("small silver"), found in the 17th century by the Spanish conquerors in a region today known as the department of Chocó in Colombia.[26] The discovery that this metal was not an alloy of known elements, but instead a distinct new element, did not occur until 1748.[27]

Chemists who studied platinum dissolved it in aqua regia (a mixture of hydrochloric and nitric acids) to create soluble salts. They always observed a small amount of a dark,

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insoluble residue.[3] Joseph Louis Proust thought that the residue was graphite.[3] The French chemists Victor Collet-Descotils, Antoine François, comte de Fourcroy, and Louis Nicolas Vauquelin also observed the black residue in 1803, but did not obtain enough for further experiments.[3]

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 alternatively with alkali and acids[9] and obtained a volatile new oxide, which he believed to be of this new metal—which he named ptene, from the Greek word πτηνος (ptènos) for winged.[28][29] 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.[3][9] He obtained dark red crystals (probably of Na2[IrCl6]·nH2O) by a sequence of reactions with sodium hydroxide and hydrochloric acid.[29] He named iridium after Iris (Ιρις), the Greek winged goddess of the rainbow and the messenger of the Olympian gods, because many of the salts he obtained were strongly colored.[note 2][30] Discovery of the new elements was documented in a letter to the Royal Society on June 21, 1804.[3][31]

The Greek goddess Iris, after whom Iridium was named.

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).[3] The first to obtain high purity iridium was Robert Hare in 1842. He found that it had a density of around 21.8 g/cm3 and noted that the metal is nearly unmalleable and very hard. The first melting in appreciable quantity was done by Henri Sainte-Claire Deville and Jules Henri Debray in 1860. They required burning more than 300 L of pure O2 and H2 for each kilogram of iridium.[3]

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 and patented the process in the United States; British company Johnson Matthey later stated that they had been using a similar process since 1837 and had already presented fused

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iridium at a number of World Fairs.[3] 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 2000 °C.[3]

In 1957 Rudolf Mössbauer, in what has been called one of the "landmark experiments in twentieth century physics",[32] discovered the resonant and recoil-free emission and absorption of gamma rays by atoms in a solid metal sample containing only 191Ir.[33] This phenomenon, known as the Mössbauer effect (which has since been observed for other nuclei, such as 57 Fe ), and developed as Mössbauer spectroscopy, has made important contributions to research in physics, chemistry, biochemistry, metallurgy, and mineralogy.[23] Mössbauer received the Nobel Prize in Physics in 1961, just three years after he published his discovery.[34]

Occurrence

The Willamette Meteorite, the sixth largest meteorite found in the world, has 4.7 ppm iridium.[35]

Iridium is one of the least abundant elements in the 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, and silver and mercury are 80 times more abundant.[2] Tellurium is about as abundant as iridium, and only three naturally occurring elements are less abundant: rhenium, ruthenium, and rhodium, iridium being 10 times more abundant than the last two.[2] In contrast to its low abundance in crustal rock, iridium is relatively common in meteorites, with concentrations of 0.5 ppm or more.[36] It is thought that the overall concentration of iridium on Earth is 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 the Earth's core when the planet was still molten.[16]

Iridium is found in nature as an uncombined element or in natural alloys; especially the iridium–osmium alloys, osmiridium (osmium rich), and iridiosmium (iridium rich).[9] In the nickel and copper deposits the platinum group metals occur as sulfides (i.e.

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(Pt,Pd)S)), tellurides (i.e. PtBiTe), antimonides (PdSb), and arsenides (i.e. PtAs2). 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.[37]

Within the 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,[38] though the large copper–nickel deposits near Norilsk in Russia, and the Sudbury Basin in Canada are also significant sources of iridium. Smaller reserves are found in the United States.[38] 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 people in the Chocó Department of Colombia are still a source for platinum-group metals. As of 2003 the world reserves had not been estimated.[9]

K–T boundary presence

The red arrow points to the K–T boundary.Main article: Cretaceous–Tertiary extinction event

The K–T boundary of 65 million years ago, marking the temporal border between the Cretaceous and Tertiary periods of geological time, was identified by a thin stratum of iridium-rich clay.[39] A team led by Luis Alvarez proposed in 1980 an extraterrestrial origin for this iridium, attributing it to an asteroid or comet impact.[39] Their theory, known as the Alvarez hypothesis, is now widely accepted to explain the demise of the dinosaurs. A large buried impact crater structure with an estimated age of about 65 million years was later identified under what is now the Yucatán Peninsula (the Chicxulub crater).[40][41] Dewey M. McLean and others argue that the iridium may have been of volcanic origin instead, as the 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.[42][43]

Production

YearPrice

($/ozt)[44][45]

2001 415.252002 294.62

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2003 93.022004 185.332005 169.512006 349.452007 440.00

Iridium is 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.[44][46] In order to separate the metals, they must first be brought into solution. Several methods are available depending on the separation process and the composition of the mixture; two representative methods are fusion with sodium peroxide followed by dissolution in aqua regia, and dissolution in a mixture of chlorine with hydrochloric acid.[16][38]

After it is dissolved, iridium is separated from the other platinum group metals by precipitating (NH4)2IrCl6 or by extracting [IrCl6]2− with organic amines.[47] The first method is similar to the procedure Tennant and Wollastone used for their 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 is reduced using hydrogen, yielding the metal as a powder or sponge that can be treated using powder metallurgy techniques.[48][49]

Annual production of iridium circa 2000 was around 3 tonnes or about 100,000 troy ounces (ozt).[note 3][9] The price of iridium as of 2007 was $440 USD/ozt,[44] but the price fluctuates considerably, as shown in the table. The high volatility of the prices of the platinum group metals has been attributed to supply, demand, speculation, and hoarding, amplified by the small size of the market and instability in the producing countries.[50]

Applications

The global demand for iridium in 2007 was 119,000 troy ounces (3,700 kg), out of which 25,000 ozt (780 kg) were used for electrical applications such as spark plugs; 34,000 ozt (1,100 kg) for electrochemical applications such as electrodes for the chloralkali process; 24,000 ozt (750 kg) for catalysis; and 36,000 ozt (1,100 kg) for other uses.[51]

Industrial and medical

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Molecular structure of Ir(mppy)3

The high melting point, hardness and corrosion resistance of iridium and its alloys determine most of its applications. Iridium and especially iridium–platinum alloys or osmium–iridium alloys have a low wear and are used, for example, for multi-pored spinnerets, through which a plastic polymer melt is extruded to form fibers, such as rayon.[52] Osmium–iridium is used for compass bearings and for balances.[9]

Corrosion and heat resistance makes iridium an important alloying agent. Certain long-life aircraft engine parts are made of an iridium alloy and an iridium–titanium alloy is used for deep-water pipes because of its corrosion resistance.[9] Iridium is also used as a hardening agent in platinum alloys. The Vickers hardness of pure platinum is 56 HV while platinum with 50% of iridium can reach over 500 HV.[53][54]

Devices that must withstand extremely high temperatures are often made from iridium. For example, high-temperature crucibles made of iridium 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.[55][56] 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 2100 °C.[3] Its resistance to arc erosion makes iridium alloys ideal for electrical contacts for spark plugs.[56][57]

Iridium compounds are used as catalysts in the Cativa process for carbonylation of methanol to produce acetic acid.[58] Iridium itself is used as a catalyst in a type of automobile engine introduced in 1996 called the direct-ignition engine.[9]

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.[59][60] Additionally, 192Ir 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, bilary duct brachytherapy, and intracavitary cervix brachytherapy.[9]

Scientific

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International 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.[9] 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,[note 4][61] but the kilogram prototype is still the international standard of mass.[62]

Iridium has been used in the radioisotope thermoelectric generators of unmanned spacecraft such as the Voyager, Viking, Pioneer, Cassini, Galileo, and New Horizons. Iridium was chosen to encapsulate the plutonium-238 fuel in the generator because it can withstand the operating temperatures of up to 2000 °C and for its great strength.[3]

Another use concerns X-ray optics, especially X-ray telescopes.[63] The mirrors of the Chandra X-ray Observatory are coated with a layer of iridium 60 nm thick. Iridium proved to be the best choice for reflecting X-rays after nickel, gold, and platinum were tested. The iridium layer, which had to be smooth to within a few atoms, was applied by depositing iridium vapor under high vacuum on a base layer of chromium.[64]

Iridium is used in particle physics for the production of antiprotons, a form of antimatter. Antiprotons are made by shooting a high-intensity proton beam at a conversion target, which needs to be made from a very high density material. Although tungsten may be used instead, iridium has the advantage of better stability under the shock waves induced by the temperature rise due to the incident beam.[65]

Oxidative addition to hydrocarbons in organoiridium chemistry.[66][67]

Carbon–hydrogen bond activation (C–H activation) is an area of research on reactions that cleave carbon–hydrogen bonds, which were traditionally regarded as unreactive. The first reported successes at activating C–H bonds in saturated hydrocarbons, published in 1982, used organometallic iridium complexes that undergo an oxidative addition with the hydrocarbon.[66][67]

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Iridium complexes are being investigated as catalysts for asymmetric hydrogenation. These catalysts have been used in the synthesis of natural products and able to hydrogenate certain difficult substrates, such as unfunctionalized alkenes, enantioselectively (generating only one of the two possible enantiomers).[68][69]

Iridium forms a variety of complexes of fundamental interest in triplet harvesting.[70][71][72]

Historical

Fountain pen nib labeled Iridium Point

Iridium–osmium alloys were used to tip fountain pen nibs. The first major use of iridium was in 1834 in nibs mounted on gold.[3] 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 tungsten have taken its place.[73]

An iridium–platinum alloy was used for the touch holes or vent pieces of cannons. 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 Withworth 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".[74]

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".[75]

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.[9] However, finely divided iridium powder can be hazardous to handle, as it is an irritant and may ignite in air.[38] Very little is known about the toxicity of iridium compounds because they are used in very small amounts, but soluble salts, such as the iridium halides, could be hazardous due to elements other than iridium or due to iridium itself.[21] However, most iridium compounds are insoluble, which makes absorption into the body difficult.[9]

A radioisotope of iridium, 192Ir, is dangerous like other radioactive isotopes. The only reported injuries related to iridium concern accidental exposure to radiation from 192Ir

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used in brachytherapy.[21] High-energy gamma radiation from 192Ir 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.[76] 192Ir, 192mIr, and 194mIr tend to deposit in the liver, and can pose health hazards from both gamma and beta radiation.[

77 osmium ← iridium → platinumRh↑Ir↓

Mt Periodic Table - Extended Periodic TableGeneral Name, Symbol, Number iridium, Ir, 77 Element category transition metals Group, Period, Block 9, 6, d Appearance silvery white

Standard atomic weight 192.217 (3)  g·mol−1 Electron configuration [Xe] 4f14 5d7 6s2 Electrons per shell 2, 8, 18, 32, 15, 2 Physical properties Phase solid Density (near r.t.) 22.56  g·cm−3 Liquid density at m.p. 19  g·cm−3 Melting point 2739 K(2466 °C, 4471 °F) Boiling point 4701 K(4428 °C, 8002 °F) Heat of fusion 41.12  kJ·mol −1 Heat of vaporization 563  kJ·mol −1 Specific heat capacity (25 °C) 25.10  J·mol−1·K−1

Vapor pressure

P(Pa) 1 10 100 1 k 10 k 100 k

at T(K) 2713 2957 3252 3614 4069 4659

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Atomic properties Crystal structure face centered cubic Oxidation states −3,−1, 0, 1, 2, 3, 4, 5, 6 Electronegativity 2.20 (Pauling scale) Ionization energies 1st: 880 kJ/mol 2nd: 1600 kJ/mol Atomic radius 136  pm Covalent radius 141±6  pm Miscellaneous Magnetic ordering paramagnetic [1] Electrical resistivity (20 °C) 47.1 n Ω·m Thermal conductivity (300 K) 147  W·m−1·K−1 Thermal expansion (25 °C) 6.4  µm·m−1·K−1 Speed of sound (thin rod) (20 °C) 4825 m/s Young's modulus 528  GPa Shear modulus 210  GPa Bulk modulus 320  GPa Poisson ratio 0.26 Mohs hardness 6.5 Vickers hardness 1760  MPa Brinell hardness 1670  MPa CAS registry number 7439-88-5 Most-stable isotopes

Main article: Isotopes of iridium

iso NA half-life DM DE (MeV) DP188Ir syn 1.73 d ε 1.64 188Os189Ir syn 13.2 d ε 0.532 189Os190Ir syn 11.8 d ε 2.000 190Os191Ir 37.3% 191Ir is stable with 114 neutrons

192Ir syn 73.827 dβ - 1.460 192Pt

ε 1.046 192Os192m2Ir syn 241 y IT 0.161 192Ir193Ir 62.7% 193Ir is stable with 116 neutrons193mIr syn 10.5 d IT 0.080 193Ir194Ir syn 19.3 h β - 2.247 194Pt194m2Ir syn 171 d IT  ? 194Ir

A chemical element, Ir, atomic number 77, relative atomic weight 192.22. Iridium is a transition metal and shares similarities with rhodium as well as the other platinum metals, including palladium, platinum, ruthenium, and osmium. The atom in the gas phase has the electronic configuration 1s2, 2s2, 2p6, 3s2, 3p6, 3d10, 4s2, 4p6 4d10, 4f14, 5s2, 5p6, 5d7, 6s2.

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The ionic radius for Ir3+ is 0.068 nanometer and its metallic radius is 0.1357 nm. Metallic iridium is slightly less dense than osmium, which is the densest of all the elements. See also Periodic table.

The abundance of iridium in the Earth's crust is very low, 0.001 ppm. For mining purposes, it is generally found alloyed with osmium in materials known as osmiridium and iridiosmium, with iridium contents ranging from 25 to 75%.

Solid iridium is a silvery metal with considerable resistance to chemical attack. Upon atmospheric exposure the surface of the metal is covered with a relatively thick layer of iridium dioxide (IrO2). Important physical properties of metallic iridium are given in the table.

Physical properties of iridium metal

Property Value

Crystal structure Face-centered cubic

Lattice constant a at 25°C, nm 0.38394

Thermal neutron capture cross section, barns 440

Density at 25°C, g/cm3 22.560

Melting point 2443°C (4429°F)

Boiling point 4500°C (8130°F)

Specific heat at 0°C, cal/g 0.0307

Thermal conductivity 0–100°C, cal cm/cm2 s °C 0.35

Linear coefficient of thermal expansion 20–100°C, μin./in./°C 6.8

Electrical resistivity at 0°C, microhm-cm 4.71

Temperature coefficient of electrical resistance 0–100°C/°C 0.00427

Tensile strength (1000 lb/in.2)

 Soft 160–180

 Hard 300–360

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Young's modulus at 20°C

 lb/in.2, static 75.0 × 106

 lb/in.2, dynamic 76.5 × 106

Hardness, diamond pyramid number

 Soft 200–240

 Hard 600–700

ΔHfusion, kJ/mol 26.4

ΔHvaporization, kJ/mol 612

ΔHf monoatomic gas, kJ/mol 669

Electronegativity 2.2

Because of its scarcity and high cost, applications of iridium are severely limited. Although iridium metal and many of its complex compounds are good catalysts, no large-scale commercial application for these has been developed. In general, other platinum metals have superior catalytic properties. The high degree of thermal stability of elemental iridium and the stability it imparts to its alloys does give rise to those applications where it has found success. Particularly relevant are its high melting point (2443°C or 4429°F), its oxidation resistance, and the fact that it is the only metal with good mechanical properties that survives atmospheric exposure above 1600°C (2910°F). Iridium is alloyed with platinum to increase tensile strength, hardness, and corrosion resistance. However, the workability of these alloys is decreased. These alloys find use as electrodes for anodic oxidation, for containing and manipulating corrosive chemicals, for electrical contacts that are exposed to corrosive chemicals, and as primary standards for weight and length. Platinum-iridium alloys are used for electrodes in spark plugs that are unusually resistant to fouling by antiknock lead additives. Iridium-rhodium thermocouples are used for high-temperature applications, where they have unique stability. Very pure iridium crucibles are used for growing single crystals of gadolinium gallium garnet for computer memory devices and of yttrium aluminum garnet for solid-state lasers. The radioactive isotope, 192Ir, which is obtained synthetically from 191Ir by irradiation of natural sources, has been used as a portable gamma source for radiographic studies in industry and medicine. See also Platinum.


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