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Iridium

Iridium is a chemical element; it has symbol Ir and atomic number 77. A very hard, brittle, silvery-white transition metal of the platinum group, it is considered the second-densest naturally occurring metal (after osmium) with a density of 22.56 g/cm3 (0.815 lb/cu in)[7] as defined by experimental X-ray crystallography.[a] 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,[10] even at temperatures as high as 2,000 °C (3,630 °F).

Iridium, 77Ir
Iridium
Pronunciation/ɪˈrɪdiəm/ (i-RID-ee-əm)
Appearancesilvery white
Standard atomic weight Ar°(Ir)
Iridium in the periodic table
Hydrogen Helium
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon
Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine Argon
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
Caesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury (element) Thallium Lead Bismuth Polonium Astatine Radon
Francium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson
Rh

Ir

Mt
osmiumiridiumplatinum
Atomic number (Z)77
Groupgroup 9
Periodperiod 6
Block  d-block
Electron configuration[Xe] 4f14 5d7 6s2
Electrons per shell2, 8, 18, 32, 15, 2
Physical properties
Phase at STPsolid
Melting point2719 K ​(2446 °C, ​4435 °F)
Boiling point4403 K ​(4130 °C, ​7466 °F)
Density (near r.t.)22.56 g/cm3
when liquid (at m.p.)19 g/cm3
Heat of fusion41.12 kJ/mol
Heat of vaporization564 kJ/mol
Molar heat capacity25.10 J/(mol·K)
Vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 2713 2957 3252 3614 4069 4659
Atomic properties
Oxidation states−3, –2, −1, 0, +1, +2, +3, +4, +5, +6, +7, +8, +9[3]
ElectronegativityPauling scale: 2.20
Ionization energies
  • 1st: 880 kJ/mol
  • 2nd: 1600 kJ/mol
Atomic radiusempirical: 136 pm
Covalent radius141±6 pm
Spectral lines of iridium
Other properties
Natural occurrenceprimordial
Crystal structureface-centered cubic (fcc)
Thermal expansion6.4 µm/(m⋅K)
Thermal conductivity147 W/(m⋅K)
Electrical resistivity47.1 nΩ⋅m (at 20 °C)
Magnetic orderingparamagnetic[4]
Molar magnetic susceptibility+25.6 × 10−6 cm3/mol (298 K)[5]
Young's modulus528 GPa
Shear modulus210 GPa
Bulk modulus320 GPa
Speed of sound thin rod4825 m/s (at 20 °C)
Poisson ratio0.26
Mohs hardness6.5
Vickers hardness1760–2200 MPa
Brinell hardness1670 MPa
CAS Number7439-88-5
History
Discovery and first isolationSmithson Tennant (1803)
Isotopes of iridium
Main isotopes[6] Decay
abun­dance half-life (t1/2) mode pro­duct
191Ir 37.3% stable
192Ir synth 73.827 d β 192Pt
ε 192Os
192m2Ir synth 241 y IT 192Ir
193Ir 62.7% stable
 Category: Iridium
| references

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 estimated annual production and consumption of only 7.3 tonnes (16 thousand pounds) in 2018.[11]

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.[12] For this reason, the unusually high abundance of iridium in the clay layer at the Cretaceous–Paleogene boundary gave rise to the Alvarez hypothesis 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 suggested the Eltanin impact of about 2.5 million years ago.[13]

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 edit

Physical properties edit

 
One troy ounce (31.1035 grams) of arc-melted iridium

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.[14] It is the only metal to maintain good mechanical properties in air at temperatures above 1,600 °C (2,910 °F).[15] It has the 10th highest boiling point among all elements and becomes a superconductor at temperatures below 0.14 K (−273.010 °C; −459.418 °F).[16]

Iridium's modulus of elasticity is the second-highest among the metals, being surpassed only by osmium.[15] 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 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.[15]

The measured density of iridium is only slightly lower (by about 0.12%) than that of osmium, the densest metal known.[17][18] 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,[19] but, with increased accuracy in factors used for calculating density, X-ray crystallographic data yielded densities of 22.56 g/cm3 (0.815 lb/cu in) for iridium and 22.59 g/cm3 (0.816 lb/cu in) for osmium.[20]

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).[21]

The Vickers hardness of pure platinum is 56 HV, whereas platinum with 50% of iridium can reach over 500 HV.[22][23]

Chemical properties edit

Iridium is the most corrosion-resistant metal known:[24] it is not attacked by acids, including aqua regia. In the presence of oxygen, it reacts with cyanide salts.[25] Traditional oxidants also react, including the halogens and oxygen[26] at higher temperatures.[27] Iridium also reacts directly with sulfur at atmospheric pressure to yield iridium disulfide.[28]

Isotopes edit

Iridium has two naturally occurring stable isotopes, 191Ir and 193Ir, with natural abundances of 37.3% and 62.7%, respectively.[29] 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 of 73.827 days, and finds application in brachytherapy[30] and in industrial radiography, 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.[29] 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. Synthetic isotopes heavier than 191 decay by β decay, although 192Ir also has a minor electron capture decay path.[29] All known isotopes of iridium were discovered between 1934 and 2008, with the most recent discoveries being 200–202Ir.[31]

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,[29] 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.[29] 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.[32]

Chemistry edit

Oxidation states[b]
−3 [Ir(CO)
3
]3−
−1 [Ir(CO)3(PPh3)]1−
0 Ir4(CO)12
+1 [IrCl(CO)(PPh3)2]
+2 Ir(C5H5)2
+3 IrCl3
+4 IrO2
+5 Ir4F20
+6 IrF
6
+7 [Ir(O2)O2]+
+8 IrO4
+9 [IrO4]+[3]

Oxidation states edit

Iridium forms compounds in oxidation states between −3 and +9, but the most common oxidation states are +1, +2, +3, and +4.[14] Well-characterized compounds containing iridium in the +6 oxidation state include IrF6 and the oxides Sr2MgIrO6 and Sr2CaIrO6.[14][33] iridium(VIII) oxide (IrO4) was generated under matrix isolation conditions at 6 K in argon.[34] The highest oxidation state (+9), which is also the highest recorded for any element, is found in gaseous [IrO4]+.[3]

Binary compounds edit

Iridium does not form binary hydrides. Only one binary oxide is well-characterized: iridium dioxide, IrO
2
. It is a blue black solid that adopts the fluorite structure.[14] A sesquioxide, Ir
2
O
3
, has been described as a blue-black powder, which is oxidized to IrO
2
by HNO
3
.[26] The corresponding disulfides, diselenides, sesquisulfides, and sesquiselenides are known, as well as IrS
3
.[14]

Binary trihalides, IrX
3
, are known for all of the halogens.[14] For oxidation states +4 and above, only the tetrafluoride, pentafluoride and hexafluoride are known.[14] Iridium hexafluoride, IrF
6
, is a volatile yellow solid, composed of octahedral molecules. It decomposes in water and is reduced to IrF
4
.[14] Iridium pentafluoride is also a strong oxidant, but it is a tetramer, Ir
4
F
20
, formed by four corner-sharing octahedra.[14]

Complexes edit

 
Hydrated iridium trichloride, a common salt of iridium.

Iridium has extensive coordination chemistry.

Iridium in its complexes is always low-spin. Ir(III) and Ir(IV) generally form octahedral complexes.[14] Polyhydride complexes are known for the +5 and +3 oxidation states.[35] One example is IrH5(PiPr3)2.[36] The ternary hydride Mg
6
Ir
2
H
11
is believed to contain both the IrH4−
5
and the 18-electron IrH5−
4
anion.[37]

Iridium also forms oxyanions with oxidation states +4 and +5. K
2
IrO
3
and KIrO
3
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.[38]

Just like many elements, iridium forms important chloride complexes. Hexachloroiridic (IV) acid, H
2
IrCl
6
, and its ammonium salt are the most common iridium compounds from both industrial and preparative perspectives.[39] 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 coatings. The IrCl2−
6
ion has an intense dark brown color, and can be readily reduced to the lighter-colored IrCl3−
6
and vice versa.[39] Iridium trichloride, IrCl
3
, which can be obtained in anhydrous form from direct oxidation of iridium powder by chlorine at 650 °C,[39] or in hydrated form by dissolving Ir
2
O
3
in hydrochloric acid, is often used as a starting material for the synthesis of other Ir(III) compounds.[14] Another compound used as a starting material is ammonium hexachloroiridate(III), (NH
4
)
3
IrCl
6
.[citation needed]

In the presence of air, iridium metal dissolves in molten alkali-metal cyanides to produce the Ir(CN)3−
6
(hexacyanoiridate) ion and upon oxidation produces the most stable oxide.[citation needed]

Organoiridium chemistry edit

 
Cyclooctadiene iridium chloride dimer is a common complex of Ir(I).

Organoiridium compounds contain iridium–carbon bonds. Early studies identified the very stable tetrairidium dodecacarbonyl, Ir
4
(CO)
12
.[14] In this compound, each of the iridium atoms is bonded to the other three, forming a tetrahedral cluster. The discovery of Vaska's complex (IrCl(CO)[P(C
6
H
5
)
3
]
2
) opened the door for oxidative addition reactions, a process fundamental to useful reactions. For example, Crabtree's catalyst, a homogeneous catalyst for hydrogenation reactions.[40][41]

 
Oxidative addition to hydrocarbons in organoiridium chemistry[42][43]

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.[44]

History edit

Platinum group edit

 
The Greek goddess Iris, after whom iridium was named.

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".[45] 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.[46]

 
This alchemical symbol for platinum was made by joining the symbols of silver (moon) and gold (sun).
 
Antonio de Ulloa 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. 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.[45]

In 1741, Charles Wood,[47] 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.[48] 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,[49] Torbern Bergman, Jöns Jakob Berzelius, William Lewis, and Pierre Macquer. 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. Scheffer described platinum as being less pliable than gold, but with similar resistance to corrosion.[45]

Discovery edit

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, insoluble residue.[15] Joseph Louis Proust thought that the residue was graphite.[15] 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.[15]

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[24] and obtained a volatile new oxide, which he believed to be of this new metal—which he named ptene, from the Greek word πτηνός ptēnós, "winged".[50][51] 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.[15][24] He obtained dark red crystals (probably of Na
2
[IrCl
6
nH
2
O
) by a sequence of reactions with sodium hydroxide and hydrochloric acid.[51] He named iridium after Iris (Ἶρις), the Greek winged goddess of the rainbow and the messenger of the Olympian gods, because many of the salts he obtained were strongly colored.[c][52] Discovery of the new elements was documented in a letter to the Royal Society on June 21, 1804.[15][53]

Metalworking and applications edit

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).[15] The first to obtain high-purity iridium was Robert Hare in 1842. He found it had a density of around 21.8 g/cm3 (0.79 lb/cu in) and noted the metal is nearly immalleable 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 litres (79 US gal) of pure O
2
and H
2
gas for each 1 kilogram (2.2 lb) of iridium.[15]

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 they had been using a similar process since 1837 and had already presented fused iridium at a number of World Fairs.[15] 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 2,000 °C (3,630 °F).[15]

In Munich, Germany in 1957 Rudolf Mössbauer, in what has been called one of the "landmark experiments in twentieth-century physics",[54] discovered the resonant and recoil-free emission and absorption of gamma rays by atoms in a solid metal sample containing only 191Ir.[55] 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.[56]

Occurrence edit

Along with all elements having atomic weights higher than that of iron, iridium is only naturally formed by the r-process (rapid neutron capture) in supernovae and neutron star mergers.[57][58]

 
Iridium is one of the least abundant elements in Earth's crust.
 
The Willamette Meteorite, the sixth-largest meteorite found in the world, has 4.7 ppm iridium.[59]

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 is 40 times more abundant, and silver and mercury are 80 times more abundant.[14] Tellurium is about as abundant as iridium.[14] In contrast to its low abundance in crustal rock, iridium is relatively common in meteorites, with concentrations of 0.5 ppm or more.[60] 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.[39]

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).[24] 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.[61] 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.[62][63][64] 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,[65] (near the largest known impact structure, the Vredefort impact structure) though the large copper–nickel deposits near Norilsk in Russia, and the Sudbury Basin (also an impact crater) in Canada are also significant sources of iridium. Smaller reserves are found in the United States.[65] 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, world reserves have not been estimated.[24]

Marine oceanography edit

Iridium is found within marine organisms, sediments, and the water column. The abundance of iridium in seawater[66] and organisms[67] is relatively low, as it does not readily form chloride complexes.[67] The abundance in organisms is about 20 parts per trillion, or about five orders of magnitude less than in sedimentary rocks at the Cretaceous–Paleogene (K–T) boundary.[67] The concentration of iridium in seawater and marine sediment is sensitive to marine oxygenation, seawater temperature, and various geological and biological processes.[68]

Iridium in sediments can come from cosmic dust, volcanoes, precipitation from seawater, microbial processes, or hydrothermal vents,[68] and its abundance can be strongly indicative of the source.[69][68] It tends to associate with other ferrous metals in manganese nodules.[66] 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.[70][71] For example, core samples from the Pacific Ocean with elevated iridium levels suggested the Eltanin impact of about 2.5 million years ago.[13]

Some of the mass extinctions, such as the Cretaceous extinction, can be identified by anomalously high concentrations of iridium in sediment, and these can be linked to major asteroid impacts.[72]

Cretaceous–Paleogene boundary presence edit

 
The red arrow points to the Cretaceous–Paleogene boundary.

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.[73] A team led by Luis Alvarez proposed in 1980 an extraterrestrial origin for this iridium, attributing it to an asteroid or comet impact.[73] 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).[74][75] 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.[76][77]

Production edit

Year Consumption
(tonnes)
Price (USD)[78]
2001 2.6 $415.25/ozt ($13.351/g)
2002 2.5 $294.62/ozt ($9.472/g)
2003 3.3 $93.02/ozt ($2.991/g)
2004 3.60 $185.33/ozt ($5.958/g)
2005 3.86 $169.51/ozt ($5.450/g)
2006 4.08 $349.45/ozt ($11.235/g)
2007 3.70 $444.43/ozt ($14.289/g)
2008 3.10 $448.34/ozt ($14.414/g)
2009 2.52 $420.4/ozt ($13.52/g)
2010 10.40 $642.15/ozt ($20.646/g)
2011 9.36 $1,035.87/ozt ($33.304/g)
2012 5.54 $1,066.23/ozt ($34.280/g)
2013 6.16 $826.45/ozt ($26.571/g)
2014 6.1 $556.19/ozt ($17.882/g)
2015 7.81 $544/ozt ($17.5/g)
2016 7.71 $586.90/ozt ($18.869/g)
2017 n.d. $908.35/ozt ($29.204/g)
2018 n.d. $1,293.27/ozt ($41.580/g)
2019 n.d. $1,485.80/ozt ($47.770/g)
2020 n.d. $1,633.51/ozt ($52.519/g)
2021 n.d. $5,400.00/ozt ($173.614/g)
2022 n.d. $3,980.00/ozt ($127.960/g)
2023 n.d. $4,652.38/ozt ($149.577/g)
2024 n.d. $5,000.00/ozt ($160.754/g)

Worldwide production of iridium was about 7,300 kilograms (16,100 lb) in 2018.[11] The price is high and varying (see table). Illustrative factors that affect the price include oversupply of Ir crucibles[78][79] and changes in LED technology.[80]

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.[81] 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.[39][65] From soluble extracts, iridium is separated by precipitating solid ammonium hexachloroiridate ((NH
4
)
2
IrCl
6
) or by extracting IrCl2−
6
with organic amines.[82] 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.[83][84] 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.[78]

Leading iridium-producing countries (kg)[85]
Country 2016 2017 2018 2019 2020
 World 7,720 7,180 7,540 7,910 8,170
  South Africa * 6,624 6,057 6,357 6,464 6,786
  Zimbabwe 598 619 586 845 836
  Canada * 300 200 400 300 300
  Russia * 200 300 200 300 250

Applications edit

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.[81]

Ir metal and alloys edit

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, 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.[86][87] 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 2,100 °C (3,810 °F).[15]

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.[24] Iridium is used for multi-pored spinnerets, through which a plastic polymer melt is extruded to form fibers, such as rayon.[88] Osmium–iridium is used for compass bearings and for balances.[15]

Because of their resistance to arc erosion, iridium alloys are used by some manufacturers for the centre electrodes of spark plugs,[86][89] and iridium-based spark plugs are particularly used in aviation.

Catalysis edit

Iridium compounds are used as catalysts in the Cativa process for carbonylation of methanol to produce acetic acid.[90][91]

Iridium complexes are often active for asymmetric hydrogenation both by traditional hydrogenation.[92] and transfer hydrogenation.[93] 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.[94]

Medical imaging edit

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.[95][96] Additionally, 192
Ir
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.[24] Iridium-192 is normally produced by neutron activation of isotope iridium-191 in natural-abundance iridium metal.[97]

Photocatalysis and OLEDs edit

Iridium complexes are key components of white OLEDs. Similar complexes are used in photocatalysis.[98]

Scientific edit

 
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.[24] 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,[d][99] 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.[100]

Historical edit

 
Fountain pen nib labelled Iridium Point

Iridium–osmium alloys were used in fountain pen nib tips. The first major use of iridium was in 1834 in nibs mounted on gold.[15] 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.[101]

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".[102]

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".[103]

Precautions edit

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.[24] Like most metals, finely divided iridium powder can be hazardous to handle, as it is an irritant and may ignite in air.[65] By 2015 very little is known about the toxicity of iridium compounds,[104] 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.[30] At the same time, most iridium compounds are insoluble, which makes absorption into the body difficult.[24]

A radioisotope of iridium, 192
Ir
, is dangerous, like other radioactive isotopes. The only reported injuries related to iridium concern accidental exposure to radiation from 192
Ir
used in brachytherapy.[30] High-energy gamma radiation from 192
Ir
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.[105] 192Ir, 192mIr, and 194mIr tend to deposit in the liver, and can pose health hazards from both gamma and beta radiation.[60]

Notes edit

  1. ^ At room temperature and standard atmospheric pressure, iridium has been calculated to have a density of 22.65 g/cm3 (0.818 lb/cu in), 0.04 g/cm3 (0.0014 lb/cu in) higher than osmium measured the same way.[8] Still, the experimental X-ray crystallography value is considered to be the most accurate, and as such iridium is considered to be the second densest element.[9]
  2. ^ Most common oxidation states of iridium are in bold. The right column lists one representative compound for each oxidation state.
  3. ^ Iridium literally means "of rainbows".
  4. ^ The definition of the meter was changed again in 1983. The meter is currently defined as the distance traveled by light in a vacuum during a time interval of 1299,792,458 of a second.

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External links edit

iridium, confused, with, indium, this, article, about, chemical, element, other, uses, disambiguation, chemical, element, symbol, atomic, number, very, hard, brittle, silvery, white, transition, metal, platinum, group, considered, second, densest, naturally, o. Not to be confused with Indium This article is about the chemical element For other uses see Iridium disambiguation Iridium is a chemical element it has symbol Ir and atomic number 77 A very hard brittle silvery white transition metal of the platinum group it is considered the second densest naturally occurring metal after osmium with a density of 22 56 g cm3 0 815 lb cu in 7 as defined by experimental X ray crystallography a 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 10 even at temperatures as high as 2 000 C 3 630 F Iridium 77IrIridiumPronunciation ɪ ˈ r ɪ d i e m wbr i RID ee em Appearancesilvery whiteStandard atomic weight Ar Ir 192 217 0 002 1 192 22 0 01 abridged 2 Iridium in the periodic tableHydrogen HeliumLithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine NeonSodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine ArgonPotassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine KryptonRubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine XenonCaesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury element Thallium Lead Bismuth Polonium Astatine RadonFrancium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson Rh Ir Mtosmium iridium platinumAtomic number Z 77Groupgroup 9Periodperiod 6Block d blockElectron configuration Xe 4f14 5d7 6s2Electrons per shell2 8 18 32 15 2Physical propertiesPhase at STPsolidMelting point2719 K 2446 C 4435 F Boiling point4403 K 4130 C 7466 F Density near r t 22 56 g cm3when liquid at m p 19 g cm3Heat of fusion41 12 kJ molHeat of vaporization564 kJ molMolar heat capacity25 10 J mol K Vapor pressureP Pa 1 10 100 1 k 10 k 100 kat T K 2713 2957 3252 3614 4069 4659Atomic propertiesOxidation states 3 2 1 0 1 2 3 4 5 6 7 8 9 3 ElectronegativityPauling scale 2 20Ionization energies1st 880 kJ mol2nd 1600 kJ molAtomic radiusempirical 136 pmCovalent radius141 6 pmSpectral lines of iridiumOther propertiesNatural occurrenceprimordialCrystal structure face centered cubic fcc Thermal expansion6 4 µm m K Thermal conductivity147 W m K Electrical resistivity47 1 nW m at 20 C Magnetic orderingparamagnetic 4 Molar magnetic susceptibility 25 6 10 6 cm3 mol 298 K 5 Young s modulus528 GPaShear modulus210 GPaBulk modulus320 GPaSpeed of sound thin rod4825 m s at 20 C Poisson ratio0 26Mohs hardness6 5Vickers hardness1760 2200 MPaBrinell hardness1670 MPaCAS Number7439 88 5HistoryDiscovery and first isolationSmithson Tennant 1803 Isotopes of iridiumveMain isotopes 6 Decayabun dance half life t1 2 mode pro duct191Ir 37 3 stable192Ir synth 73 827 d b 192Pte 192Os192m2Ir synth 241 y IT 192Ir193Ir 62 7 stable Category Iridiumviewtalkedit referencesIridium 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 estimated annual production and consumption of only 7 3 tonnes 16 thousand pounds in 2018 11 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 12 For this reason the unusually high abundance of iridium in the clay layer at the Cretaceous Paleogene boundary gave rise to the Alvarez hypothesis 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 suggested the Eltanin impact of about 2 5 million years ago 13 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 Contents 1 Characteristics 1 1 Physical properties 1 2 Chemical properties 1 3 Isotopes 2 Chemistry 2 1 Oxidation states 2 2 Binary compounds 2 3 Complexes 2 4 Organoiridium chemistry 3 History 3 1 Platinum group 3 2 Discovery 3 3 Metalworking and applications 4 Occurrence 4 1 Marine oceanography 4 2 Cretaceous Paleogene boundary presence 5 Production 6 Applications 6 1 Ir metal and alloys 6 2 Catalysis 6 3 Medical imaging 6 4 Photocatalysis and OLEDs 6 5 Scientific 6 6 Historical 7 Precautions 8 Notes 9 References 10 External linksCharacteristics editPhysical properties edit nbsp One troy ounce 31 1035 grams of arc melted iridiumA 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 14 It is the only metal to maintain good mechanical properties in air at temperatures above 1 600 C 2 910 F 15 It has the 10th highest boiling point among all elements and becomes a superconductor at temperatures below 0 14 K 273 010 C 459 418 F 16 Iridium s modulus of elasticity is the second highest among the metals being surpassed only by osmium 15 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 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 15 The measured density of iridium is only slightly lower by about 0 12 than that of osmium the densest metal known 17 18 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 19 but with increased accuracy in factors used for calculating density X ray crystallographic data yielded densities of 22 56 g cm3 0 815 lb cu in for iridium and 22 59 g cm3 0 816 lb cu in for osmium 20 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 21 The Vickers hardness of pure platinum is 56 HV whereas platinum with 50 of iridium can reach over 500 HV 22 23 Chemical properties edit Iridium is the most corrosion resistant metal known 24 it is not attacked by acids including aqua regia In the presence of oxygen it reacts with cyanide salts 25 Traditional oxidants also react including the halogens and oxygen 26 at higher temperatures 27 Iridium also reacts directly with sulfur at atmospheric pressure to yield iridium disulfide 28 Isotopes edit 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 29 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 of 73 827 days and finds application in brachytherapy 30 and in industrial radiography 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 29 Isotopes with masses below 191 decay by some combination of b decay a decay and rare proton emission with the exception of 189Ir which decays by electron capture Synthetic isotopes heavier than 191 decay by b decay although 192Ir also has a minor electron capture decay path 29 All known isotopes of iridium were discovered between 1934 and 2008 with the most recent discoveries being 200 202Ir 31 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 29 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 ms 29 The isotope 191Ir was the first one of any element to be shown to present a Mossbauer effect This renders it useful for Mossbauer spectroscopy for research in physics chemistry biochemistry metallurgy and mineralogy 32 Chemistry editSee also Category Iridium compounds Oxidation states b 3 Ir CO 3 3 1 Ir CO 3 PPh3 1 0 Ir4 CO 12 1 IrCl CO PPh3 2 2 Ir C5H5 2 3 IrCl3 4 IrO2 5 Ir4F20 6 IrF6 7 Ir O2 O2 8 IrO4 9 IrO4 3 Oxidation states edit Iridium forms compounds in oxidation states between 3 and 9 but the most common oxidation states are 1 2 3 and 4 14 Well characterized compounds containing iridium in the 6 oxidation state include IrF6 and the oxides Sr2MgIrO6 and Sr2CaIrO6 14 33 iridium VIII oxide IrO4 was generated under matrix isolation conditions at 6 K in argon 34 The highest oxidation state 9 which is also the highest recorded for any element is found in gaseous IrO4 3 Binary compounds edit Iridium does not form binary hydrides Only one binary oxide is well characterized iridium dioxide IrO2 It is a blue black solid that adopts the fluorite structure 14 A sesquioxide Ir2 O3 has been described as a blue black powder which is oxidized to IrO2 by HNO3 26 The corresponding disulfides diselenides sesquisulfides and sesquiselenides are known as well as IrS3 14 Binary trihalides IrX3 are known for all of the halogens 14 For oxidation states 4 and above only the tetrafluoride pentafluoride and hexafluoride are known 14 Iridium hexafluoride IrF6 is a volatile yellow solid composed of octahedral molecules It decomposes in water and is reduced to IrF4 14 Iridium pentafluoride is also a strong oxidant but it is a tetramer Ir4 F20 formed by four corner sharing octahedra 14 Complexes edit nbsp Hydrated iridium trichloride a common salt of iridium Iridium has extensive coordination chemistry Iridium in its complexes is always low spin Ir III and Ir IV generally form octahedral complexes 14 Polyhydride complexes are known for the 5 and 3 oxidation states 35 One example is IrH5 PiPr3 2 36 The ternary hydride Mg6 Ir2 H11 is believed to contain both the IrH4 5 and the 18 electron IrH5 4 anion 37 Iridium also forms oxyanions with oxidation states 4 and 5 K2 IrO3 and KIrO3 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 38 Just like many elements iridium forms important chloride complexes Hexachloroiridic IV acid H2 IrCl6 and its ammonium salt are the most common iridium compounds from both industrial and preparative perspectives 39 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 coatings The IrCl2 6 ion has an intense dark brown color and can be readily reduced to the lighter colored IrCl3 6 and vice versa 39 Iridium trichloride IrCl3 which can be obtained in anhydrous form from direct oxidation of iridium powder by chlorine at 650 C 39 or in hydrated form by dissolving Ir2 O3 in hydrochloric acid is often used as a starting material for the synthesis of other Ir III compounds 14 Another compound used as a starting material is ammonium hexachloroiridate III NH4 3 IrCl6 citation needed In the presence of air iridium metal dissolves in molten alkali metal cyanides to produce the Ir CN 3 6 hexacyanoiridate ion and upon oxidation produces the most stable oxide citation needed Organoiridium chemistry edit nbsp Cyclooctadiene iridium chloride dimer is a common complex of Ir I Organoiridium compounds contain iridium carbon bonds Early studies identified the very stable tetrairidium dodecacarbonyl Ir4 CO 12 14 In this compound each of the iridium atoms is bonded to the other three forming a tetrahedral cluster The discovery of Vaska s complex IrCl CO P C6 H5 3 2 opened the door for oxidative addition reactions a process fundamental to useful reactions For example Crabtree s catalyst a homogeneous catalyst for hydrogenation reactions 40 41 nbsp Oxidative addition to hydrocarbons in organoiridium chemistry 42 43 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 44 History editPlatinum group edit nbsp The Greek goddess Iris after whom iridium was named 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 Darien and Mexico which no fire nor any Spanish artifice has yet been able to liquefy 45 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 46 nbsp This alchemical symbol for platinum was made by joining the symbols of silver moon and gold sun nbsp Antonio de Ulloa 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 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 45 In 1741 Charles Wood 47 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 48 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 49 Torbern Bergman Jons Jakob Berzelius William Lewis and Pierre Macquer 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 Scheffer described platinum as being less pliable than gold but with similar resistance to corrosion 45 Discovery edit 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 insoluble residue 15 Joseph Louis Proust thought that the residue was graphite 15 The French chemists Victor Collet Descotils Antoine Francois comte de Fourcroy and Louis Nicolas Vauquelin also observed the black residue in 1803 but did not obtain enough for further experiments 15 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 24 and obtained a volatile new oxide which he believed to be of this new metal which he named ptene from the Greek word pthnos ptenos winged 50 51 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 15 24 He obtained dark red crystals probably of Na2 IrCl6 nH2 O by a sequence of reactions with sodium hydroxide and hydrochloric acid 51 He named iridium after Iris Ἶris the Greek winged goddess of the rainbow and the messenger of the Olympian gods because many of the salts he obtained were strongly colored c 52 Discovery of the new elements was documented in a letter to the Royal Society on June 21 1804 15 53 Metalworking and applications edit 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 15 The first to obtain high purity iridium was Robert Hare in 1842 He found it had a density of around 21 8 g cm3 0 79 lb cu in and noted the metal is nearly immalleable 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 litres 79 US gal of pure O2 and H2 gas for each 1 kilogram 2 2 lb of iridium 15 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 they had been using a similar process since 1837 and had already presented fused iridium at a number of World Fairs 15 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 2 000 C 3 630 F 15 In Munich Germany in 1957 Rudolf Mossbauer in what has been called one of the landmark experiments in twentieth century physics 54 discovered the resonant and recoil free emission and absorption of gamma rays by atoms in a solid metal sample containing only 191Ir 55 This phenomenon known as the Mossbauer 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 56 Occurrence editAlong with all elements having atomic weights higher than that of iron iridium is only naturally formed by the r process rapid neutron capture in supernovae and neutron star mergers 57 58 nbsp Iridium is one of the least abundant elements in Earth s crust nbsp The Willamette Meteorite the sixth largest meteorite found in the world has 4 7 ppm iridium 59 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 is 40 times more abundant and silver and mercury are 80 times more abundant 14 Tellurium is about as abundant as iridium 14 In contrast to its low abundance in crustal rock iridium is relatively common in meteorites with concentrations of 0 5 ppm or more 60 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 39 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 24 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 61 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 62 63 64 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 65 near the largest known impact structure the Vredefort impact structure though the large copper nickel deposits near Norilsk in Russia and the Sudbury Basin also an impact crater in Canada are also significant sources of iridium Smaller reserves are found in the United States 65 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 Choco Department of Colombia are still a source for platinum group metals As of 2003 world reserves have not been estimated 24 Marine oceanography edit Iridium is found within marine organisms sediments and the water column The abundance of iridium in seawater 66 and organisms 67 is relatively low as it does not readily form chloride complexes 67 The abundance in organisms is about 20 parts per trillion or about five orders of magnitude less than in sedimentary rocks at the Cretaceous Paleogene K T boundary 67 The concentration of iridium in seawater and marine sediment is sensitive to marine oxygenation seawater temperature and various geological and biological processes 68 Iridium in sediments can come from cosmic dust volcanoes precipitation from seawater microbial processes or hydrothermal vents 68 and its abundance can be strongly indicative of the source 69 68 It tends to associate with other ferrous metals in manganese nodules 66 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 70 71 For example core samples from the Pacific Ocean with elevated iridium levels suggested the Eltanin impact of about 2 5 million years ago 13 Some of the mass extinctions such as the Cretaceous extinction can be identified by anomalously high concentrations of iridium in sediment and these can be linked to major asteroid impacts 72 Cretaceous Paleogene boundary presence edit nbsp The red arrow points to the Cretaceous Paleogene boundary Main article Cretaceous Paleogene extinction event 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 73 A team led by Luis Alvarez proposed in 1980 an extraterrestrial origin for this iridium attributing it to an asteroid or comet impact 73 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 Yucatan Peninsula the Chicxulub crater 74 75 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 Reunion are still releasing iridium 76 77 Production editYear Consumption tonnes Price USD 78 2001 2 6 415 25 ozt 13 351 g 2002 2 5 294 62 ozt 9 472 g 2003 3 3 93 02 ozt 2 991 g 2004 3 60 185 33 ozt 5 958 g 2005 3 86 169 51 ozt 5 450 g 2006 4 08 349 45 ozt 11 235 g 2007 3 70 444 43 ozt 14 289 g 2008 3 10 448 34 ozt 14 414 g 2009 2 52 420 4 ozt 13 52 g 2010 10 40 642 15 ozt 20 646 g 2011 9 36 1 035 87 ozt 33 304 g 2012 5 54 1 066 23 ozt 34 280 g 2013 6 16 826 45 ozt 26 571 g 2014 6 1 556 19 ozt 17 882 g 2015 7 81 544 ozt 17 5 g 2016 7 71 586 90 ozt 18 869 g 2017 n d 908 35 ozt 29 204 g 2018 n d 1 293 27 ozt 41 580 g 2019 n d 1 485 80 ozt 47 770 g 2020 n d 1 633 51 ozt 52 519 g 2021 n d 5 400 00 ozt 173 614 g 2022 n d 3 980 00 ozt 127 960 g 2023 n d 4 652 38 ozt 149 577 g 2024 n d 5 000 00 ozt 160 754 g Worldwide production of iridium was about 7 300 kilograms 16 100 lb in 2018 11 The price is high and varying see table Illustrative factors that affect the price include oversupply of Ir crucibles 78 79 and changes in LED technology 80 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 81 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 39 65 From soluble extracts iridium is separated by precipitating solid ammonium hexachloroiridate NH4 2 IrCl6 or by extracting IrCl2 6 with organic amines 82 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 83 84 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 78 Leading iridium producing countries kg 85 Country 2016 2017 2018 2019 2020 World 7 720 7 180 7 540 7 910 8 170 nbsp South Africa 6 624 6 057 6 357 6 464 6 786 nbsp Zimbabwe 598 619 586 845 836 nbsp Canada 300 200 400 300 300 nbsp Russia 200 300 200 300 250Applications editDue 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 81 Ir metal and alloys edit 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 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 86 87 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 2 100 C 3 810 F 15 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 24 Iridium is used for multi pored spinnerets through which a plastic polymer melt is extruded to form fibers such as rayon 88 Osmium iridium is used for compass bearings and for balances 15 Because of their resistance to arc erosion iridium alloys are used by some manufacturers for the centre electrodes of spark plugs 86 89 and iridium based spark plugs are particularly used in aviation Catalysis edit Iridium compounds are used as catalysts in the Cativa process for carbonylation of methanol to produce acetic acid 90 91 Iridium complexes are often active for asymmetric hydrogenation both by traditional hydrogenation 92 and transfer hydrogenation 93 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 94 Medical imaging edit The radioisotope iridium 192 is one of the two most important sources of energy for use in industrial g radiography for non destructive testing of metals 95 96 Additionally 192 Ir 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 24 Iridium 192 is normally produced by neutron activation of isotope iridium 191 in natural abundance iridium metal 97 Photocatalysis and OLEDs edit Iridium complexes are key components of white OLEDs Similar complexes are used in photocatalysis 98 Scientific edit nbsp International Prototype Meter barAn 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 24 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 d 99 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 100 Historical edit nbsp Fountain pen nib labelled Iridium PointIridium osmium alloys were used in fountain pen nib tips The first major use of iridium was in 1834 in nibs mounted on gold 15 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 101 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 102 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 103 Precautions editThis section needs to be updated Please help update this article to reflect recent events or newly available information January 2023 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 24 Like most metals finely divided iridium powder can be hazardous to handle as it is an irritant and may ignite in air 65 By 2015 very little is known about the toxicity of iridium compounds 104 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 30 At the same time most iridium compounds are insoluble which makes absorption into the body difficult 24 A radioisotope of iridium 192 Ir is dangerous like other radioactive isotopes The only reported injuries related to iridium concern accidental exposure to radiation from 192 Ir used in brachytherapy 30 High energy gamma radiation from 192 Ir 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 105 192Ir 192mIr and 194mIr tend to deposit in the liver and can pose health hazards from both gamma and beta radiation 60 Notes edit At room temperature and standard atmospheric pressure iridium has been calculated to have a density of 22 65 g cm3 0 818 lb cu in 0 04 g cm3 0 0014 lb cu in higher than osmium measured the same way 8 Still the experimental X ray crystallography value is considered to be the most accurate and as such iridium is considered to be the second densest element 9 Most common oxidation states of iridium are in bold The right column lists one representative compound for each oxidation state Iridium literally means of rainbows The definition of the meter was changed again in 1983 The meter is currently defined as the distance traveled by light in a vacuum during a time interval of 1 299 792 458 of a second References edit Standard Atomic Weights Iridium CIAAW 2017 Prohaska Thomas Irrgeher Johanna Benefield Jacqueline Bohlke John K Chesson Lesley A Coplen Tyler B Ding Tiping Dunn Philip J H Groning Manfred Holden Norman E Meijer Harro A J 2022 05 04 Standard atomic weights of the elements 2021 IUPAC Technical Report Pure and Applied Chemistry doi 10 1515 pac 2019 0603 ISSN 1365 3075 a b c Wang Guanjun Zhou Mingfei Goettel James T Schrobilgen Gary G Su Jing Li Jun Schloder Tobias Riedel Sebastian 2014 Identification of an iridium containing compound with a formal oxidation state of IX Nature 514 7523 475 477 Bibcode 2014Natur 514 475W doi 10 1038 nature13795 PMID 25341786 S2CID 4463905 Lide D R ed 2005 Magnetic susceptibility of the elements and inorganic compounds CRC Handbook of Chemistry and Physics PDF 86th ed Boca Raton FL CRC Press ISBN 0 8493 0486 5 Weast Robert 1984 CRC Handbook of Chemistry and Physics Boca Raton Florida Chemical Rubber Company Publishing pp E110 ISBN 0 8493 0464 4 Kondev F G Wang M Huang W J Naimi S Audi G 2021 The NUBASE2020 evaluation of nuclear 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their discoveries Platinum Metals Review 48 4 182 189 doi 10 1595 147106704x4844 Weeks M E 1968 Discovery of the Elements 7th ed Journal of Chemical Education pp 414 418 ISBN 978 0 8486 8579 9 OCLC 23991202 Tennant S 1804 On Two Metals Found in the Black Powder Remaining after the Solution of Platina Philosophical Transactions of the Royal Society of London 94 411 418 doi 10 1098 rstl 1804 0018 JSTOR 107152 Trigg G L 1995 Recoilless Emission and Absorption of Radiation Landmark Experiments in Twentieth Century Physics Courier Dover Publications pp 179 190 ISBN 978 0 486 28526 9 OCLC 31409781 Mossbauer R L 1958 Gammastrahlung in Ir191 Zeitschrift fur Physik A in German 151 2 124 143 Bibcode 1958ZPhy 151 124M doi 10 1007 BF01344210 S2CID 121129342 Waller I 1964 The Nobel Prize in Physics 1961 presentation speech Nobel Lectures Physics 1942 1962 Elsevier History Origin of Chemicals NASA Retrieved 1 January 2013 Chen Hsin Yu Vitale Salvatore Foucart Francois 2021 10 01 The Relative 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elements as geochemical markers in sedimentary environments Palaeogeography Palaeoclimatology Palaeoecology 104 4 253 270 Bibcode 1993PPP 104 253S doi 10 1016 0031 0182 93 90136 7 Crocket Macdougall Harriss R 1973 Gold palladium and iridium in marine sediments Geochimica et Cosmochimica Acta 37 12 2547 2556 Bibcode 1973GeCoA 37 2547C doi 10 1016 0016 7037 73 90264 0 Peucker Ehrenbrink B 2001 Iridium and Osmium as Tracers of Extraterrestrial Matter in Marine Sediments Accretion of Extraterrestrial Matter Throughout Earth s History pp 163 178 doi 10 1007 978 1 4419 8694 8 10 ISBN 978 1 4613 4668 5 Barker J Edward A 1968 Accretion rate of cosmic matter from iridium and osmium contents of deep sea sediments Geochimica et Cosmochimica Acta 32 6 627 645 Bibcode 1968GeCoA 32 627B doi 10 1016 0016 7037 68 90053 7 Colodner D Edmond J 1992 Post depositional mobility of platinum iridium and rhenium in marine sediments Nature 358 6385 402 404 Bibcode 1992Natur 358 402C doi 10 1038 358402a0 S2CID 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Fournaise Indian Ocean Geophysical Research Letters 16 12 1391 1394 Bibcode 1989GeoRL 16 1391T doi 10 1029 GL016i012p01391 a b c Platinum Group Metals U S Geological Survey Mineral Commodity Summaries Hageluken C 2006 Markets for the catalysts metals platinum palladium and rhodium PDF Metall 60 1 2 31 42 Archived from the original PDF on March 4 2009 Platinum 2013 Interim Review PDF Platinum Today Johnson Matthey Retrieved 2014 01 10 a b Ryan Marge 2022 11 16 Recycling and thrifting the answer to the iridium question in electrolyser growth Gilchrist Raleigh 1943 The Platinum Metals Chemical Reviews 32 3 277 372 doi 10 1021 cr60103a002 S2CID 96640406 Ohriner E K 2008 Processing of Iridium and Iridium Alloys Platinum Metals Review 52 3 186 197 doi 10 1595 147106708X333827 Hunt L B Lever F M 1969 Platinum Metals A Survey of Productive Resources to industrial Uses PDF Platinum Metals Review 13 4 126 138 doi 10 1595 003214069X134126138 S2CID 267561907 Archived from the original PDF on 2008 10 29 Retrieved 2008 10 01 Mineral Yearbook 2020 tables only release USGS a b Handley J R 1986 Increasing Applications for Iridium Platinum Metals Review 30 1 12 13 doi 10 1595 003214086X3011213 Crookes W 1908 On the Use of Iridium Crucibles in Chemical Operations Proceedings of the Royal Society of London Series A Containing Papers of a Mathematical and Physical Character 80 541 535 536 Bibcode 1908RSPSA 80 535C doi 10 1098 rspa 1908 0046 JSTOR 93031 Egorova R V Korotkov B V Yaroshchuk E G Mirkus K A Dorofeev N A Serkov A T 1979 Spinnerets for viscose rayon cord yarn Fibre Chemistry 10 4 377 378 doi 10 1007 BF00543390 S2CID 135705244 Graff Muriel Kempf Bernd Breme Jurgen 2005 12 23 Iridium Alloy for Spark Plug Electrodes Materials for Transportation Technology Weinheim FRG Wiley VCH Verlag GmbH amp Co KGaA pp 1 8 doi 10 1002 3527606025 ch1 ISBN 9783527301249 Cheung H Tanke R S Torrence G P 2000 Acetic acid Ullmann s Encyclopedia of Industrial Chemistry Wiley doi 10 1002 14356007 a01 045 ISBN 978 3527306732 Jones Jane H 2000 The cativa process for the manufacture of acetic acid Platinum Metals Review 44 3 94 105 doi 10 1595 003214000X44394105 Roseblade S J Pfaltz A 2007 Iridium catalyzed asymmetric hydrogenation of olefins Accounts of Chemical Research 40 12 1402 1411 doi 10 1021 ar700113g PMID 17672517 Ikariya Takao Blacker A John 2007 Asymmetric Transfer Hydrogenation of Ketones with Bifunctional Transition Metal Based Molecular Catalysts Accounts of Chemical Research 40 12 1300 1308 doi 10 1021 ar700134q PMID 17960897 Matthias Beller Hans Ulrich Blaser ed 2012 Organometallics as Catalysts in the Fine Chemical Industry Topics in Organometallic Chemistry Vol 42 Berlin Heidelberg Springer ISBN 978 3 642 32832 9 Halmshaw R 1954 The use and scope of Iridium 192 for the radiography of steel British Journal of Applied Physics 5 7 238 243 Bibcode 1954BJAP 5 238H doi 10 1088 0508 3443 5 7 302 Hellier Chuck 2001 Handbook of Nondestructive Evlaluation The McGraw Hill Companies ISBN 978 0 07 028121 9 Jean Pouliot Luc Beaulieu 2010 13 Modern Principles of Brachytherapy Physics From 2 D to 3 D to Dynamic Planning and Delivery In Richard T Hoppe Theodore Locke Phillips Mack Roach eds Leibel and Phillips Textbook of Radiation Oncology 3rd ed W B Saunders pp 224 244 doi 10 1016 B978 1 4160 5897 7 00013 5 ISBN 9781416058977 Ulbricht Christoph Beyer Beatrice Friebe Christian Winter Andreas Schubert Ulrich S 2009 Recent Developments in the Application of Phosphorescent Iridium III Complex Systems Advanced Materials 21 44 4418 4441 Bibcode 2009AdM 21 4418U doi 10 1002 adma 200803537 S2CID 96268110 Penzes W B 2001 Time Line for the Definition of the Meter National Institute for Standards and Technology Retrieved 2008 09 16 General section citations Recalibration of the U S National Prototype Kilogram R S Davis Journal of Research of the National Bureau of Standards 90 No 4 July August 1985 5 5 MB PDF Archived 2017 02 01 at the Wayback Machine and The Kilogram and Measurements of Mass and Force Z J Jabbour et al J Res Natl Inst Stand Technol 106 2001 25 46 3 5 MB PDF Mottishaw J 1999 Notes from the Nib Works Where s the Iridium The PENnant XIII 2 Crookes W ed 1867 The Paris Exhibition The Chemical News and Journal of Physical Science XV 182 Pepper J H 1861 The Playbook of Metals Including Personal Narratives of Visits to Coal Lead Copper and Tin Mines with a Large Number of Interesting Experiments Relating to Alchemy and the Chemistry of the Fifty Metallic Elements Routledge Warne and Routledge p 455 Iavicoli Ivo Leso Veruscka 2015 Iridium Handbook on the Toxicology of Metals pp 855 878 doi 10 1016 B978 0 444 59453 2 00040 8 ISBN 9780444594532 Radioisotope Brief Iridium 192 Ir 192 PDF Radiation Emergencies Centers for Disease Control and Prevention 2004 08 18 Retrieved 2008 09 20 External links edit nbsp Wikimedia Commons has media related to Iridium nbsp Look up iridium in Wiktionary the free dictionary Iridium at The Periodic Table of Videos University of Nottingham Iridium in Encyclopaedia Britannica Retrieved from https en wikipedia org w index php title Iridium amp oldid 1211882099, wikipedia, wiki, book, books, library,

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