Tag Archives: Iridium
Iridium was discovered in 1803 among insoluble impurities in natural platinum. Smithson Tennant, the primary discoverer, named the iridium for 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 the Earth’s crust, with annual production and consumption of only three tonnes. 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.
The most important iridium compounds in use are the salts and acids it forms with chlorine, though iridium also forms a number of organometallic compounds used in industrial catalysis, and in research. Iridium metal is employed when high corrosion resistance at high temperatures is needed, as in high-end spark plugs, crucibles for recrystallization of semiconductors at high temperatures, and electrodes for the production of chlorine in the chloralkali process. Iridium radioisotopes are used in some radioisotope thermoelectric generators.
Iridium‘s modulus of elasticity is the second-highest among the metals, only being surpassed by osmium. This, together with a high shear modulus and a very low figure for Poisson’s ratio, 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.
Iridium is the most corrosion-resistant metal known: it isn’t attacked by almost any acid, aqua regia, molten metals or silicates at high temperatures. It can, however, be attacked by some molten salts, such as sodium cyanide and potassium cyanide, as well as oxygen and the halogens at higher temperatures.
Iridium forms compounds in oxidation states between −3 to +6; the most common oxidation states are +3 and +4. Well-characterized examples of the highest oxidation state are rare, but include IrF6 and two mixed oxides Sr2MgIrO6 and Sr2CaIrO6. In addition, it was reported in 2009 that iridium oxide (IrO4) was prepared under matrix isolation conditions (6 K in Ar) by UV irradiation of an iridium-peroxo complex. This species, however, isn’t expected to be stable as a bulk solid at higher temperatures.
While no binary hydrides of iridium, IrxHy are known, complexes are known that contain IrH4−5 and IrH3−6, where iridium has the +1 and +3 oxidation states, respectively. The ternary hydride Mg6Ir2H11 is believed to contain both the IrH4−5 and the 18-electron IrH5−4 anion.
No monohalides or dihalides are known, whereas trihalides, IrX3, are known for all of the halogens. For oxidation states +4 and above, only the tetrafluoride, pentafluoride and hexafluoride are known. 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. Iridium pentafluoride has similar properties but it is actually a tetramer, Ir4F20, formed by four corner-sharing octahedra.
The discovery of iridium is intertwined with that of platinum and the other metals of the platinum group. Native platinum used by ancient Ethiopians and by South American cultures always contained a small amount of the other platinum group metals, including iridium. Platinum reached Europe as platina, found in the 17th century by the Spanish conquerors in a region today known as the department of Chocx in Colombia. The discovery that the metal wasn’t an alloy of known elements, but instead a distinct new element, didn’t occur until 1748.
Chemists who studied platinum dissolved it in aqua regia to create soluble salts. They always observed a small amount of a dark, insoluble residue. Joseph Louis Proust thought that the residue was graphite. The French chemists Victor Collet-Descotils, Antoine Franxois, comte de Fourcroy, and Louis Nicolas Vauquelin also observed the black residue in 1803, but didn’t obtain enough for further experiments.
In 1803, British scientist Smithson Tennant analyzed the insoluble residue and concluded that it must contain a new metal. Vauquelin treated the powder alternately with alkali and acids and obtained a volatile new oxide, which he believed to be of this new metal—which he named ptene, from the Greek word πτηνός ptēnxs, “winged”. Tennant, who had the advantage of a much greater amount of residue, continued his research and identified the two previously undiscovered elements in the black residue, iridium and osmium. He obtained dark red crystals (probably of Na2[IrCl6]xnH2O) by a sequence of reactions with sodium hydroxide and hydrochloric acid. 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.[note 2] Discovery of the new elements was documented in a letter to the Royal Society on June 21, 1804.
In 1957 Rudolf Mxssbauer, in what has been called one of the “landmark experiments in twentieth century physics”, discovered the resonant and recoil-free emission and absorption of gamma rays by atoms in a solid metal sample containing only 191Ir. This phenomenon, known as the Mxssbauer effect, and developed as Mxssbauer spectroscopy, has made important contributions to research in physics, chemistry, biochemistry, metallurgy, and mineralogy. Mxssbauer received the Nobel Prize in Physics in 1961, at the age 32, just three years after he published his discovery.
Iridium is found in nature as an uncombined element or in natural alloys; especially the iridium–osmium alloys, osmiridium, and iridiosmium (iridium rich). In the nickel and copper deposits the platinum group metals occur as sulfides (i.e. (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.
Within the Earth’s crust, iridium is found at highest concentrations in three types of geologic structure: igneous deposits, 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, 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. 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 Chocx Department of Colombia are still a source for platinum-group metals. As of 2003 the world reserves had not been estimated.
The Cretaceous–Paleogene boundary of 65 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. A team led by Luis Alvarez proposed in 1980 an extraterrestrial origin for this iridium, attributing it to an asteroid or comet impact. Their theory, known as the Alvarez hypothesis, 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 Yucatxn Peninsula. 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 Rxunion, are still releasing iridium.
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. To separate the metals, they must 1st 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.
After it is dissolved, iridium is separated from the other platinum group metals by precipitating 2IrCl6 or by extracting IrCl2−6 with organic amines. The 1st method is similar to the procedure Tennant and Wollaston used for their separation. The 2nd 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.
The price of iridium fluctuates considerably, as shown in the table, because of unstable supply, demand, speculation, and hoarding, amplified by the small size of the market and instability in the producing countries. The sharp decrease around 2003 has been related to the oversupply of Ir crucibles used for industrial growth of large single crystals.
The demand for iridium surged from 2.5 tonnes in 2009 to 10.4 tonnes in 2010, mostly because of electronics-related applications that saw a rise from 0.2 to 6 tonnes – iridium crucibles are commonly used for growing large high-quality single crystals, demand for which has increased sharply. This increase in iridium consumption is predicted to saturate due to accumulating stocks of crucibles, as happened earlier in the 2000s. Other major applications include spark plugs that consumed 0.78 tonnes of Ir in 2007, electrodes for the chloralkali process and chemical catalysts (0.75 t in 2007).
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. Osmium–iridium is used for compass bearings and for balances.
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 for use in computer memory devices and in solid state lasers. The crystals, such as gadolinium gallium garnet and yttrium gallium garnet, are grown by melting pre-sintered charges of mixed oxides under oxidizing conditions at temperatures up to 2100 xC. Its resistance to arc erosion makes iridium alloys ideal for electrical contacts for spark plugs.
Iridium compounds are used as catalysts in the Cativa process for carbonylation of methanol to produce acetic acid.
The radioisotope iridium-192 is one of the two most important sources of energy for use in industrial γ-radiography for non-destructive testing of metals. Additionally, 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.
An alloy of 90% platinum and 10% iridium was used in 1889 to construct the International Prototype Metre and kilogram mass, kept by the International Bureau of Weights and Measures near Paris. 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 3] but the kilogram prototype is still the international standard of mass.
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.