Osmium

Osmium (from Greek grc, ὀσμή, osme, smell, label=none) is a chemical element with the symbol Os and atomic number 76. It is a hard, brittle, bluish-white transition metal in the platinum group that is found as a trace element in alloys, mostly in platinum ores. Osmium is the densest naturally occurring element. When experimentally measured using X-ray crystallography, it has a density of . Manufacturers use its alloys with platinum, iridium, and other platinum-group metals to make fountain pen nib tipping, electrical contacts, and in other applications that require extreme durability and hardness.

Osmium is among the rarest elements in the Earth's crust, making up only 50 parts per trillion ( ppt). It is estimated to be about 0.6 parts per billion in the universe and is therefore the rarest precious metal.

Characteristics

Physical properties

Osmium has a blue-gray tint and is the densest stable element; it is approximately twice as dense as lead and narrowly denser than iridium. Calculations of density from the X-ray diffraction data may produce the most reliable data for these elements, giving a value of for osmium, slightly denser than the of iridium; both metals are nearly 23 times as dense as water, and times as dense as gold.

Osmium is a hard but brittle metal that remains lustrous even at high temperatures. It has a very low compressibility. Correspondingly, its bulk modulus is extremely high, reported between and , which rivals that of diamond (). The hardness of osmium is moderately high at . Because of its hardness, brittleness, low vapor pressure (the lowest of the platinum-group metals), and very high melting point (the fourth highest of all elements, after carbon, tungsten, and rhenium), solid osmium is difficult to machine, form, or work.

Chemical properties

Osmium forms compounds with oxidation states ranging from −2 to +8. The most common oxidation states are +2, +3, +4, and +8. The +8 oxidation state is notable for being the highest attained by any chemical element aside from iridium's +9 and is encountered only in xenon, ruthenium, hassium, iridium, and plutonium. The oxidation states −1 and −2 represented by the two reactive compounds and are used in the synthesis of osmium cluster compounds.

The most common compound exhibiting the +8 oxidation state is osmium tetroxide. This toxic compound is formed when powdered osmium is exposed to air. It is a very volatile, water-soluble, pale yellow, crystalline solid with a strong smell. Osmium powder has the characteristic smell of osmium tetroxide. Osmium tetroxide forms red osmates upon reaction with a base. With ammonia, it forms the nitrido-osmates . Osmium tetroxide boils at 130 ° C and is a powerful oxidizing agent. By contrast, osmium dioxide () is black, non-volatile, and much less reactive and toxic.

Only two osmium compounds have major applications: osmium tetroxide for staining tissue in electron microscopy and for the oxidation of alkenes in organic synthesis, and the non-volatile osmates for organic oxidation reactions.

Osmium pentafluoride () is known, but osmium trifluoride () has not yet been synthesized. The lower oxidation states are stabilized by the larger halogens, so that the trichloride, tribromide, triiodide, and even diiodide are known. The oxidation state +1 is known only for osmium monoiodide (OsI), whereas several carbonyl complexes of osmium, such as triosmium dodecacarbonyl (), represent oxidation state 0.

In general, the lower oxidation states of osmium are stabilized by ligands that are good σ-donors (such as amines) and π-acceptors ( heterocycles containing nitrogen). The higher oxidation states are stabilized by strong σ- and π-donors, such as and .

Despite its broad range of compounds in numerous oxidation states, osmium in bulk form at ordinary temperatures and pressures resists attack by all acids, including aqua regia, but is attacked by fused alkalis, hot nitric acid, and hot aqua regia.

Isotopes

Osmium has seven naturally occurring isotopes, five of which are stable: , , , , and (most abundant) . undergoes alpha decay with such a long half-life years, approximately times the age of the universe, that for practical purposes it can be considered stable. is also known to undergo alpha decay with a half-life of years. Alpha decay is predicted for all the other naturally occurring isotopes, but this has never been observed, presumably due to very long half-lives. It is predicted that and can undergo double beta decay, but this radioactivity has not been observed yet.

is the descendant of (half-life ) and is used extensively in dating terrestrial as well as meteoric rocks (see rhenium-osmium dating). It has also been used to measure the intensity of continental weathering over geologic time and to fix minimum ages for stabilization of the mantle roots of continental cratons. This decay is a reason why rhenium-rich minerals are abnormally rich in . However, the most notable application of osmium isotopes in geology has been in conjunction with the abundance of iridium, to characterise the layer of shocked quartz along the Cretaceous–Paleogene boundary that marks the extinction of the non-avian dinosaurs 65 million years ago.

History

Osmium was discovered in 1803 by Smithson Tennant and William Hyde Wollaston in London, England. The discovery of osmium is intertwined with that of platinum and the other metals of the platinum group. Platinum reached Europe as ''platina'' ("small silver"), first encountered in the late 17th century in silver mines around the Chocó Department, in Colombia. The discovery that this metal was not an alloy, but a distinct new element, was published in 1748.
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. Joseph Louis Proust thought that the residue was graphite. Victor Collet-Descotils, Antoine François, comte de Fourcroy, and Louis Nicolas Vauquelin also observed iridium in the black platinum residue in 1803, but did not obtain enough material for further experiments. Later the two French chemists Fourcroy and Vauquelin identified a metal in a platinum residue they called ‘''ptène''’.

In 1803, 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 was of this new metal—which he named ''ptene'', from the Greek word (ptènos) for winged. However, Tennant, who had the advantage of a much larger amount of residue, continued his research and identified two previously undiscovered elements in the black residue, iridium and osmium. He obtained a yellow solution (probably of ''cis''– /nowiki>Os(OH)₂O₄/nowiki>²⁻) by reactions with sodium hydroxide at red heat. After acidification he was able to distill the formed OsO₄. He named it osmium after Greek ''osme'' meaning "a smell", because of the ashy and smoky smell of the volatile osmium tetroxide. Discovery of the new elements was documented in a letter to the Royal Society on June 21, 1804.

Uranium and osmium were early successful catalysts in the Haber process, the nitrogen fixation reaction of nitrogen and hydrogen to produce ammonia, giving enough yield to make the process economically successful. At the time, a group at BASF led by Carl Bosch bought most of the world's supply of osmium to use as a catalyst. Shortly thereafter, in 1908, cheaper catalysts based on iron and iron oxides were introduced by the same group for the first pilot plants, removing the need for the expensive and rare osmium.

Nowadays osmium is obtained primarily from the processing of platinum and nickel ores.

Occurrence

Osmium is the least abundant stable element in Earth's crust, with an average mass fraction of 50  parts per trillion in the continental crust.

Osmium is found in nature as an uncombined element or in natural alloys; especially the iridium–osmium alloys, osmiridium (iridium rich), and iridosmium (osmium rich). In nickel and copper deposits, the platinum-group metals occur as sulfides (i.e., ), tellurides (e.g., ), antimonides (e.g., ), and arsenides (e.g., ); in all these compounds platinum is exchanged by a small amount of iridium and osmium. As with all of the platinum-group metals, osmium can be found naturally in alloys with nickel or copper.

Within Earth's crust, osmium, like 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, though the large copper–nickel deposits near Norilsk in Russia, and the Sudbury Basin in Canada are also significant sources of osmium. Smaller reserves can be found in the United States. The alluvial deposits used by pre-Columbian people in the Chocó Department, Colombia are still a source for platinum-group metals. The second large alluvial deposit was found in the Ural Mountains, Russia, which is still mined.

Production

Osmium 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, together with non-metallic elements such as selenium and tellurium, settle to the bottom of the cell as ''anode mud'', which forms the starting material for their extraction. Separating the metals requires that they first be brought into solution. Several methods can achieve this, 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. Osmium, ruthenium, rhodium, and iridium can be separated from platinum, gold, and base metals by their insolubility in aqua regia, leaving a solid residue. Rhodium can be separated from the residue by treatment with molten sodium bisulfate. The insoluble residue, containing ruthenium, osmium, and iridium, is treated with sodium oxide, in which Ir is insoluble, producing water-soluble ruthenium and osmium salts. After oxidation to the volatile oxides, is separated from by precipitation of (NH₄)₃RuCl₆ with ammonium chloride.

After it is dissolved, osmium is separated from the other platinum-group metals by distillation or extraction with organic solvents of the volatile osmium tetroxide. The first method is similar to the procedure used by Tennant and Wollaston. Both methods are 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.

Neither the producers nor the United States Geological Survey published any production amounts for osmium. In 1971, estimations of the United States production of osmium as a byproduct of copper refining was 2000  troy ounces (62 kg). Between 2010 and 2019, annual US imports of osmium ranged from less than 0.5 kg to 856 kg, averaging 157 kg/year.

One another method for producing osmium is from rhenium. , which occurs 62.6% in nature, could absorb a neutron to become . This has a short half-life of approximately 17 hours; the nucleus converts to , which occurs 13.24% in nature.

Applications

Because of the volatility and extreme toxicity of its oxide, osmium is rarely used in its pure state, but is instead often alloyed with other metals for high-wear applications. Osmium alloys such as osmiridium are very hard and, along with other platinum-group metals, are used in the tips of fountain pens, instrument pivots, and electrical contacts, as they can resist wear from frequent operation. They were also used for the tips of phonograph styli during the late 78 rpm and early " LP" and " 45" record era, circa 1945 to 1955. Osmium-alloy tips were significantly more durable than steel and chromium needle points, but wore out far more rapidly than competing, and costlier, sapphire and diamond tips, so they were discontinued.

Osmium tetroxide has been used in fingerprint detection and in staining fatty tissue for optical and electron microscopy. As a strong oxidant, it cross-links lipids mainly by reacting with unsaturated carbon–carbon bonds and thereby both fixes biological membranes in place in tissue samples and simultaneously stains them. Because osmium atoms are extremely electron-dense, osmium staining greatly enhances image contrast in transmission electron microscopy (TEM) studies of biological materials. Those carbon materials otherwise have very weak TEM contrast. Another osmium compound, osmium ferricyanide (OsFeCN), exhibits similar fixing and staining action.

The tetroxide and its derivative potassium osmate are important oxidants in organic synthesis. For the Sharpless asymmetric dihydroxylation, which uses osmate for the conversion of a double bond into a vicinal diol, Karl Barry Sharpless was awarded the Nobel Prize in Chemistry in 2001. OsO₄ is very expensive for this use, so KMnO₄ is often used instead, even though the yields are less for this cheaper chemical reagent.

In 1898, the Austrian chemist Auer von Welsbach developed the Oslamp with a filament made of osmium, which he introduced commercially in 1902. After only a few years, osmium was replaced by tungsten, which is more abundant (and thus cheaper) and more stable. Tungsten has the highest melting point among all metals, and its use in light bulbs increases the luminous efficacy and life of incandescent lamps.

The light bulb manufacturer Osram (founded in 1906, when three German companies, Auer-Gesellschaft, AEG and Siemens & Halske, combined their lamp production facilities) derived its name from the elements of osmium and Wolfram (the latter is German for tungsten).

Like palladium, powdered osmium effectively absorbs hydrogen atoms. This could make osmium a potential candidate for a metal-hydride battery electrode. However, osmium is expensive and would react with potassium hydroxide, the most common battery electrolyte.

Osmium has high reflectivity in the ultraviolet range of the electromagnetic spectrum; for example, at 600 Å osmium has a reflectivity twice that of gold. This high reflectivity is desirable in space-based UV spectrometers, which have reduced mirror sizes due to space limitations. Osmium-coated mirrors were flown in several space missions aboard the Space Shuttle, but it soon became clear that the oxygen radicals in low Earth orbit are abundant enough to significantly deteriorate the osmium layer.

The only known clinical use of osmium is synovectomy in arthritic patients in Scandinavia. It involves the local administration of osmium tetroxide (OsO₄), which is a highly toxic compound. The lack of reports of long-term side effects suggest that osmium itself can be biocompatible, though this depends on the osmium compound administered. In 2011, osmium(VI) and osmium(II) compounds were reported to show anticancer activity ''in vivo''; this indicated a promising future for using osmium compounds as anticancer drugs.

Image:Sharpless Dihydroxylation Scheme.png, The Sharpless dihydroxylation:
R_L = largest substituent; R_M = medium-sized substituent; R_S = smallest substituent
Image:NASAmirroroxidation.jpg, Post-flight appearance of Os, Ag, and Au mirrors from the front (left images) and rear panels of the Space Shuttle. Blackening reveals oxidation due to irradiation by oxygen atoms.

Precautions

Metallic osmium is harmless in its metallic state, but finely divided metallic osmium is pyrophoric and reacts with oxygen at room temperature, forming volatile osmium tetroxide. Because all osmium metal slowly oxidizes in air, with the exception of crystallized osmium and various alloys, the degree of hazard comes from its surface area. Some osmium compounds are also converted to the tetroxide if oxygen is present. This makes osmium tetroxide the main source of contact with the environment.

Osmium tetroxide is highly volatile and penetrates skin readily, and is very toxic by inhalation, ingestion, and skin contact. Airborne low concentrations of osmium tetroxide vapor can cause lung congestion and skin or eye damage, and should therefore be used in a fume hood. Osmium tetroxide is rapidly reduced to relatively inert compounds by e.g. ascorbic acid or polyunsaturated vegetable oils (such as corn oil).

Price

Osmium, like other precious metals, is measured by troy weight and grams. The market price of osmium has not changed in decades, primarily because little change has occurred in supply and demand. In addition to being scarce, osmium is difficult to work with, has few uses, and is a challenge to store safely because of the metal's toxic gas made when oxygenated.

While the price of $400 per troy ounce has remained steady since the 1990s, inflation since that time has led to the metal losing about one-third of its value in the two decades prior to 2018.

References

External links

*

Osmium
at '' The Periodic Table of Videos'' (University of Nottingham)
* Flegenheimer, J. (2014). The mystery of the disappearing isotope. ''Revista Virtual de Química''. V. XX. Available a
Wayback Machine
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Chemical elements
Transition metals
Noble metals
Precious metals
Native element minerals
Chemical elements with hexagonal close-packed structure
Platinum-group metals