Cobaltis a chemical element; it has symbol Co and atomic number 27. As with nickel, cobalt is found in the Earth's crust only in a chemically combined form, save for small deposits found in alloys of natural meteoric iron. The free element, produced by reductive smelting, is a hard, lustrous, somewhat brittle, gray metal.
Cobalt-based blue pigments (cobalt blue) have been used since antiquity for jewelry and paints, and to impart a distinctive blue tint to glass. The color was long thought to be due to the metal bismuth. Miners had long used the name kobold ore (German for goblin ore) for some of the blue pigment-producing minerals. They were so named because they were poor in known metals and gave off poisonous arsenic-containing fumes when smelted.[7] In 1735, such ores were found to be reducible to a new metal (the first discovered since ancient times), which was ultimately named for the kobold.
Today, some cobalt is produced specifically from one of a number of metallic-lustered ores, such as cobaltite (CoAsS). The element is more usually produced as a by-product of copper and nickel mining. The Copperbelt in the Democratic Republic of the Congo (DRC) and Zambia yields most of the global cobalt production. World production in 2016 was 116,000 tonnes (114,000 long tons; 128,000 short tons) (according to Natural Resources Canada), and the DRC alone accounted for more than 50%.[8]
Cobalt is primarily used in lithium-ion batteries, and in the manufacture of magnetic, wear-resistant and high-strength alloys. The compounds cobalt silicate and cobalt(II) aluminate (CoAl2O4, cobalt blue) give a distinctive deep blue color to glass, ceramics, inks, paints and varnishes. Cobalt occurs naturally as only one stable isotope, cobalt-59. Cobalt-60 is a commercially important radioisotope, used as a radioactive tracer and for the production of high-energy gamma rays. Cobalt is also used in the petroleum industry as a catalyst when refining crude oil. This is to purge it of sulfur, which is very polluting when burned and causes acid rain.[9]
Cobalt is the active center of a group of coenzymes called cobalamins. Vitamin B12, the best-known example of the type, is an essential vitamin for all animals. Cobalt in inorganic form is also a micronutrient for bacteria, algae, and fungi.
Cobalt is a weakly reducing metal that is protected from oxidation by a passivating oxide film. It is attacked by halogens and sulfur. Heating in oxygen produces Co3O4 which loses oxygen at 900 C (1,650 F) to give the monoxide CoO.[16] The metal reacts with fluorine (F2) at 520 K to give CoF3; with chlorine (Cl2), bromine (Br2) and iodine (I2), producing equivalent binary halides. It does not react with hydrogen gas (H2) or nitrogen gas (N2) even when heated, but it does react with boron, carbon, phosphorus, arsenic and sulfur.[17] At ordinary temperatures, it reacts slowly with mineral acids, and very slowly with moist, but not dry, air.[citation needed]
The inventory of complexes is very large. Starting with higher oxidation states, complexes of Co(IV) and Co(V) are rare. Examples are found in caesium hexafluorocobaltate(IV) (Cs2CoF6) and potassium percobaltate (K3CoO4).[16]
59Co is the only stable cobalt isotope and the only isotope that exists naturally on Earth. Twenty-two radioisotopes have been characterized: the most stable, 60Co, has a half-life of 5.2714 years; 57Co has a half-life of 271.8 days; 56Co has a half-life of 77.27 days; and 58Co has a half-life of 70.86 days. All the other radioactive isotopes of cobalt have half-lives shorter than 18 hours, and in most cases shorter than 1 second. This element also has 4 meta states, all of which have half-lives shorter than 15 minutes.[29]
The isotopes of cobalt range in atomic weight from 50 u (50Co) to 73 u (73Co). The primary decay mode for isotopes with atomic mass unit values less than that of the only stable isotope, 59Co, is electron capture and the primary mode of decay in isotopes with atomic mass greater than 59 atomic mass units is beta decay. The primary decay products below 59Co are element 26 (iron) isotopes; above that the decay products are element 28 (nickel) isotopes.[29]
The word cobalt is derived from the German kobalt, from kobold meaning "goblin", a superstitious term used for the ore of cobalt by miners. The first attempts to smelt those ores for copper or silver failed, yielding simply powder (cobalt(II) oxide) instead. Because the primary ores of cobalt always contain arsenic, smelting the ore oxidized the arsenic into the highly toxic and volatile arsenic oxide, adding to the notoriety of the ore.[34] Paracelsus, Georgius Agricola, and Basil Valentine all referred to such silicates as "cobalt".[35]
During the 19th century, a significant part of the world's production of cobalt blue (a pigment made with cobalt compounds and alumina) and smalt (cobalt glass powdered for use for pigment purposes in ceramics and painting) was carried out at the Norwegian Blaafarvevrket.[39][40] The first mines for the production of smalt in the 16th century were located in Norway, Sweden, Saxony and Hungary. With the discovery of cobalt ore in New Caledonia in 1864, the mining of cobalt in Europe declined. With the discovery of ore deposits in Ontario, Canada, in 1904 and the discovery of even larger deposits in the Katanga Province in the Congo in 1914, mining operations shifted again.[34] When the Shaba conflict started in 1978, the copper mines of Katanga Province nearly stopped production.[41][42] The impact on the world cobalt economy from this conflict was smaller than expected: cobalt is a rare metal, the pigment is highly toxic, and the industry had already established effective ways for recycling cobalt materials. In some cases, industry was able to change to cobalt-free alternatives.[41][42]
In 1938, John Livingood and Glenn T. Seaborg discovered the radioisotope cobalt-60.[43] This isotope was famously used at Columbia University in the 1950s to establish parity violation in radioactive beta decay.[44][45]
After World War II, the US wanted to guarantee the supply of cobalt ore for military uses (as the Germans had been doing) and prospected for cobalt within the US. High purity cobalt was highly sought after for its use in jet engines and gas turbines.[46] An adequate supply of the ore was found in Idaho near Blackbird canyon. Calera Mining Company started production at the site.[47]
Cobalt demand has further accelerated in the 21st century as an essential constituent of materials used in rechargeable batteries, superalloys, and catalysts.[46] It has been argued that cobalt will be one of the main objects of geopolitical competition in a world running on renewable energy and dependent on batteries, but this perspective has also been criticised for underestimating the power of economic incentives for expanded production.[48]
The stable form of cobalt is produced in supernovae through the r-process.[49] It comprises 0.0029% of the Earth's crust. Except as recently delivered in meteoric iron, free cobalt (the native metal) is not found on Earth's surface because of its tendency to react with oxygen in the atmosphere. Small amounts of cobalt compounds are found in most rocks, soils, plants, and animals.[50] In the ocean cobalt typically reacts with chlorine.
In nature, cobalt is frequently associated with nickel. Both are characteristic components of meteoric iron, though cobalt is much less abundant in iron meteorites than nickel. As with nickel, cobalt in meteoric iron alloys may have been well enough protected from oxygen and moisture to remain as the free (but alloyed) metal.[51]
Cobalt in compound form occurs in copper and nickel minerals. It is the major metallic component that combines with sulfur and arsenic in the sulfidic cobaltite (CoAsS), safflorite (CoAs2), glaucodot ((Co,Fe)AsS), and skutterudite (CoAs3) minerals.[16] The mineral cattierite is similar to pyrite and occurs together with vaesite in the copper deposits of Katanga Province.[52] When it reaches the atmosphere, weathering occurs; the sulfide minerals oxidize and form pink erythrite ("cobalt glance": Co3(AsO4)28H2O) and spherocobaltite (CoCO3).[53][54]
Cobalt is also a constituent of tobacco smoke.[55] The tobacco plant readily absorbs and accumulates heavy metals like cobalt from the surrounding soil in its leaves. These are subsequently inhaled during tobacco smoking.[56]
The main ores of cobalt are cobaltite, erythrite, glaucodot and skutterudite (see above), but most cobalt is obtained by reducing the cobalt by-products of nickel and copper mining and smelting.[58][59]
Since cobalt is generally produced as a by-product, the supply of cobalt depends to a great extent on the economic feasibility of copper and nickel mining in a given market. Demand for cobalt was projected to grow 6% in 2017.[60]
Primary cobalt deposits are rare, such as those occurring in hydrothermal deposits, associated with ultramafic rocks, typified by the Bou-Azzer district of Morocco. At such locations, cobalt ores are mined exclusively, albeit at a lower concentration, and thus require more downstream processing for cobalt extraction.[61][62]
Several methods exist to separate cobalt from copper and nickel, depending on the concentration of cobalt and the exact composition of the used ore. One method is froth flotation, in which surfactants bind to ore components, leading to an enrichment of cobalt ores. Subsequent roasting converts the ores to cobalt sulfate, and the copper and the iron are oxidized to the oxide. Leaching with water extracts the sulfate together with the arsenates. The residues are further leached with sulfuric acid, yielding a solution of copper sulfate. Cobalt can also be leached from the slag of copper smelting.[63]
The products of the above-mentioned processes are transformed into the cobalt oxide (Co3O4). This oxide is reduced to metal by the aluminothermic reaction or reduction with carbon in a blast furnace.[16]
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