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Barium is a chemical element; it has symbol Ba and atomic number 56. It is the fifth element in group 2 and is a soft, silvery alkaline earth metal. Because of its high chemical reactivity, barium is never found in nature as a free element.
The most common minerals of barium are barite (barium sulfate, BaSO4) and witherite (barium carbonate, BaCO3). The name barium originates from the alchemical derivative "baryta" from Greek language βαρὺς (), meaning 'heavy'. Baric is the adjectival form of barium. Barium was identified as a new element in 1772, but not reduced to a metal until 1808 with the advent of electrolysis.
Barium has few industrial applications. Historically, it was used as a getter for and in oxide form as the emissive coating on indirectly heated cathodes. It is a component of YBCO (high-temperature superconductors) and electroceramics, and is added to steel and cast iron to reduce the size of carbon grains within the microstructure. Barium compounds are added to fireworks to impart a green color. Barium sulfate is used as an insoluble additive to oil well drilling fluid. In a purer form it is used as X-ray radiocontrast agents for imaging the human gastrointestinal tract. Water-soluble barium compounds are poisonous and have been used as .
At room temperature and pressure, barium metal adopts a body-centered cubic structure, with a barium–barium distance of 503 , expanding with heating at a rate of approximately 1.8/°C. It is a soft metal with a Mohs hardness of 1.25. Its melting temperature of is intermediate between those of the lighter strontium () and heavier radium (); however, its boiling point of exceeds that of strontium (). The density (3.62 g/cm3) is again intermediate between those of strontium (2.36 g/cm3) and radium (≈5 g/cm3).
Barium reacts with ammonia to form the electride , which near room temperature gives the amide .
The metal is readily attacked by acids. Sulfuric acid is a notable exception because passivation stops the reaction by forming the insoluble barium sulfate on the surface. Barium combines with several other metals, including aluminium, zinc, lead, and tin, forming intermetallics and alloys.
| Selected alkaline earth and zinc salts densities, g/cm3 |
Barium salts are typically white when solid and colorless when dissolved. They are denser than the strontium or calcium analogs (see table; zinc is given for comparison).
Barium hydroxide ("baryta") was known to alchemists, who produced it by heating barium carbonate. Unlike calcium hydroxide, it absorbs very little CO2 in aqueous solutions and is therefore insensitive to atmospheric fluctuations. This property is used in calibrating pH equipment.
Barium compounds burn with a green to pale green flame test, which is an efficient test to detect a barium compound. The color results from at 455.4, 493.4, 553.6, and 611.1 nm.
Organobarium compounds are a growing field of knowledge: recently discovered are dialkylbariums and alkylhalobariums.
Barium found in the Earth's crust is a mixture of seven primordial nuclides, barium-130, 132, and 134 through 138. Barium-130 undergoes very slow radioactive decay to xenon-130 by double Beta decay, with a half-life of (0.5–2.7)×1021 years (about 1011 times the age of the universe). Its abundance is about 0.11% that of natural barium. Though barium-132 can theoretically undergo the same decay, giving xenon-132, experimental evidence has not detected this.
Of the stable isotopes, barium-138 composes 71.7% of all barium; other isotopes have decreasing abundance with decreasing mass number (except for a probable inversion for the p-nuclei 130Ba and 132Ba).
In total, barium has 41 known isotopes, ranging in mass between 114 and 154. The most stable artificial radioisotope is barium-133 with a half-life of 10.538 years. Five other isotopes have half-lives longer than a day. The longest-lived nuclear isomer are 133mBa at 38.90 hours and 135m1Ba at 28.11 hours. The analogous 137m1Ba (half-life 2.552 minutes) occurs in the decay of the common fission product caesium-137.
Carl Scheele determined that baryte contained a new element in 1772, but could not isolate barium, only barium oxide. Johan Gottlieb Gahn also isolated barium oxide two years later in similar studies. Oxidized barium was at first called "barote" by Guyton de Morveau, a name that was changed by Antoine Lavoisier to baryte (in French) or baryta (in Latin). Also in the 18th century, English mineralogist William Withering noted a heavy mineral in the lead mines of Cumberland, now known to be witherite. Barium was first isolated by electrolysis of molten barium salts in 1808 by Sir Humphry Davy in England. Davy, by analogy with calcium, named "barium" after baryta, with the "-ium" ending signifying a metallic element. Robert Bunsen and Augustus Matthiessen obtained pure barium by electrolysis of a molten mixture of barium chloride and ammonium chloride.
The production of pure oxygen in the Brin process was a large-scale application of barium peroxide in the 1880s, before it was replaced by electrolysis and fractional distillation of liquefied air in the early 1900s. In this process barium oxide reacts at with air to form barium peroxide, which decomposes above by releasing oxygen:
Barium sulfate was first applied as a radiocontrast agent in medical imaging of the digestive system in 1908.
The baryte reserves are estimated between 0.7 and 2 billion . The highest production, 8.3 million tonnes, was achieved in 1981, but only 7–8% was used for barium metal or compounds. Baryte production has risen since the second half of the 1990s from 5.6 million tonnes in 1996 to 7.6 in 2005 and 7.8 in 2011. China accounts for more than 50% of this output, followed by India (14% in 2011), Morocco (8.3%), US (8.2%), Iran and Kazakhstan (2.6% each) and Turkey (2.5%).Miller, M. M. Barite. USGS.gov
The mined ore is washed, crushed, classified, and separated from quartz. If the quartz penetrates too deeply into the ore, or the iron, zinc, or lead content is abnormally high, then froth flotation is used. The product is a 98% pure baryte (by mass); the purity should be no less than 95%, with a minimal content of iron and silicon dioxide. It is then reduced by carbon to barium sulfide:
The water-soluble barium sulfide is the starting point for other compounds: treating BaS with oxygen produces the sulfate, with nitric acid the nitrate, with aqueous carbon dioxide the carbonate, and so on. The nitrate can be thermally decomposed to yield the oxide. Barium metal is produced by reduction with aluminium at . The intermetallic compound BaAl4 is produced first:
Barium vapor is condensed and packed into molds in an atmosphere of argon. This method is used commercially, yielding ultrapure barium. Commonly sold barium is about 99% pure, with main impurities being strontium and calcium (up to 0.8% and 0.25%) and other contaminants contributing less than 0.1%.
A similar reaction with silicon at yields barium and barium metasilicate. Electrolysis is not used because barium readily dissolves in molten halides and the product is rather impure.
Barium shows a relatively consistent concentration in upper ocean seawater, excepting regions of high river inputs and regions with strong upwelling. There is little depletion of barium concentrations in the upper ocean for an ion with a nutrient-like profile, thus lateral mixing is important. Barium isotopic values show Oceanic basin-scale balances instead of local or short-term processes.
Other uses of elemental barium are minor and include an additive to silumin (aluminium–silicon alloys) that refines their structure, as well as
Barium sulfate has a low toxicity and relatively high density of ca. 4.5 g/cm3 (and thus opacity to X-rays). For this reason it is used as a radiocontrast agent in medical imaging of the digestive system ("" and "barium enemas"). Lithopone, a pigment that contains barium sulfate and zinc sulfide, is a permanent white with good covering power that does not darken when exposed to sulfides.
Dissolved barium's correlation with silicic acid can be seen both vertically and spatially. Particulate barium shows a strong correlation with particulate organic carbon or POC. Barium is becoming more popular as a base for palaeoceanographic proxies. With both dissolved and particulate barium's links with silicic acid and POC, it can be used to determine historical variations in the biological pump, carbon cycle, and global climate.
The barium particulate Baryte (), as one of many proxies, can be used to provide a host of historical information on processes in different oceanic settings (water column, Ocean sediment, and hydrothermal sites). In each setting there are differences in isotopic and elemental composition of the barite particulate. Barite in the water column, known as marine or pelagic barite, reveals information on seawater chemistry variation over time. Barite in sediments, known as diagenetic or cold seeps barite, gives information about sedimentary redox processes. Barite formed via hydrothermal activity at hydrothermal vents, known as hydrothermal barite, reveals alterations in the condition of the earth's crust around those vents.
Little is known about the long term effects of barium exposure. The US EPA considers it unlikely that barium is carcinogenic when consumed orally. Inhaled dust containing insoluble barium compounds can accumulate in the lungs, causing a benign condition called baritosis.
Barium carbonate has been used as a rodenticide. Though considered obsolete, it may still be in use in some countries.
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