Uranium
Chemical element, symbol U and atomic number 92 / From Wikipedia, the free encyclopedia
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Uranium is a chemical element; it has symbol U and atomic number 92. It is a silvery-grey metal in the actinide series of the periodic table. A uranium atom has 92 protons and 92 electrons, of which 6 are valence electrons. Uranium radioactively decays, usually by emitting an alpha particle. The half-life of this decay varies between 159,200 and 4.5 billion years for different isotopes, making them useful for dating the age of the Earth. The most common isotopes in natural uranium are uranium-238 (which has 146 neutrons and accounts for over 99% of uranium on Earth) and uranium-235 (which has 143 neutrons). Uranium has the highest atomic weight of the primordially occurring elements. Its density is about 70% higher than that of lead and slightly lower than that of gold or tungsten. It occurs naturally in low concentrations of a few parts per million in soil, rock and water, and is commercially extracted from uranium-bearing minerals such as uraninite.[7]
Many contemporary uses of uranium exploit its unique nuclear properties. Uranium-235 is the only naturally occurring fissile isotope, which makes it widely used in nuclear power plants and nuclear weapons. However, because of the low abundance of uranium-235 in natural uranium (which is, overwhelmingly, mostly uranium-238), uranium needs to undergo enrichment so that enough uranium-235 is present. Uranium-238 is fissionable by fast neutrons and is fertile, meaning it can be transmuted to fissile plutonium-239 in a nuclear reactor. Another fissile isotope, uranium-233, can be produced from natural thorium and is studied for future industrial use in nuclear technology. Uranium-238 has a small probability for spontaneous fission or even induced fission with fast neutrons; uranium-235, and to a lesser degree uranium-233, have a much higher fission cross-section for slow neutrons. In sufficient concentration, these isotopes maintain a sustained nuclear chain reaction. This generates the heat in nuclear power reactors and produces the fissile material for nuclear weapons. Depleted uranium (238U) is used in kinetic energy penetrators and armor plating.[8]
The 1789 discovery of uranium in the mineral pitchblende is credited to Martin Heinrich Klaproth, who named the new element after the recently discovered planet Uranus. Eugène-Melchior Péligot was the first person to isolate the metal, and its radioactive properties were discovered in 1896 by Henri Becquerel. Research by Otto Hahn, Lise Meitner, Enrico Fermi and others, such as J. Robert Oppenheimer starting in 1934 led to its use as a fuel in the nuclear power industry and in Little Boy, the first nuclear weapon used in war. An ensuing arms race during the Cold War between the United States and the Soviet Union produced tens of thousands of nuclear weapons that used uranium metal and uranium-derived plutonium-239. Dismantling of these weapons and related nuclear facilities is carried out within various nuclear disarmament programs and costs billions of dollars. Weapon-grade uranium obtained from nuclear weapons is diluted with uranium-238 and reused as fuel for nuclear reactors. The development and deployment of these nuclear reactors continue globally as they are powerful sources of CO2-free energy. Spent nuclear fuel forms radioactive waste, which mostly consists of uranium-238 and poses a significant health threat and environmental impact.
Uranium is a silvery white, weakly radioactive metal. It has a Mohs hardness of 6, sufficient to scratch glass and roughly equal to that of titanium, rhodium, manganese and niobium. It is malleable, ductile, slightly paramagnetic, strongly electropositive and a poor electrical conductor.[9][10] Uranium metal has a very high density of 19.1 g/cm3,[11] denser than lead (11.3 g/cm3),[12] but slightly less dense than tungsten and gold (19.3 g/cm3).[13][14]
Uranium metal reacts with almost all non-metallic elements (except noble gases) and their compounds, with reactivity increasing with temperature.[15] Hydrochloric and nitric acids dissolve uranium, but non-oxidizing acids other than hydrochloric acid attack the element very slowly.[9] When finely divided, it can react with cold water; in air, uranium metal becomes coated with a dark layer of uranium oxide.[10] Uranium in ores is extracted chemically and converted into uranium dioxide or other chemical forms usable in industry.
Uranium-235 was the first isotope that was found to be fissile. Other naturally occurring isotopes are fissionable, but not fissile. On bombardment with slow neutrons, uranium-235 most of the time splits into two smaller nuclei, releasing nuclear binding energy and more neutrons. If too many of these neutrons are absorbed by other uranium-235 nuclei, a nuclear chain reaction occurs that results in a burst of heat or (in some circumstances) an explosion. In a nuclear reactor, such a chain reaction is slowed and controlled by a neutron poison, absorbing some of the free neutrons. Such neutron absorbent materials are often part of reactor control rods (see nuclear reactor physics for a description of this process of reactor control).
As little as 15 lb (6.8 kg) of uranium-235 can be used to make an atomic bomb.[16] The nuclear weapon detonated over Hiroshima, called Little Boy, relied on uranium fission. However, the first nuclear bomb (the Gadget used at Trinity) and the bomb that was detonated over Nagasaki (Fat Man) were both plutonium bombs.
Uranium metal has three allotropic forms:[17]
- α (orthorhombic) stable up to 668 °C (1,234 °F). Orthorhombic, space group No. 63, Cmcm, lattice parameters a = 285.4 pm, b = 587 pm, c = 495.5 pm.[18]
- β (tetragonal) stable from 668 to 775 °C (1,234 to 1,427 °F). Tetragonal, space group P42/mnm, P42nm, or P4n2, lattice parameters a = 565.6 pm, b = c = 1075.9 pm.[18]
- γ (body-centered cubic) from 775 °C (1,427 °F) to melting point—this is the most malleable and ductile state. Body-centered cubic, lattice parameter a = 352.4 pm.[18]
Military
The major application of uranium in the military sector is in high-density penetrators. This ammunition consists of depleted uranium (DU) alloyed with 1–2% other elements, such as titanium or molybdenum.[19] At high impact speed, the density, hardness, and pyrophoricity of the projectile enable the destruction of heavily armored targets. Tank armor and other removable vehicle armor can also be hardened with depleted uranium plates. The use of depleted uranium became politically and environmentally contentious after the use of such munitions by the US, UK and other countries during wars in the Persian Gulf and the Balkans raised questions concerning uranium compounds left in the soil (see Gulf War syndrome).[16]
Depleted uranium is also used as a shielding material in some containers used to store and transport radioactive materials. While the metal itself is radioactive, its high density makes it more effective than lead in halting radiation from strong sources such as radium.[9] Other uses of depleted uranium include counterweights for aircraft control surfaces, as ballast for missile re-entry vehicles and as a shielding material.[10] Due to its high density, this material is found in inertial guidance systems and in gyroscopic compasses.[10] Depleted uranium is preferred over similarly dense metals due to its ability to be easily machined and cast as well as its relatively low cost.[20] The main risk of exposure to depleted uranium is chemical poisoning by uranium oxide rather than radioactivity (uranium being only a weak alpha emitter).
During the later stages of World War II, the entire Cold War, and to a lesser extent afterwards, uranium-235 has been used as the fissile explosive material to produce nuclear weapons. Initially, two major types of fission bombs were built: a relatively simple device that uses uranium-235 and a more complicated mechanism that uses plutonium-239 derived from uranium-238. Later, a much more complicated and far more powerful type of fission/fusion bomb (thermonuclear weapon) was built, that uses a plutonium-based device to cause a mixture of tritium and deuterium to undergo nuclear fusion. Such bombs are jacketed in a non-fissile (unenriched) uranium case, and they derive more than half their power from the fission of this material by fast neutrons from the nuclear fusion process.[21]
Civilian
The main use of uranium in the civilian sector is to fuel nuclear power plants. One kilogram of uranium-235 can theoretically produce about 20 terajoules of energy (2×1013 joules), assuming complete fission; as much energy as 1.5 million kilograms (1,500 tonnes) of coal.[8]
Commercial nuclear power plants use fuel that is typically enriched to around 3% uranium-235.[8] The CANDU and Magnox designs are the only commercial reactors capable of using unenriched uranium fuel. Fuel used for United States Navy reactors is typically highly enriched in uranium-235 (the exact values are classified). In a breeder reactor, uranium-238 can also be converted into plutonium-239 through the following reaction:[10]
Before (and, occasionally, after) the discovery of radioactivity, uranium was primarily used in small amounts for yellow glass and pottery glazes, such as uranium glass and in Fiestaware.[22]
The discovery and isolation of radium in uranium ore (pitchblende) by Marie Curie sparked the development of uranium mining to extract the radium, which was used to make glow-in-the-dark paints for clock and aircraft dials.[23][24] This left a prodigious quantity of uranium as a waste product, since it takes three tonnes of uranium to extract one gram of radium. This waste product was diverted to the glazing industry, making uranium glazes very inexpensive and abundant. Besides the pottery glazes, uranium tile glazes accounted for the bulk of the use, including common bathroom and kitchen tiles which can be produced in green, yellow, mauve, black, blue, red and other colors.
Uranium was also used in photographic chemicals (especially uranium nitrate as a toner),[10] in lamp filaments for stage lighting bulbs,[25] to improve the appearance of dentures,[26] and in the leather and wood industries for stains and dyes. Uranium salts are mordants of silk or wool. Uranyl acetate and uranyl formate are used as electron-dense "stains" in transmission electron microscopy, to increase the contrast of biological specimens in ultrathin sections and in negative staining of viruses, isolated cell organelles and macromolecules.
The discovery of the radioactivity of uranium ushered in additional scientific and practical uses of the element. The long half-life of uranium-238 (4.47×109 years) makes it well-suited for use in estimating the age of the earliest igneous rocks and for other types of radiometric dating, including uranium–thorium dating, uranium–lead dating and uranium–uranium dating. Uranium metal is used for X-ray targets in the making of high-energy X-rays.[10]
Pre-discovery use
The use of uranium in its natural oxide form dates back to at least the year 79 AD, when it was used in the Roman Empire to add a yellow color to ceramic glazes.[10] Yellow glass with 1% uranium oxide was found in a Roman villa on Cape Posillipo in the Bay of Naples, Italy, by R. T. Gunther of the University of Oxford in 1912.[27] Starting in the late Middle Ages, pitchblende was extracted from the Habsburg silver mines in Joachimsthal, Bohemia (now Jáchymov in the Czech Republic), and was used as a coloring agent in the local glassmaking industry.[28] In the early 19th century, the world's only known sources of uranium ore were these mines. Mining for uranium in the Ore Mountains ceased on the German side after the Cold War ended and SDAG Wismut was wound down. On the Czech side there were attempts during the uranium price bubble of 2007 to restart mining, but those were quickly abandoned following a fall in uranium prices.[29][30]
Discovery
The discovery of the element is credited to the German chemist Martin Heinrich Klaproth. While he was working in his experimental laboratory in Berlin in 1789, Klaproth was able to precipitate a yellow compound (likely sodium diuranate) by dissolving pitchblende in nitric acid and neutralizing the solution with sodium hydroxide.[28] Klaproth assumed the yellow substance was the oxide of a yet-undiscovered element and heated it with charcoal to obtain a black powder, which he thought was the newly discovered metal itself (in fact, that powder was an oxide of uranium).[28][31] He named the newly discovered element after the planet Uranus (named after the primordial Greek god of the sky), which had been discovered eight years earlier by William Herschel.[32]
In 1841, Eugène-Melchior Péligot, Professor of Analytical Chemistry at the Conservatoire National des Arts et Métiers (Central School of Arts and Manufactures) in Paris, isolated the first sample of uranium metal by heating uranium tetrachloride with potassium.[28][33]
Henri Becquerel discovered radioactivity by using uranium in 1896.[15] Becquerel made the discovery in Paris by leaving a sample of a uranium salt, K2UO2(SO4)2 (potassium uranyl sulfate), on top of an unexposed photographic plate in a drawer and noting that the plate had become "fogged".[34] He determined that a form of invisible light or rays emitted by uranium had exposed the plate.
During World War I when the Central Powers suffered a shortage of molybdenum to make artillery gun barrels and high speed tool steels, they routinely used ferrouranium alloy as a substitute, as it presents many of the same physical characteristics as molybdenum. When this practice became known in 1916 the US government requested several prominent universities to research the use of uranium in manufacturing and metalwork. Tools made with these formulas remained in use for several decades,[35][36] until the Manhattan Project and the Cold War placed a large demand on uranium for fission research and weapon development.
Fission research
A team led by Enrico Fermi in 1934 found that bombarding uranium with neutrons produces beta rays (electrons or positrons from the elements produced; see beta particle).[37] The fission products were at first mistaken for new elements with atomic numbers 93 and 94, which the Dean of the Sapienza University of Rome, Orso Mario Corbino, named ausenium and hesperium, respectively.[38][39][40][41] The experiments leading to the discovery of uranium's ability to fission (break apart) into lighter elements and release binding energy were conducted by Otto Hahn and Fritz Strassmann[37] in Hahn's laboratory in Berlin. Lise Meitner and her nephew, physicist Otto Robert Frisch, published the physical explanation in February 1939 and named the process "nuclear fission".[42] Soon after, Fermi hypothesized that fission of uranium might release enough neutrons to sustain a fission reaction. Confirmation of this hypothesis came in 1939, and later work found that on average about 2.5 neutrons are released by each fission of uranium-235.[37] Fermi urged Alfred O. C. Nier to separate uranium isotopes for determination of the fissile component, and on 29 February 1940, Nier used an instrument he built at the University of Minnesota to separate the world's first uranium-235 sample in the Tate Laboratory. Using Columbia University's cyclotron, John Dunning confirmed the sample to be the isolated fissile material on 1 March.[43] Further work found that the far more common uranium-238 isotope can be transmuted into plutonium, which, like uranium-235, is also fissile by thermal neutrons. These discoveries led numerous countries to begin working on the development of nuclear weapons and nuclear power. Despite fission having been discovered in Germany, the Uranverein ("uranium club") Germany's wartime project to research nuclear power and/or weapons was hampered by limited resources, infighting, the exile or non-involvement of several prominent scientists in the field and several crucial mistakes such as failing to account for impurities in available graphite samples which made it appear less suitable as a neutron moderator than it is in reality. Germany's attempts to build a natural uranium / heavy water reactor had not come close to reaching criticality by the time the Americans reached Haigerloch, the site of the last German wartime reactor experiment.[44]
On 2 December 1942, as part of the Manhattan Project, another team led by Enrico Fermi was able to initiate the first artificial self-sustained nuclear chain reaction, Chicago Pile-1. An initial plan using enriched uranium-235 was abandoned as it was as yet unavailable in sufficient quantities.[45] Working in a lab below the stands of Stagg Field at the University of Chicago, the team created the conditions needed for such a reaction by piling together 360 tonnes of graphite, 53 tonnes of uranium oxide, and 5.5 tonnes of uranium metal, most of which was supplied by Westinghouse Lamp Plant in a makeshift production process.[37][46]
Nuclear weaponry
Two types of atomic bomb were developed by the United States during World War II: a uranium-based device (codenamed "Little Boy") whose fissile material was highly enriched uranium, and a plutonium-based device (see Trinity test and "Fat Man") whose plutonium was derived from uranium-238. Little Boy became the first nuclear weapon used in war when it was detonated over Hiroshima, Japan, on 6 August 1945. Exploding with a yield equivalent to 12,500 tonnes of TNT, the blast and thermal wave of the bomb destroyed nearly 50,000 buildings and killed about 75,000 people (see Atomic bombings of Hiroshima and Nagasaki).[34] Initially it was believed that uranium was relatively rare, and that nuclear proliferation could be avoided by simply buying up all known uranium stocks, but within a decade large deposits of it were discovered in many places around the world.[47]
Reactors
The X-10 Graphite Reactor at Oak Ridge National Laboratory (ORNL) in Oak Ridge, Tennessee, formerly known as the Clinton Pile and X-10 Pile, was the world's second artificial nuclear reactor (after Enrico Fermi's Chicago Pile) and was the first reactor designed and built for continuous operation. Argonne National Laboratory's Experimental Breeder Reactor I, located at the Atomic Energy Commission's National Reactor Testing Station near Arco, Idaho, became the first nuclear reactor to create electricity on 20 December 1951.[48] Initially, four 150-watt light bulbs were lit by the reactor, but improvements eventually enabled it to power the whole facility (later, the town of Arco became the first in the world to have all its electricity come from nuclear power generated by BORAX-III, another reactor designed and operated by Argonne National Laboratory).[49][50] The world's first commercial scale nuclear power station, Obninsk in the Soviet Union, began generation with its reactor AM-1 on 27 June 1954. Other early nuclear power plants were Calder Hall in England, which began generation on 17 October 1956,[51] and the Shippingport Atomic Power Station in Pennsylvania, which began on 26 May 1958. Nuclear power was used for the first time for propulsion by a submarine, the USS Nautilus, in 1954.[37][52]
Prehistoric naturally occurring fission
In 1972, French physicist Francis Perrin discovered fifteen ancient and no longer active natural nuclear fission reactors in three separate ore deposits at the Oklo mine in Gabon, Africa, collectively known as the Oklo Fossil Reactors. The ore deposit is 1.7 billion years old; then, uranium-235 constituted about 3% of uranium on Earth.[53] This is high enough to permit a sustained chain reaction, if other supporting conditions exist. The capacity of the surrounding sediment to contain the health-threatening nuclear waste products has been cited by the U.S. federal government as supporting evidence for the feasibility to store spent nuclear fuel at the Yucca Mountain nuclear waste repository.[53]
Contamination and the Cold War legacy
Above-ground nuclear tests by the Soviet Union and the United States in the 1950s and early 1960s and by France into the 1970s and 1980s[20] spread a significant amount of fallout from uranium daughter isotopes around the world.[54] Additional fallout and pollution occurred from several nuclear accidents.[55]
Uranium miners have a higher incidence of cancer. An excess risk of lung cancer among Navajo uranium miners, for example, has been documented and linked to their occupation.[56] The Radiation Exposure Compensation Act, a 1990 law in the US, required $100,000 in "compassion payments" to uranium miners diagnosed with cancer or other respiratory ailments.[57]
During the Cold War between the Soviet Union and the United States, huge stockpiles of uranium were amassed and tens of thousands of nuclear weapons were created using enriched uranium and plutonium made from uranium. After the break-up of the Soviet Union in 1991, an estimated 600 short tons (540 metric tons) of highly enriched weapons grade uranium (enough to make 40,000 nuclear warheads) had been stored in often inadequately guarded facilities in the Russian Federation and several other former Soviet states.[16] Police in Asia, Europe, and South America on at least 16 occasions from 1993 to 2005 have intercepted shipments of smuggled bomb-grade uranium or plutonium, most of which was from ex-Soviet sources.[16] From 1993 to 2005 the Material Protection, Control, and Accounting Program, operated by the federal government of the United States, spent about US$550 million to help safeguard uranium and plutonium stockpiles in Russia. This money was used for improvements and security enhancements at research and storage facilities.[16]
Safety of nuclear facilities in Russia has been significantly improved since the stabilization of political and economical turmoil of the early 1990s. For example, in 1993 there were 29 incidents ranking above level 1 on the International Nuclear Event Scale, and this number dropped under four per year in 1995–2003. The number of employees receiving annual radiation doses above 20 mSv, which is equivalent to a single full-body CT scan,[58] saw a strong decline around 2000. In November 2015, the Russian government approved a federal program for nuclear and radiation safety for 2016 to 2030 with a budget of 562 billion rubles (ca. 8 billion USD). Its key issue is "the deferred liabilities accumulated during the 70 years of the nuclear industry, particularly during the time of the Soviet Union". About 73% of the budget will be spent on decommissioning aged and obsolete nuclear reactors and nuclear facilities, especially those involved in state defense programs; 20% will go in processing and disposal of nuclear fuel and radioactive waste, and 5% into monitoring and ensuring of nuclear and radiation safety.[59]