Uranium(IV,VI) Compounds

Uranium is a chemical element with the 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 is weakly radioactive because all isotopes of uranium are unstable; the half-lives of its naturally occurring isotopes range between 159,200 years and 4.5 billion years. 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.

In nature, uranium is found as uranium-238 (99.2739–99.2752%), uranium-235 (0.7198–0.7202%), and a very small amount of uranium-234 (0.0050–0.0059%). Uranium decays slowly by emitting an alpha particle. The half-life of uranium-238 is about 4.47 billion years and that of uranium-235 is 704 million years, making them useful in dating the age of the Earth.

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 tiny amounts found in nature, 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.. Uranium is used as a colorant in uranium glass, producing lemon yellow to green colors. Uranium glass fluoresces green in ultraviolet light. It was also used for tinting and shading in early photography.

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. The security of those weapons is closely monitored. Since around 2000, plutonium obtained by dismantling Cold War-era bombs is used as fuel for nuclear reactors. The development and deployment of these nuclear reactors continue on a global base as they are powerful sources of CO₂-free energy.

Characteristics

When refined, uranium is a silvery white, weakly radioactive metal. It has a Mohs hardness of 6, sufficient to scratch glass and approximately equal to that of titanium, rhodium, manganese and niobium. It is malleable, ductile, slightly paramagnetic, strongly electropositive and a poor electrical conductor. Uranium metal has a very high density of 19.1 g/cm³, denser than lead (11.3 g/cm³), but slightly less dense than tungsten and gold (19.3 g/cm³).

Uranium metal reacts with almost all non-metal elements (with the exception of the noble gases) and their compounds, with reactivity increasing with temperature. Hydrochloric and nitric acids dissolve uranium, but non-oxidizing acids other than hydrochloric acid attack the element very slowly. When finely divided, it can react with cold water; in air, uranium metal becomes coated with a dark layer of uranium oxide. 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, its uranium-235 isotope will most of the time divide 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 special 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 of uranium-235 can be used to make an atomic bomb. 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:
* α (orthorhombic) stable up to . Orthorhombic, space group No. 63, ''Cmcm'', lattice parameters ''a''= 285.4 pm, ''b'' = 587 pm, ''c'' = 495.5 pm.
* β ( tetragonal) stable from . Tetragonal, space group ''P''4₂/''mnm'', ''P''4₂''nm'', or ''P''4''n''2, lattice parameters ''a'' = 565.6 pm, ''b'' = ''c'' = 1075.9 pm.
* γ ( body-centered cubic) from to melting point—this is the most malleable and ductile state. Body-centered cubic, lattice parameter ''a'' = 352.4 pm.

Applications

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. 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).

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. Other uses of depleted uranium include counterweights for aircraft control surfaces, as ballast for missile re-entry vehicles and as a shielding material. Due to its high density, this material is found in inertial guidance systems and in gyroscopic compasses. 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.. 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.

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 joules), assuming complete fission; as much energy as 1.5 million kilograms (1,500 tonnes) of coal.

Commercial nuclear power plants use fuel that is typically enriched to around 3% uranium-235. 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 through the following reaction:

: + n +

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.

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. 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), in lamp filaments for stage lighting bulbs, to improve the appearance of dentures, 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 the isotope uranium-238 (4.47 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.

History

Pre-discovery use

The use of uranium in its natural oxide form dates back to at least the year 79 CE, when it was used in the Roman Empire to add a yellow color to ceramic glazes. 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.. 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. 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.

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.. 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). 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.

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.

Henri Becquerel discovered radioactivity by using uranium in 1896. 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". 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 substituted ferrouranium alloys which present many of the same physical characteristics. When this practice became known in 1916 the USA government requested several prominent universities to research these uses for uranium and tools made with these formulas remained in use for several decades only ending when 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 observed that bombarding uranium with neutrons produces the emission of beta rays (electrons or positrons from the elements produced; see beta particle). The fission products were at first mistaken for new elements with atomic numbers 93 and 94, which the Dean of the Faculty of Rome, Orso Mario Corbino, christened ''ausonium'' and ''hesperium'', respectively. 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. in Hahn's laboratory in Berlin. Lise Meitner and her nephew, the physicist Otto Robert Frisch, published the physical explanation in February 1939 and named the process "nuclear fission". Soon after, Fermi hypothesized that the 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 the rare uranium isotope uranium-235. 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. After mailed to Columbia University's cyclotron, John Dunning confirmed the sample to be the isolated fissile material on 1 March. 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.

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. 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 400 short tons (360 metric tons) of graphite, 58 short tons (53 metric tons) of uranium oxide, and six short tons (5.5 metric tons) of uranium metal, a majority of which was supplied by Westinghouse Lamp Plant in a makeshift production process.

Nuclear weaponry

Two major types of atomic bombs 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. The uranium-based Little Boy device became the first nuclear weapon used in war when it was detonated over the Japanese city of Hiroshima 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 approximately 75,000 people (see Atomic bombings of Hiroshima and Nagasaki). 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.

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. 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). 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, 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.

Prehistoric naturally occurring fission

In 1972, the 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, West Africa, collectively known as the Oklo Fossil Reactors. The ore deposit is 1.7 billion years old; then, uranium-235 constituted about 3% of the total uranium on Earth. This is high enough to permit a sustained nuclear fission chain reaction to occur, provided other supporting conditions exist. The capacity of the surrounding sediment to contain the 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.

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 spread a significant amount of fallout from uranium daughter isotopes around the world. Additional fallout and pollution occurred from several nuclear accidents.

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. 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.

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. Since 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) have been stored in often inadequately guarded facilities in the Russian Federation and several other former Soviet states. 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. From 1993 to 2005 the Material Protection, Control, and Accounting Program, operated by the federal government of the United States, spent approximately 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. ''Scientific American'' reported in February 2006 that in some of the facilities security consisted of chain link fences which were in severe states of disrepair. According to an interview from the article, one facility had been storing samples of enriched (weapons grade) uranium in a broom closet before the improvement project; another had been keeping track of its stock of nuclear warheads using index cards kept in a shoe box.

Occurrence

Origin

Along with all elements having atomic weights higher than that of iron, uranium is only naturally formed by the r-process (rapid neutron capture) in supernovae and neutron star mergers. Primordial thorium and uranium are only produced in the r-process, because the s-process (slow neutron capture) is too slow and cannot pass the gap of instability after bismuth. Besides the two extant primordial uranium isotopes, ²³⁵U and ²³⁸U, the r-process also produced significant quantities of ²³⁶U, which has a shorter half-life and so is an extinct radionuclide, having long since decayed completely to ²³²Th. Uranium-236 was itself enriched by the decay of ²⁴⁴Pu, accounting for the observed higher-than-expected abundance of thorium and lower-than-expected abundance of uranium. While the natural abundance of uranium has been supplemented by the decay of extinct ²⁴²Pu (half-life 0.375 million years) and ²⁴⁷Cm (half-life 16 million years), producing ²³⁸U and ²³⁵U respectively, this occurred to an almost negligible extent due to the shorter half-lives of these parents and their lower production than ²³⁶U and ²⁴⁴Pu, the parents of thorium: the ²⁴⁷Cm:²³⁵U ratio at the formation of the Solar System was .

Biotic and abiotic

Uranium is a naturally occurring element that can be found in low levels within all rock, soil, and water. Uranium is the 51st element in order of abundance in the Earth's crust. Uranium is also the highest-numbered element to be found naturally in significant quantities on Earth and is almost always found combined with other elements. The decay of uranium, thorium, and potassium-40 in the Earth's mantle is thought to be the main source of heat that keeps the Earth's outer core in the liquid state and drives mantle convection, which in turn drives plate tectonics.

Uranium's average concentration in the Earth's crust is (depending on the reference) 2 to 4 parts per million, or about 40 times as abundant as silver. The Earth's crust from the surface to 25 km (15 mi) down is calculated to contain 10¹⁷ kg (2 lb) of uranium while the oceans may contain 10¹³ kg (2 lb). The concentration of uranium in soil ranges from 0.7 to 11 parts per million (up to 15 parts per million in farmland soil due to use of phosphate fertilizers), and its concentration in sea water is 3 parts per billion.

Uranium is more plentiful than antimony, tin, cadmium, mercury, or silver, and it is about as abundant as arsenic or molybdenum. Uranium is found in hundreds of minerals, including uraninite (the most common uranium ore), carnotite, autunite, uranophane, torbernite, and coffinite. Significant concentrations of uranium occur in some substances such as phosphate rock deposits, and minerals such as lignite, and monazite sands in uranium-rich ores (it is recovered commercially from sources with as little as 0.1% uranium).

Some bacteria, such as '' Shewanella putrefaciens'', ''Geobacter metallireducens'' and some strains of ''Burkholderia fungorum'', use uranium for their growth and convert U(VI) to U(IV). Recent research suggests that this pathway includes reduction of the soluble U(VI) via an intermediate U(V) pentavalent state.

Other organisms, such as the lichen ''Trapelia involuta'' or microorganisms such as the bacterium ''Citrobacter'', can absorb concentrations of uranium that are up to 300 times the level of their environment. ''Citrobacter'' species absorb uranyl ions when given glycerol phosphate

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