Thorium dioxide

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Thorium dioxide
Fluorite-unit-cell-3D-ionic.png
Names
IUPAC names
Thorium dioxide
Thorium(IV) oxide
Other names
Thoria
Thorium anhydride
Identifiers
3D model (JSmol)
ECHA InfoCard 100.013.842
PubChem CID
Properties
ThO2
Molar mass 264.037 g/mol [1]
Appearancewhite solid [1]
Odor odorless
Density 10.0 g/cm3 [1]
Melting point 3,350 °C (6,060 °F; 3,620 K) [1]
Boiling point 4,400 °C (7,950 °F; 4,670 K) [1]
insoluble [1]
Solubility insoluble in alkali
slightly soluble in acid [1]
16.0·10−6 cm3/mol [2]
2.200 (thorianite) [3]
Structure
Fluorite (cubic), cF12
Fm3m, No. 225
a = 559.74(6) pm [4]
Tetrahedral (O2−); cubic (ThIV)
Thermochemistry
65.2(2) JK1mol1
1226(4) kJ/mol
Hazards
NFPA 704
Flammability code 0: Will not burn. E.g. waterHealth code 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformReactivity code 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazard RA: Radioactive. E.g. plutoniumThorium dioxide
0
2
0
Radiation warning symbol 3.svg
Flash point Non-flammable
Lethal dose or concentration (LD, LC):
400 mg/kg
Related compounds
Other cations
Hafnium(IV) oxide
Cerium(IV) oxide
Related compounds
Protactinium(IV) oxide
Uranium(IV) oxide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Thorium dioxide (ThO2), also called thorium(IV) oxide, is a crystalline solid, often white or yellow in color. Also known as thoria, it is produced mainly as a by-product of lanthanide and uranium production. [4] Thorianite is the name of the mineralogical form of thorium dioxide. It is moderately rare and crystallizes in an isometric system. The melting point of thorium oxide is 3300 °C – the highest of all known oxides. Only a few elements (including tungsten and carbon) and a few compounds (including tantalum carbide) have higher melting points. [5] All thorium compounds are radioactive because there are no stable isotopes of thorium.

The lanthanide or lanthanoid series of chemical elements comprises the 15 metallic chemical elements with atomic numbers 57 through 71, from lanthanum through lutetium. These elements, along with the chemically similar elements scandium and yttrium, are often collectively known as the rare earth elements.

Uranium Chemical element with atomic number 92

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 and uranium-235. 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.

Thorianite oxide mineral

Thorianite is a rare thorium oxide mineral, ThO2. It was originally described by Ananda Coomaraswamy in 1904 as uraninite, but recognized as a new species by Wyndham R. Dunstan. It was so named on account of its high percentage of thorium; it also contains the oxides of uranium, lanthanum, cerium, praseodymium and neodymium. Helium is present, and the mineral is slightly less radioactive than pitchblende, but is harder to shield due to its high energy gamma rays. It is common in the alluvial gem-gravels of Sri Lanka, where it occurs mostly as water worn, small, heavy, black, cubic crystals. The largest crystals are usually near 1.5 cm. Larger crystals, up to 6 cm (2.4 in), have been reported from Madagascar.

Contents

Structure and reactions

Thoria exists as two polymorphs. One has a fluorite crystal structure. This is uncommon among binary dioxides (others with fluorite structure include cerium dioxide, uranium dioxide and plutonium dioxide).[ clarification needed ] The band gap of thoria is about 6  eV. A tetragonal form of thoria is also known.

Fluorite mineral, calcium fluoride

Fluorite (also called fluorspar) is the mineral form of calcium fluoride, CaF2. It belongs to the halide minerals. It crystallizes in isometric cubic habit, although octahedral and more complex isometric forms are not uncommon.

Uranium dioxide chemical compound

Uranium dioxide or uranium(IV) oxide (UO2), also known as urania or uranous oxide, is an oxide of uranium, and is a black, radioactive, crystalline powder that naturally occurs in the mineral uraninite. It is used in nuclear fuel rods in nuclear reactors. A mixture of uranium and plutonium dioxides is used as MOX fuel. Prior to 1960, it was used as yellow and black color in ceramic glazes and glass.

Thorium dioxide is more stable than thorium monoxide (ThO). [6] Only with careful control of reaction conditions can oxidation of thorium metal give the monoxide rather than the dioxide. At extremely high temperatures, the dioxide can convert to the monoxide either by a disproportionation reaction (equilibrium with liquid thorium metal) above 1,850 K (1,580 °C; 2,870 °F) or by simple dissociation (evolution of oxygen) above 2,500 K (2,230 °C; 4,040 °F). [7]

Thorium monoxide, is the binary oxide of thorium having chemical formula ThO. The covalent bond in this diatomic molecule is highly polar. The effective electric between the two atoms has been calculated to be about 80 gigavolts per centimeter, one of the largest known internal effective electric fields.

Applications

Nuclear fuels

Thorium dioxide (thoria) can be used in nuclear reactors as ceramic fuel pellets, typically contained in nuclear fuel rods clad with zirconium alloys. Thorium is not fissile (but is "fertile", breeding fissile uranium-233 under neutron bombardment); hence, it must be used as a nuclear reactor fuel in conjunction with fissile isotopes of either uranium or plutonium. This can be achieved by blending thorium with uranium or plutonium, or using it in its pure form in conjunction with separate fuel rods containing uranium or plutonium. Thorium dioxide offers advantages over conventional uranium dioxide fuel pellets, because of its higher thermal conductivity (lower operating temperature), considerably higher melting point, and chemical stability (does not oxidize in the presence of water/oxygen, unlike uranium dioxide).

Uranium-233 is a fissile isotope of uranium that is bred from thorium-232 as part of the thorium fuel cycle. Uranium-233 was investigated for use in nuclear weapons and as a reactor fuel. It has been used successfully in experimental nuclear reactors and has been proposed for much wider use as a nuclear fuel. It has a half-life of 160,000 years.

Thorium dioxide can be turned into a nuclear fuel by breeding it into uranium-233 (see below and refer to the article on thorium for more information on this). The high thermal stability of thorium dioxide allows applications in flame spraying and high-temperature ceramics.

Nuclear reaction Process in which two nuclei collide to produce one or more nuclides

In nuclear physics and nuclear chemistry, a nuclear reaction is semantically considered to be the process in which two nuclei, or else a nucleus of an atom and a subatomic particle from outside the atom, collide to produce one or more nuclides that are different from the nuclide(s) that began the process. Thus, a nuclear reaction must cause a transformation of at least one nuclide to another. If a nucleus interacts with another nucleus or particle and they then separate without changing the nature of any nuclide, the process is simply referred to as a type of nuclear scattering, rather than a nuclear reaction.

Thermal stability also describes, as defined by Schmidt (1928), the stability of a water body and its resistance to mixing. This is the amount of work needed to transform the water. to a uniform water density. The Schmidt stability 'S' is commonly measured in Joule per square meter or g*cm/cm. Compare Stratification. "thermal stability can also be defined as the no change at micro-structural level."

Alloys

Thorium dioxide is used as a stabilizer in tungsten electrodes in TIG welding, electron tubes, and aircraft engines. As an alloy, thoriated tungsten metal is not easily deformed because the high-fusion material thoria augments the high-temperature mechanical properties, and thorium helps stimulate the emission of electrons (thermions). It is the most popular oxide additive because of its low cost, but is being phased out in favor of non-radioactive elements such as cerium, lanthanum and zirconium.

Tungsten Chemical element with atomic number 74

Tungsten, or wolfram, is a chemical element with the symbol W and atomic number 74. The name tungsten comes from the former Swedish name for the tungstate mineral scheelite, tung sten or "heavy stone". Tungsten is a rare metal found naturally on Earth almost exclusively combined with other elements in chemical compounds rather than alone. It was identified as a new element in 1781 and first isolated as a metal in 1783. Its important ores include wolframite and scheelite.

Electron subatomic particle with negative electric charge

The electron is a subatomic particle, symbol
e
or
β
, whose electric charge is negative one elementary charge. Electrons belong to the first generation of the lepton particle family, and are generally thought to be elementary particles because they have no known components or substructure. The electron has a mass that is approximately 1/1836 that of the proton. Quantum mechanical properties of the electron include an intrinsic angular momentum (spin) of a half-integer value, expressed in units of the reduced Planck constant, ħ. Being fermions, no two electrons can occupy the same quantum state, in accordance with the Pauli exclusion principle. Like all elementary particles, electrons exhibit properties of both particles and waves: they can collide with other particles and can be diffracted like light. The wave properties of electrons are easier to observe with experiments than those of other particles like neutrons and protons because electrons have a lower mass and hence a longer de Broglie wavelength for a given energy.

Cerium Chemical element with atomic number 58

Cerium is a chemical element with the symbol Ce and atomic number 58. Cerium is a soft, ductile and silvery-white metal that tarnishes when exposed to air, and it is soft enough to be cut with a knife. Cerium is the second element in the lanthanide series, and while it often shows the +3 oxidation state characteristic of the series, it also exceptionally has a stable +4 state that does not oxidize water. It is also considered one of the rare-earth elements. Cerium has no biological role in humans and is not very toxic.

Thoria dispersed nickel finds its applications in various high temperature operations like combustion engines because it is a good creep resistant material. It can also be used for hydrogen trapping. [8] [9] [10] [11] [12]

Catalysis

Thorium dioxide has almost no value as a commercial catalyst, but such applications have been well investigated. It is a catalyst in the Ruzicka large ring synthesis. Other applications that have been explored include petroleum cracking, conversion of ammonia to nitric acid and preparation of sulfuric acid. [13]

Radiocontrast agents

Thorium dioxide was the primary ingredient in Thorotrast, a once-common radiocontrast agent used for cerebral angiography, however, it causes a rare form of cancer (hepatic angiosarcoma) many years after administration. [14] This use was replaced with injectable iodine or ingestable barium sulfate suspension as standard X-ray contrast agents.

Lamp mantles

Another major use in the past was in gas mantle of lanterns developed by Carl Auer von Welsbach in 1890, which are composed of 99 percent ThO2 and 1% cerium(IV) oxide. Even as late as the 1980s it was estimated that about half of all ThO2 produced (several hundred tonnes per year) was used for this purpose. [15] Some mantles still use thorium, but yttrium oxide (or sometimes zirconium oxide) is used increasingly as a replacement.

Glass manufacture

Yellowed thorium dioxide lens (left), a similar lens partially de-yellowed with ultraviolet radiation (centre), and lens without yellowing (right) Yellowing of thorium lenses.jpg
Yellowed thorium dioxide lens (left), a similar lens partially de-yellowed with ultraviolet radiation (centre), and lens without yellowing (right)

When added to glass, thorium dioxide helps increase its refractive index and decrease dispersion. Such glass finds application in high-quality lenses for cameras and scientific instruments. [16] The radiation from these lenses can darken them and turn them yellow over a period of years and degrade film, but the health risks are minimal. [17] Yellowed lenses may be restored to their original colourless state by lengthy exposure to intense ultraviolet radiation. Thorium dioxide has since been replaced by rare-earth oxides such as lanthanum oxide in almost all modern high-index glasses, as they provide similar effects and are not radioactive. [18]

Related Research Articles

Lanthanum Chemical element with atomic number 57

Lanthanum is a chemical element with the symbol La and atomic number 57. It is a soft, ductile, silvery-white metal that tarnishes slowly when exposed to air and is soft enough to be cut with a knife. It is the eponym of the lanthanide series, a group of 15 similar elements between lanthanum and lutetium in the periodic table, of which lanthanum is the first and the prototype. It is also sometimes considered the first element of the 6th-period transition metals, which would put it in group 3, although lutetium is sometimes placed in this position instead. Lanthanum is traditionally counted among the rare earth elements. The usual oxidation state is +3. Lanthanum has no biological role in humans but is essential to some bacteria. It is not particularly toxic to humans but does show some antimicrobial activity.

Pyrophoricity property of some thinly dispersed solids to ignite spontaneously in air without heating

A pyrophoric substance is a substance that ignites spontaneously in air at or below 54 °C (129 °F) or within 5 minutes after coming into contact with air. Examples are iron sulfide and many reactive metals including plutonium and uranium, when powdered or thinly sliced. Pyrophoric materials are often water-reactive as well and will ignite when they contact water or humid air. They can be handled safely in atmospheres of argon or nitrogen. Most pyrophoric fires should be extinguished with a Class D fire extinguisher for burning metals.

Nuclear fuel cycle Process of manufacturing and consuming nuclear fuel

The nuclear fuel cycle, also called nuclear fuel chain, is the progression of nuclear fuel through a series of differing stages. It consists of steps in the front end, which are the preparation of the fuel, steps in the service period in which the fuel is used during reactor operation, and steps in the back end, which are necessary to safely manage, contain, and either reprocess or dispose of spent nuclear fuel. If spent fuel is not reprocessed, the fuel cycle is referred to as an open fuel cycle ; if the spent fuel is reprocessed, it is referred to as a closed fuel cycle.

Breeder reactor type of fast neutron reactor that produces more fissile material than it consumes

A breeder reactor is a nuclear reactor that generates more fissile material than it consumes. Breeder reactors achieve this because their neutron economy is high enough to create more fissile fuel than they use, by irradiation of a fertile material, such as uranium-238 or thorium-232 that is loaded into the reactor along with fissile fuel. Breeders were at first found attractive because they made more complete use of uranium fuel than light water reactors, but interest declined after the 1960s as more uranium reserves were found, and new methods of uranium enrichment reduced fuel costs.

Molten salt reactor class of nuclear fission reactors with molten salt as the primary coolant or the fuel

A molten salt reactor (MSR) is a class of nuclear fission reactor in which the primary nuclear reactor coolant and/or the fuel is a molten salt mixture. MSRs offer multiple advantages over conventional nuclear power plants, although for historical reasons, they have not been deployed.

Nuclear fuel material that can be used in nuclear fission or fusion to derive nuclear energy

Nuclear fuel is material used in nuclear power stations to produce heat to power turbines. Heat is created when nuclear fuel undergoes nuclear fission.

Hot cathode Type of electrode.

In vacuum tubes and gas-filled tubes, a hot cathode or thermionic cathode is a cathode electrode which is heated to make it emit electrons due to thermionic emission. This is in contrast to a cold cathode, which does not have a heating element. The heating element is usually an electrical filament heated by a separate electric current passing through it. Hot cathodes typically achieve much higher power density than cold cathodes, emitting significantly more electrons from the same surface area. Cold cathodes rely on field electron emission or secondary electron emission from positive ion bombardment, and do not require heating. There are two types of hot cathode. In a directly heated cathode, the filament is the cathode and emits the electrons. In an indirectly heated cathode, the filament or heater heats a separate metal cathode electrode which emits the electrons.

Thorium fuel cycle nuclear fuel cycle using 232Th as fertile material, which absorbs neutrons to become into 233U (the nuclear fuel), which fissions to produce energy

The thorium fuel cycle is a nuclear fuel cycle that uses an isotope of thorium, 232
Th
, as the fertile material. In the reactor, 232
Th
is transmuted into the fissile artificial uranium isotope 233
U
which is the nuclear fuel. Unlike natural uranium, natural thorium contains only trace amounts of fissile material, which are insufficient to initiate a nuclear chain reaction. Additional fissile material or another neutron source is necessary to initiate the fuel cycle. In a thorium-fuelled reactor, 232
Th
absorbs neutrons to produce 233
U
. This parallels the process in uranium breeder reactors whereby fertile 238
U
absorbs neutrons to form fissile 239
Pu
. Depending on the design of the reactor and fuel cycle, the generated 233
U
either fissions in situ or is chemically separated from the used nuclear fuel and formed into new nuclear fuel.

Spent nuclear fuel nuclear fuel that has been irradiated in a nuclear reactor (usually at a nuclear power plant)

Spent nuclear fuel, occasionally called used nuclear fuel, is nuclear fuel that has been irradiated in a nuclear reactor. It is no longer useful in sustaining a nuclear reaction in an ordinary thermal reactor and depending on its point along the nuclear fuel cycle, it may have considerably different isotopic constituents.

Actinides in the environment refer to the sources, environmental behaviour and effects of actinides in Earth's environment. Environmental radioactivity is not limited solely to actinides; non-actinides such as radon and radium are of note.

Plutonium Chemical element with atomic number 94

Plutonium is a radioactive chemical element with the symbol Pu and atomic number 94. It is an actinide metal of silvery-gray appearance that tarnishes when exposed to air, and forms a dull coating when oxidized. The element normally exhibits six allotropes and four oxidation states. It reacts with carbon, halogens, nitrogen, silicon, and hydrogen. When exposed to moist air, it forms oxides and hydrides that can expand the sample up to 70% in volume, which in turn flake off as a powder that is pyrophoric. It is radioactive and can accumulate in bones, which makes the handling of plutonium dangerous.

Delay composition, also called delay charge or delay train, is a pyrotechnic composition, a sort of pyrotechnic initiator, a mixture of oxidizer and fuel that burns in a slow, constant rate that should not be significantly dependent on temperature and pressure. Delay compositions are used to introduce a delay into the firing train, e.g. to properly sequence firing of fireworks, to delay firing of ejection charges in e.g. model rockets, or to introduce a few seconds of time between triggering a hand grenade and its explosion. Typical delay times range between several milliseconds and several seconds.

Actinide chemistry branch of nuclear chemistry

Actinide chemistry is one of the main branches of nuclear chemistry that investigates the processes and molecular systems of the actinides. The actinides derive their name from the group 3 element actinium. The informal chemical symbol An is used in general discussions of actinide chemistry to refer to any actinide. All but one of the actinides are f-block elements, corresponding to the filling of the 5f electron shell; lawrencium, a d-block element, is also generally considered an actinide. In comparison with the lanthanides, also mostly f-block elements, the actinides show much more variable valence. The actinide series encompasses the 15 metallic chemical elements with atomic numbers from 89 to 103, actinium through lawrencium.

The Ames Project was a research and development project that was part of the larger Manhattan Project to build the first atomic bombs during World War II. It was founded by Frank Spedding from Iowa State College in Ames, Iowa as an offshoot of the Metallurgical Laboratory at the University of Chicago devoted to chemistry and metallurgy, but became a separate project in its own right. The Ames Project developed the Ames Process, a method for preparing pure uranium metal that the Manhattan Project needed for its atomic bombs and nuclear reactors. Between 1942 and 1945, it produced over 1,000 short tons (910 t) of uranium metal. It also developed methods of preparing and casting thorium, cerium and beryllium. In October 1945 Iowa State College received the Army-Navy "E" Award for Excellence in Production, an award usually only given to industrial organizations. In 1947 it became the Ames Laboratory, a national laboratory under the Atomic Energy Commission.

Compounds of thorium any chemical compound having at least one thorium atom

Many compounds of thorium are known: this is because thorium and uranium are the most stable and accessible actinides and are the only actinides that can be studied safely and legally in bulk in a normal laboratory. As such, they have the best-known chemistry of the actinides, along with that of plutonium, as the self-heating and radiation from them is not enough to cause radiolysis of chemical bonds as it is for the other actinides. While the later actinides from americium onwards are predominantly trivalent and behave more similarly to the corresponding lanthanides, as one would expect from periodic trends, the early actinides up to plutonium have relativistically destabilised and hence delocalised 5f and 6d electrons that participate in chemistry in a similar way to the early transition metals of group 3 through 8: thus, all their valence electrons can participate in chemical reactions, although this is not common for neptunium and plutonium.

Yttralox transparent ceramic

Yttralox is a transparent ceramic consisting of yttria (Y2O3) containing approximately 10% thorium dioxide (ThO2). It was one of the first transparent ceramics produced, and was invented in 1966 by Richard C. Anderson at the General Electric Research Laboratory while sintering mixtures of rare earth minerals.

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Cited sources