Thorium dioxide (ThO₂), also called thorium(IV) oxide, is a crystalline solid, often white or yellow in colour. Also known as thoria, it is produced mainly as a by-product of

lanthanide The lanthanide () or lanthanoid () series of chemical elements comprises the 15 metallic chemical elements with atomic numbers 57–71, from lanthanum through lutetium. These elements, along with the chemically similar elements scandium and yt ...

and

uranium 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 weak ...

production.

Thorianite 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 by Dunstan on account of its high percentage of th ...

is the name of the mineralogical form of

thorium Thorium is a weakly radioactive metallic chemical element with the symbol Th and atomic number 90. Thorium is silvery and tarnishes black when it is exposed to air, forming thorium dioxide; it is moderately soft and malleable and has a high ...

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 Tungsten, or wolfram, is a chemical element with the symbol W and atomic number 74. Tungsten is a rare metal found naturally on Earth almost exclusively as compounds with other elements. It was identified as a new element in 1781 and first isol ...

and

carbon Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent—its atom making four electrons available to form covalent chemical bonds. It belongs to group 14 of the periodic table. Carbon ma ...

) and a few compounds (including

tantalum carbide Tantalum carbides (TaC) form a family of binary chemical compounds of tantalum and carbon with the empirical formula TaC''x'', where ''x'' usually varies between 0.4 and 1. They are extremely hard, brittle, refractory ceramic materials with metal ...

) have higher melting points. All thorium compounds, including the dioxide, are radioactive because there are no stable

isotopes of thorium Thorium (90Th) has seven naturally occurring isotopes but none are stable. One isotope, 232Th, is ''relatively'' stable, with a half-life of 1.405×1010 years, considerably longer than the age of the Earth, and even slightly longer than the gene ...

Structure and reactions

Thoria exists as two polymorphs. One has a

fluorite 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. The Mohs sca ...

crystal structure. This is uncommon among binary dioxides. (Other binary oxides with fluorite structure include

cerium dioxide Cerium(IV) oxide, also known as ceric oxide, ceric dioxide, ceria, cerium oxide or cerium dioxide, is an oxide of the rare-earth metal cerium. It is a pale yellow-white powder with the chemical formula CeO2. It is an important commercial produc ...

uranium dioxide Uranium dioxide or uranium(IV) oxide (), 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 re ...

and

plutonium dioxide Plutonium(IV) oxide or (plutonia) is the chemical compound with the formula Pu O2. This high melting-point solid is a principal compound of plutonium. It can vary in color from yellow to olive green, depending on the particle size, temperature a ...

.) The

band gap In solid-state physics, a band gap, also called an energy gap, is an energy range in a solid where no electronic states can exist. In graphs of the electronic band structure of solids, the band gap generally refers to the energy difference ( ...

of thoria is about 6 eV. A tetragonal form of thoria is also known. Thorium dioxide is more stable than thorium monoxide (ThO). 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 or by simple dissociation (evolution of oxygen) above .

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 Uranium-233 (233U or U-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 exp ...

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). Thorium dioxide can be turned into a

nuclear Nuclear may refer to: Physics Relating to the nucleus of the atom: *Nuclear engineering *Nuclear physics *Nuclear power *Nuclear reactor *Nuclear weapon *Nuclear medicine *Radiation therapy *Nuclear warfare Mathematics *Nuclear space *Nuclear ...

fuel by breeding it into uranium-233 (see below and refer to the article on

for more information on this). The high thermal stability of thorium dioxide allows applications in flame spraying and high-temperature ceramics.

Alloys

Thorium dioxide is used as a stabilizer in

electrodes in

TIG welding Gas tungsten arc welding (GTAW), also known as tungsten inert gas (TIG) welding, is an arc welding process that uses a non-consumable tungsten electrode to produce the weld. The weld area and electrode are protected from oxidation or other atmo ...

, electron tubes, and aircraft gas turbine 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

electron The electron ( or ) is a subatomic particle with a negative one elementary electric charge. Electrons belong to the first generation of the lepton particle family, and are generally thought to be elementary particles because they have n ...

s (

thermion Thermionic emission is the liberation of electrons from an electrode by virtue of its temperature (releasing of energy supplied by heat). This occurs because the thermal energy given to the charge carrier overcomes the work function of the mater ...

s). 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 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. Cerium is the second element in the lanthanide series, and while it often shows the +3 ...

lanthanum 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. It is the eponym of the lanthanide series, a group of 15 similar elements between l ...

and

zirconium Zirconium is a chemical element with the symbol Zr and atomic number 40. The name ''zirconium'' is taken from the name of the mineral zircon, the most important source of zirconium. The word is related to Persian '' zargun'' (zircon; ''zar-gun'' ...

. 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.

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 In petrochemistry, petroleum geology and organic chemistry, cracking is the process whereby complex organic compound, organic molecules such as kerogens or long-chain hydrocarbons are broken down into simpler molecules such as light hydrocarbons, b ...

, conversion of

ammonia Ammonia is an inorganic compound of nitrogen and hydrogen with the formula . A stable binary hydride, and the simplest pnictogen hydride, ammonia is a colourless gas with a distinct pungent smell. Biologically, it is a common nitrogenous ...

nitric acid Nitric acid is the inorganic compound with the formula . It is a highly corrosive mineral acid. The compound is colorless, but older samples tend to be yellow cast due to decomposition into oxides of nitrogen. Most commercially available ni ...

and preparation of

sulfuric acid Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid ( Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen and hydrogen, with the molecular fo ...

.Stoll, Wolfgang (2012) "Thorium and Thorium Compounds" in ''Ullmann's Encyclopedia of Industrial Chemistry''. Wiley-VCH, Weinheim.

Radiocontrast agents

Thorium dioxide was the primary ingredient in

Thorotrast Thorotrast is a suspension containing particles of the radioactive compound thorium dioxide, ThO2; it was used as a radiocontrast agent in clinical radiography in the 1930s to 1950s. It is no longer used clinically. Thorium compounds produce ...

, a once-common

radiocontrast agent Radiocontrast agents are substances used to enhance the visibility of internal structures in X-ray-based imaging techniques such as computed tomography ( contrast CT), projectional radiography, and fluoroscopy. Radiocontrast agents are typically i ...

used for

cerebral angiography Cerebral angiography is a form of angiography which provides images of blood vessels in and around the brain, thereby allowing detection of abnormalities such as arteriovenous malformations and aneurysms. It was pioneered in 1927 by the Portugue ...

, however, it causes a rare form of cancer (hepatic

angiosarcoma Angiosarcoma is a rare and aggressive cancer that starts in the endothelial cells that line the walls of blood vessels or lymphatic vessels. Since they are made from vascular lining, they can appear anywhere and at any age, but older people are ...

) many years after administration. This use was replaced with injectable iodine or ingestable

barium sulfate suspension Barium sulfate suspension, often simply called barium, is a contrast agent used during X-rays. Specifically it is used to improve visualization of the gastrointestinal tract (esophagus, stomach, intestines) on plain X-ray or computed tomography ...

as standard

X-ray An X-ray, or, much less commonly, X-radiation, is a penetrating form of high-energy electromagnetic radiation. Most X-rays have a wavelength ranging from 10 picometers to 10 nanometers, corresponding to frequencies in the range 30&nb ...

contrast agents.

Lamp mantles

Another major use in the past was in

gas mantle A Coleman white gas lantern mantle glowing at full brightness An incandescent gas mantle, gas mantle or Welsbach mantle is a device for generating incandescent bright white light when heated by a flame. The name refers to its original heat sou ...

of lanterns developed by

Carl Auer von Welsbach Carl Auer von Welsbach (1 September 1858 – 4 August 1929), who received the Austrian noble title of Freiherr Auer von Welsbach in 1901, was an Austrian scientist and inventor, who separated didymium into the elements neodymium and praseo ...

in 1890, which are composed of 99 percent ThO₂ and 1%

cerium(IV) oxide Cerium(IV) oxide, also known as ceric oxide, ceric dioxide, ceria, cerium oxide or cerium dioxide, is an oxide of the rare-earth metal cerium. It is a pale yellow-white powder with the chemical formula CeO2. It is an important commercial produc ...

. 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. Some mantles still use thorium, but

yttrium oxide Yttrium oxide may refer to: * Yttrium(II) oxide, YO, a dark brown solid * Yttrium(III) oxide Yttrium oxide, also known as yttria, is Y2 O3. It is an air-stable, white solid substance. The thermal conductivity of yttrium oxide is 27 W/(m·K). ...

(or sometimes

zirconium oxide Zirconium dioxide (), sometimes known as zirconia (not to be confused with zircon), is a white crystalline oxide of zirconium. Its most naturally occurring form, with a monoclinic crystalline structure, is the mineral baddeleyite. A dopant stabi ...

) is used increasingly as a replacement.

Glass manufacture

When added to

glass Glass is a non- crystalline, often transparent, amorphous solid that has widespread practical, technological, and decorative use in, for example, window panes, tableware, and optics. Glass is most often formed by rapid cooling (quenchin ...

, thorium dioxide helps increase its

refractive index In optics, the refractive index (or refraction index) of an optical medium is a dimensionless number that gives the indication of the light bending ability of that medium. The refractive index determines how much the path of light is bent, ...

and decrease

dispersion Dispersion may refer to: Economics and finance *Dispersion (finance), a measure for the statistical distribution of portfolio returns *Price dispersion, a variation in prices across sellers of the same item *Wage dispersion, the amount of variatio ...

. Such glass finds application in high-quality lenses for cameras and scientific instruments. 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. 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.

References

Cited sources

* {{Authority control Hepatotoxins Oxides Thorium compounds Refractory materials Fluorite crystal structure