|Pronunciation|| / /|
|Appearance||silvery, often with black tarnish|
|Standard atomic weight Ar, std(Th)||232.0377(4)|
|Thorium in the periodic table|
|Atomic number (Z)||90|
|Electron configuration||[ Rn ] 6d2 7s2|
Electrons per shell
|2, 8, 18, 32, 18, 10, 2|
|Phase at STP||solid|
|Melting point||2023 K (1750 °C,3182 °F)|
|Boiling point||5061 K(4788 °C,8650 °F)|
|Density (near r.t.)||11.7 g/cm3|
|Heat of fusion||13.81 kJ/mol|
|Heat of vaporisation||514 kJ/mol|
|Molar heat capacity||26.230 J/(mol·K)|
| Vapour pressure |
|Oxidation states||+1, +2, +3, +4 (a weakly basic oxide)|
|Electronegativity||Pauling scale: 1.3|
|Atomic radius||empirical:179.8 pm|
|Covalent radius||206±6 pm|
|Spectral lines of thorium|
|Crystal structure|| face-centred cubic (fcc)|
|Speed of sound thin rod||2490 m/s(at 20 °C)|
|Thermal expansion||11.0 µm/(m·K)(at 25 °C)|
|Thermal conductivity||54.0 W/(m·K)|
|Electrical resistivity||157 nΩ·m(at 0 °C)|
|Magnetic susceptibility||132.0·10−6 cm3/mol(293 K)|
|Young's modulus||79 GPa|
|Shear modulus||31 GPa|
|Bulk modulus||54 GPa|
|Vickers hardness||295–685 MPa|
|Brinell hardness||390–1500 MPa|
|Naming||after Thor, the Norse god of thunder|
|Discovery||Jöns Jakob Berzelius (1829)|
|Main isotopes 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 hard, malleable, and has a high melting point. Thorium is an electropositive actinide whose chemistry is dominated by the +4 oxidation state; it is quite reactive and can ignite in air when finely divided.
Radioactive decay is the process by which an unstable atomic nucleus loses energy by emitting radiation, such as an alpha particle, beta particle with neutrino or only a neutrino in the case of electron capture, or a gamma ray or electron in the case of internal conversion. A material containing unstable nuclei is considered radioactive. Certain highly excited short-lived nuclear states can decay through neutron emission, or more rarely, proton emission.
A chemical element is a species of atom having the same number of protons in their atomic nuclei. For example, the atomic number of oxygen is 8, so the element oxygen consists of all atoms which have 8 protons.
In chemistry, a symbol is an abbreviation for a chemical element. Symbols for chemical elements normally consist of one or two letters from the Latin alphabet and are written with the first letter capitalised.
All known thorium isotopes are unstable. The most stable isotope, 232Th, has a half-life of 14.05 billion years, or about the age of the universe; it decays very slowly via alpha decay, starting a decay chain named the thorium series that ends at stable 208 Pb. On Earth, thorium, bismuth, and uranium are the only three radioactive elements that still occur naturally in large quantities as primordial elements. It is estimated to be over three times as abundant as uranium in the Earth's crust, and is chiefly refined from monazite sands as a by-product of extracting rare-earth metals.
Isotopes are variants of a particular chemical element which differ in neutron number, and consequently in nucleon number. All isotopes of a given element have the same number of protons but different numbers of neutrons in each atom.
In physical cosmology, the age of the universe is the time elapsed since the Big Bang. The current measurement of the age of the universe is 13.787±0.020 billion (109) years within the Lambda-CDM concordance model. The uncertainty has been narrowed down to 20 million years, based on a number of studies which all gave extremely similar figures for the age. These include studies of the microwave background radiation, and measurements by the Planck spacecraft, the Wilkinson Microwave Anisotropy Probe and other probes. Measurements of the cosmic background radiation give the cooling time of the universe since the Big Bang, and measurements of the expansion rate of the universe can be used to calculate its approximate age by extrapolating backwards in time.
Alpha decay or α-decay is a type of radioactive decay in which an atomic nucleus emits an alpha particle and thereby transforms or 'decays' into a different atomic nucleus, with a mass number that is reduced by four and an atomic number that is reduced by two. An alpha particle is identical to the nucleus of a helium-4 atom, which consists of two protons and two neutrons. It has a charge of +2 e and a mass of 4 u. For example, uranium-238 decays to form thorium-234. Alpha particles have a charge +2 e, but as a nuclear equation describes a nuclear reaction without considering the electrons – a convention that does not imply that the nuclei necessarily occur in neutral atoms – the charge is not usually shown.
Thorium was discovered in 1829 by the Norwegian amateur mineralogist Morten Thrane Esmark and identified by the Swedish chemist Jöns Jacob Berzelius, who named it after Thor, the Norse god of thunder. Its first applications were developed in the late 19th century. Thorium's radioactivity was widely acknowledged during the first decades of the 20th century. In the second half of the century, thorium was replaced in many uses due to concerns about its radioactivity.
Hans Morten Thrane Esmark was a Norwegian priest and mineralogist. He is most noted for first locating the mineral thorite.
Baron Jöns Jacob Berzelius, known throughout his life as Jacob Berzelius, was a Swedish chemist. Berzelius is considered, along with Robert Boyle, John Dalton, and Antoine Lavoisier, to be one of the founders of modern chemistry.
In Germanic mythology, Thor is a hammer-wielding god associated with thunder, lightning, storms, oak trees, strength, the protection of mankind and also hallowing and fertility. Besides Old Norse Þórr, extensions of the god occur in Old English as Þunor and in Old High German as Donar. All forms of the deity stem from a Common Germanic *Þunraz.
Thorium is still being used as an alloying element in TIG welding electrodes but is slowly being replaced in the field with different compositions. It was also material in high-end optics and scientific instrumentation, and as the light source in gas mantles, but these uses have become marginal. It has been suggested as a replacement for uranium as nuclear fuel in nuclear reactors, and several thorium reactors have been built.
An incandescent gas mantle, gas mantle or Welsbach mantle is a device for generating bright white light when heated by a flame. The name refers to its original heat source in gas lights, which filled the streets of Europe and North America in the late 19th century, mantle referring to the way it is hung above the flame. Today it is still used in portable camping lanterns, pressure lanterns and some oil lamps.
A nuclear reactor, formerly known as an atomic pile, is a device used to initiate and control a self-sustained nuclear chain reaction. Nuclear reactors are used at nuclear power plants for electricity generation and in nuclear marine propulsion. Heat from nuclear fission is passed to a working fluid, which in turn runs through steam turbines. These either drive a ship's propellers or turn electrical generators' shafts. Nuclear generated steam in principle can be used for industrial process heat or for district heating. Some reactors are used to produce isotopes for medical and industrial use, or for production of weapons-grade plutonium. As of early 2019, the IAEA reports there are 454 nuclear power reactors and 226 nuclear research reactors in operation around the world.
Thorium is a moderately soft, paramagnetic, bright silvery radioactive actinide metal. In the periodic table, it lies to the right of actinium, to the left of protactinium, and below cerium. Pure thorium is very ductile and, as normal for metals, can be cold-rolled, swaged, and drawn. °C; body-centred cubic) and one at high pressure (around 100 GPa; body-centred tetragonal).At room temperature, thorium metal has a face-centred cubic crystal structure; it has two other forms, one at high temperature (over 1360
Paramagnetism is a form of magnetism whereby some materials are weakly attracted by an externally applied magnetic field, and form internal, induced magnetic fields in the direction of the applied magnetic field. In contrast with this behavior, diamagnetic materials are repelled by magnetic fields and form induced magnetic fields in the direction opposite to that of the applied magnetic field. Paramagnetic materials include most chemical elements and some compounds; they have a relative magnetic permeability slightly greater than 1 and hence are attracted to magnetic fields. The magnetic moment induced by the applied field is linear in the field strength and rather weak. It typically requires a sensitive analytical balance to detect the effect and modern measurements on paramagnetic materials are often conducted with a SQUID magnetometer.
The periodic table, also known as the periodic table of elements, is a tabular display of the chemical elements, which are arranged by atomic number, electron configuration, and recurring chemical properties. The structure of the table shows periodic trends. The seven rows of the table, called periods, generally have metals on the left and non-metals on the right. The columns, called groups, contain elements with similar chemical behaviours. Six groups have accepted names as well as assigned numbers: for example, group 17 elements are the halogens; and group 18 are the noble gases. Also displayed are four simple rectangular areas or blocks associated with the filling of different atomic orbitals.
Actinium is a chemical element with the symbol Ac and atomic number 89. It was first isolated by French chemist André-Louis Debierne in 1899. Friedrich Oskar Giesel later independently isolated it in 1902 and, unaware that it was already known, gave it the name emanium. Actinium gave the name to the actinide series, a group of 15 similar elements between actinium and lawrencium in the periodic table. It is also sometimes considered the first of the 7th-period transition metals, although lawrencium is less commonly given that position. Together with polonium, radium, and radon, actinium was one of the first non-primordial radioactive elements to be isolated.
Thorium metal has a bulk modulus (a measure of resistance to compression of a material) of 54 GPa, about the same as tin's (58.2 GPa). Aluminium's is 75.2 GPa; copper's 137.8 GPa; and mild steel's is 160–169 GPa. Thorium is about as hard as soft steel, so when heated it can be rolled into sheets and pulled into wire.
The bulk modulus of a substance is a measure of how resistant to compression that substance is. It is defined as the ratio of the infinitesimal pressure increase to the resulting relative decrease of the volume. Other moduli describe the material's response (strain) to other kinds of stress: the shear modulus describes the response to shear, and Young's modulus describes the response to linear stress. For a fluid, only the bulk modulus is meaningful. For a complex anisotropic solid such as wood or paper, these three moduli do not contain enough information to describe its behaviour, and one must use the full generalized Hooke's law.
Tin is a chemical element with the symbol Sn (from Latin: stannum) and atomic number 50. Tin is a silvery metal that characteristicly has a faint yellow hue. Tin, like indium, is soft enough to be cut without much force. When a bar of tin is bent the so-called "tin cry" can be heard as a result of sliding tin crystals reforming; this trait is shared by indium, cadmium and frozen mercury. Pure tin after solidifying keeps a mirror-like appearance similar to most metals. However, in most tin alloys (such as pewter) the metal solidifies with a dull gray color. Tin is a post-transition metal in group 14 of the periodic table of elements. It is obtained chiefly from the mineral cassiterite, which contains stannic oxide, SnO2. Tin shows a chemical similarity to both of its neighbors in group 14, germanium and lead, and has two main oxidation states, +2 and the slightly more stable +4. Tin is the 49th most abundant element on Earth and has, with 10 stable isotopes, the largest number of stable isotopes in the periodic table, thanks to its magic number of protons. It has two main allotropes: at room temperature, the stable allotrope is β-tin, a silvery-white, malleable metal, but at low temperatures, it transforms into the less dense grey α-tin, which has the diamond cubic structure. Metallic tin does not easily oxidize in air.
Aluminium is a chemical element with the symbol Al and atomic number 13. It is a silvery-white, soft, non-magnetic and ductile metal in the boron group. By mass, aluminium makes up about 8% of the Earth's crust; it is the third most abundant element after oxygen and silicon and the most abundant metal in the crust, though it is less common in the mantle below. The chief ore of aluminium is bauxite. Aluminium metal is highly reactive, such that native specimens are rare and limited to extreme reducing environments. Instead, it is found combined in over 270 different minerals.
Thorium is nearly half as dense as uranium and plutonium and is harder than either of them. K. Thorium's melting point of 1750 °C is above both those of actinium (1227 °C) and protactinium (1568 °C). At the start of period 7, from francium to thorium, the melting points of the elements increase (as in other periods), because the number of delocalised electrons each atom contributes increases from one in francium to four in thorium, leading to greater attraction between these electrons and the metal ions as their charge increases from one to four. After thorium, there is a new downward trend in melting points from thorium to plutonium, where the number of f electrons increases from about 0.4 to about 6: this trend is due to the increasing hybridisation of the 5f and 6d orbitals and the formation of directional bonds resulting in more complex crystal structures and weakened metallic bonding. (The f-electron count for thorium is a non-integer due to a 5f–6d overlap.) Among the actinides up to californium, which can be studied in at least milligram quantities, thorium has the highest melting and boiling points and second-lowest density; only actinium is lighter. Thorium's boiling point of 4788 °C is the fifth-highest among all the elements with known boiling points.It becomes superconductive below 1.4
The properties of thorium vary widely depending on the degree of impurities in the sample. The major impurity is usually thorium dioxide (ThO2); even the purest thorium specimens usually contain about a tenth of a percent of the dioxide. and 11.66 g/cm3: these are slightly lower than the theoretically expected value of 11.7 g/cm3 calculated from thorium's lattice parameters, perhaps due to microscopic voids forming in the metal when it is cast. These values lie between those of its neighbours actinium (10.1 g/cm3) and protactinium (15.4 g/cm3), part of a trend across the early actinides.Experimental measurements of its density give values between 11.5
Thorium can form alloys with many other metals. Addition of small proportions of thorium improves the mechanical strength of magnesium, and thorium-aluminum alloys have been considered as a way to store thorium in proposed future thorium nuclear reactors. Thorium forms eutectic mixtures with chromium and uranium, and it is completely miscible in both solid and liquid states with its lighter congener cerium.
All but two elements up to bismuth (element 83) have an isotope that is practically stable for all purposes ("classically stable"), with the exceptions being technetium and promethium (elements 43 and 61). All elements from polonium (element 84) onward are measurably radioactive. 232Th is one of the three nuclides beyond bismuth (the other two being 235U and 238U) that have half-lives measured in billions of years; its half-life is 14.05 billion years, about three times the age of the earth, and slightly longer than the age of the universe. Four-fifths of the thorium present at Earth's formation has survived to the present. 232Th is the only isotope of thorium occurring in quantity in nature. Its stability is attributed to its closed nuclear shell with 142 neutrons. Thorium has a characteristic terrestrial isotopic composition, with atomic weight 232.0377(4). It is one of only four radioactive elements (along with bismuth, protactinium and uranium) that occur in large enough quantities on Earth for a standard atomic weight to be determined.
Thorium nuclei are susceptible to alpha decay because the strong nuclear force cannot overcome the electromagnetic repulsion between their protons. years and alpha decay predominates.The alpha decay of 232Th initiates the 4n decay chain which includes isotopes with a mass number divisible by 4 (hence the name; it is also called the thorium series after its progenitor). This chain of consecutive alpha and beta decays begins with the decay of 232Th to 228Ra and terminates at 208Pb. Any sample of thorium or its compounds contains traces of these daughters, which are isotopes of thallium, lead, bismuth, polonium, radon, radium, and actinium. Natural thorium samples can be chemically purified to extract useful daughter nuclides, such as 212Pb, which is used in nuclear medicine for cancer therapy. 227Th (alpha emitter with a 18.68 days half-life) can also be used in cancer treatments such as targeted alpha therapies. 232Th also very occasionally undergoes spontaneous fission rather than alpha decay, and has left evidence of doing so in its minerals (as trapped xenon gas formed as a fission product), but the partial half-life of this process is very large at over 1021
Thirty radioisotopes have been characterised, which range in mass number from 209 years), 229Th (7,340 years), 228Th (1.92 years), 234Th (24.10 days), and 227Th (18.68 days). All of these isotopes occur in nature as trace radioisotopes due to their presence in the decay chains of 232Th, 235U, 238U, and 237 Np: the last of these is long extinct in nature due to its short half-life (2.14 million years), but is continually produced in minute traces from neutron capture in uranium ores. All of the remaining thorium isotopes have half-lives that are less than thirty days and the majority of these have half-lives that are less than ten minutes.to 238. After 232Th, the most stable of them (with respective half-lives) are 230Th (75,380
In deep seawaters the isotope 230Th makes up to 0.04% of natural thorium.This is because its parent 238U is soluble in water, but 230Th is insoluble and precipitates into the sediment. Uranium ores with low thorium concentrations can be purified to produce gram-sized thorium samples of which over a quarter is the 230Th isotope, since 230Th is one of the daughters of 238U. The International Union of Pure and Applied Chemistry (IUPAC) reclassified thorium as a binuclidic element in 2013; it had formerly been considered a mononuclidic element.
Thorium has three known nuclear isomers (or metastable states), 216m1Th, 216m2Th, and 229mTh. 229mTh has the lowest known excitation energy of any isomer, 7.6±0.5 eV. This is so low that when it undergoes isomeric transition, the emitted gamma radiation is in the ultraviolet range.measured to be
Different isotopes of thorium are chemically identical, but have slightly differing physical properties: for example, the densities of pure 228Th, 229Th, 230Th, and 232Th are respectively expected to be 11.5, 11.6, 11.6, and 11.7 g/cm3. The isotope 229Th is expected to be fissionable with a bare critical mass of 2839 kg, although with steel reflectors this value could drop to 994 kg. 232Th is not fissionable, but it is fertile as it can be converted to fissile 233U by neutron capture and subsequent beta decay.
Two radiometric dating methods involve thorium isotopes: uranium–thorium dating, based on the decay of 234U to 230Th, and ionium–thorium dating, which measures the ratio of 232Th to 230Th.These rely on the fact that 232Th is a primordial radioisotope, but 230Th only occurs as an intermediate decay product in the decay chain of 238U. Uranium–thorium dating is a relatively short-range process because of the short half-lives of 234U and 230Th relative to the age of the Earth: it is also accompanied by a sister process involving the alpha decay of 235U into 231Th, which very quickly becomes the longer-lived 231Pa, and this process is often used to check the results of uranium–thorium dating. Uranium–thorium dating is commonly used to determine the age of calcium carbonate materials such as speleothem or coral, because uranium is more soluble in water than thorium and protactinium, which are selectively precipitated into ocean-floor sediments, where their ratios are measured. The scheme has a range of several hundred thousand years. Ionium–thorium dating is a related process, which exploits the insolubility of thorium (both 232Th and 230Th) and thus its presence in ocean sediments to date these sediments by measuring the ratio of 232Th to 230Th. Both of these dating methods assume that the proportion of 230Th to 232Th is a constant during the period when the sediment layer was formed, that the sediment did not already contain thorium before contributions from the decay of uranium, and that the thorium cannot migrate within the sediment layer.
A thorium atom has 90 electrons, of which four are valence electrons. Three atomic orbitals are theoretically available for the valence electrons to occupy: 5f, 6d, and 7s.Despite thorium's position in the f-block of the periodic table, it has an anomalous [Rn]6d27s2 electron configuration in the ground state, as the 5f and 6d subshells in the early actinides are very close in energy, even more so than the 4f and 5d subshells of the lanthanides: thorium's 6d subshells are lower in energy than its 5f subshells, because its 5f subshells are not well-shielded by the filled 6s and 6p subshells and are destabilized. This is due to relativistic effects, which become stronger near the bottom of the periodic table, specifically the relativistic spin–orbit interaction. The closeness in energy levels of the 5f, 6d, and 7s energy levels of thorium results in thorium almost always losing all four valence electrons and occurring in its highest possible oxidation state of +4. This is different from its lanthanide congener cerium, in which +4 is also the highest possible state, but +3 plays an important role and is more stable. Thorium is much more similar to the transition metals zirconium and hafnium than to cerium in its ionization energies and redox potentials, and hence also in its chemistry: this transition-metal-like behaviour is the norm in the first half of the actinide series.
Despite the anomalous electron configuration for gaseous thorium atoms, metallic thorium shows significant 5f involvement. This was first realized in 1995, when it was pointed out that a hypothetical metallic state of thorium that had the [Rn]6d27s2 configuration with the 5f orbitals above the Fermi level should be hexagonal close packed like the group 4 elements titanium, zirconium, and hafnium, and not face-centred cubic as it actually is. The actual crystal structure can only be explained when the 5f states are invoked, proving that thorium, and not protactinium, acts as the first actinide metallurgically.The 5f character of thorium is also clear in the rare and highly unstable +3 oxidation state, in which thorium exhibits the electron configuration [Rn]5f1.
Tetravalent thorium compounds are usually colourless or yellow, like those of silver or lead, as the Th4+ ion has no 5f or 6d electrons.Thorium chemistry is therefore largely that of an electropositive metal forming a single diamagnetic ion with a stable noble-gas configuration, indicating a similarity between thorium and the main group elements of the s-block. Thorium and uranium are the most investigated of the radioactive elements because their radioactivity is low enough not to require special handling in the laboratory.
Thorium is a highly reactive and electropositive metal. With a standard reduction potential of −1.90 V for the Th4+/Th couple, it is somewhat more electropositive than zirconium or aluminium. Finely divided thorium metal can exhibit pyrophoricity, spontaneously igniting in air. When heated in air, thorium turnings ignite and burn with a brilliant white light to produce the dioxide. In bulk, the reaction of pure thorium with air is slow, although corrosion may occur after several months; most thorium samples are contaminated with varying degrees of the dioxide, which greatly accelerates corrosion. Such samples slowly tarnish, becoming grey and finally black at the surface.
At standard temperature and pressure, thorium is slowly attacked by water, but does not readily dissolve in most common acids, with the exception of hydrochloric acid, where it dissolves leaving a black insoluble residue of ThO(OH,Cl)H.It dissolves in concentrated nitric acid containing a small quantity of catalytic fluoride or fluorosilicate ions; if these are not present, passivation by the nitrate can occur, as with uranium and plutonium.
Most binary compounds of thorium with nonmetals may be prepared by heating the elements together. °C) of any known oxide. It is somewhat hygroscopic and reacts readily with water and many gases; it dissolves easily in concentrated nitric acid in the presence of fluoride.In air, thorium burns to form ThO2, which has the fluorite structure. Thorium dioxide is a refractory material, with the highest melting point (3390
When heated in air, thorium dioxide emits intense blue light; the light becomes white when ThO2 is mixed with its lighter homologue cerium dioxide (CeO2, ceria): this is the basis for its previously common application in gas mantles. : Ce acts as a catalyst for the recombination of free radicals that appear in high concentration in a flame, whose deexcitation releases large amounts of energy. The addition of 1% cerium dioxide, as in gas mantles, heightens the effect by increasing emissivity in the visible region of the spectrum; and because cerium, unlike thorium, can occur in multiple oxidation states, its charge and hence visible emissivity will depend on the region on the flame it is found in (as such regions vary in their chemical composition and hence how oxidising or reducing they are).A flame is not necessary for this effect: in 1901, it was discovered that a hot Welsbach gas mantle (using ThO2 with 1% CeO2) remained at "full glow" when exposed to a cold unignited mixture of flammable gas and air. The light emitted by thorium dioxide is higher in wavelength than the blackbody emission expected from incandescence at the same temperature, an effect called candoluminescence. It occurs because ThO2
Several binary thorium chalcogenides and oxychalcogenides are also known with sulfur, selenium, and tellurium.
All four thorium tetrahalides are known, as are some low-valent bromides and iodides: ThF2−
6, which precipitates as an insoluble salt, K2ThF6.
Thorium borides, carbides, silicides, and nitrides are refractory materials, like those of uranium and plutonium, and have thus received attention as possible nuclear fuels. K; at standard temperature and pressure, it conducts electricity like a metal. The hydrides are thermally unstable and readily decompose upon exposure to air or moisture.All four heavier pnictogens (phosphorus, arsenic, antimony, and bismuth) also form binary thorium compounds. Thorium germanides are also known. Thorium reacts with hydrogen to form the thorium hydrides ThH2 and Th4H15, the latter of which is superconducting below 7.5–8
In an acidic aqueous solution, thorium occurs as the tetrapositive aqua ion [Th(H2O)9]4+, which has tricapped trigonal prismatic molecular geometry: < 3, the solutions of thorium salts are dominated by this cation. The Th4+ ion is the largest of the tetrapositive actinide ions, and depending on the coordination number can have a radius between 0.95 and 1.14 Å. It is quite acidic due to its high charge, slightly stronger than sulfurous acid: thus it tends to undergo hydrolysis and polymerisation (though to a lesser extent than Fe3+), predominantly to [Th2(OH)2]6+ in solutions with pH 3 or below, but in more alkaline solution polymerisation continues until the gelatinous hydroxide Th(OH)4 forms and precipitates out (though equilibrium may take weeks to be reached, because the polymerisation usually slows down before the precipitation). As a hard Lewis acid, Th4+ favours hard ligands with oxygen atoms as donors: complexes with sulfur atoms as donors are less stable and are more prone to hydrolysis.at pH
High coordination numbers are the rule for thorium due to its large size. Thorium nitrate pentahydrate was the first known example of coordination number 11, the oxalate tetrahydrate has coordination number 10, and the borohydride (first prepared in the Manhattan Project) has coordination number 14.These thorium salts are known for their high solubility in water and polar organic solvents.
Many other inorganic thorium compounds with polyatomic anions are known, such as the perchlorates, sulfates, sulfites, nitrates, carbonates, phosphates, vanadates, molybdates, and chromates, and their hydrated forms.They are important in thorium purification and the disposal of nuclear waste, but most of them have not yet been fully characterized, especially regarding their structural properties. For example, thorium nitrate is produced by reacting thorium hydroxide with nitric acid: it is soluble in water and alcohols and is an important intermediate in the purification of thorium and its compounds. Thorium complexes with organic ligands, such as oxalate, citrate, and EDTA, are much more stable. In natural thorium-containing waters, organic thorium complexes usually occur in concentrations orders of magnitude higher than the inorganic complexes, even when the concentrations of inorganic ligands are much greater than those of organic ligands.
Most of the work on organothorium compounds has focused on the cyclopentadienyl complexes and cyclooctatetraenyls. Like many of the early and middle actinides (up to americium, and also expected for curium), thorium forms a cyclooctatetraenide complex: the yellow Th(C8H8)2, thorocene. It is isotypic with the better-known analogous uranium compound uranocene. °C. Half sandwich compounds are also known, such as (η8-C8H8)ThCl2(THF)2, which has a piano-stool structure and is made by reacting thorocene with thorium tetrachloride in tetrahydrofuran.It can be prepared by reacting K2C8H8 with thorium tetrachloride in tetrahydrofuran (THF) at the temperature of dry ice, or by reacting thorium tetrafluoride with MgC8H8. It is unstable in air and decomposes in water or at 190
The simplest of the cyclopentadienyls are Th(C5H5)3 and Th(C5H5)4: many derivatives are known. The former (which has two forms, one purple and one green) is a rare example of thorium in the formal +3 oxidation state;a formal +2 oxidation state occurs in a derivative. The chloride derivative [Th(C5H5)3Cl] is prepared by heating thorium tetrachloride with limiting K(C5H5) used (other univalent metal cyclopentadienyls can also be used). The alkyl and aryl derivatives are prepared from the chloride derivative and have been used to study the nature of the Th–C sigma bond.
Other organothorium compounds are not well-studied. Tetrabenzylthorium, Th(CH2C6H5), and tetraallylthorium, Th(C3H5)4, are known, but their structures have not been determined. They decompose slowly at room temperature. Thorium forms the monocapped trigonal prismatic anion [Th(CH3)7]3−, heptamethylthorate, which forms the salt [Li(tmeda)]3[ThMe7] (tmeda= Me2NCH2CH2NMe2). Although one methyl group is only attached to the thorium atom (Th–C distance 257.1 pm) and the other six connect the lithium and thorium atoms (Th–C distances 265.5–276.5 pm), they behave equivalently in solution. Tetramethylthorium, Th(CH3)4, is not known, but its adducts are stabilised by phosphine ligands.
232Th is a primordial nuclide, having existed in its current form for over ten billion years; it was forged in the cores of dying stars through the r-process and scattered across the galaxy by supernovae and neutron star mergers.The letter "r" stands for "rapid neutron capture", and occurs in core-collapse supernovae, where heavy seed nuclei such as 56Fe rapidly capture neutrons, running up against the neutron drip line, as neutrons are captured much faster than the resulting nuclides can beta decay back toward stability. Neutron capture is the only way for stars to synthesise elements beyond iron because of the increased Coulomb barriers that make interactions between charged particles difficult at high atomic numbers and the fact that fusion beyond 56Fe is endothermic. Because of the abrupt loss of stability past 209Bi, the r-process is the only process of stellar nucleosynthesis that can create thorium and uranium; all other processes are too slow and the intermediate nuclei alpha decay before they capture enough neutrons to reach these elements.
In the universe, thorium is among the rarest of the primordial elements, because it is one of the two elements that can be produced only in the r-process (the other being uranium), and also because it has slowly been decaying away from the moment it formed. The only primordial elements rarer than thorium are thulium, lutetium, tantalum, and rhenium, the odd-numbered elements just before the third peak of r-process abundances around the heavy platinum group metals, as well as uranium.In the distant past the abundances of thorium and uranium were enriched by the decay of plutonium and curium isotopes, and thorium was enriched relative to uranium by the decay of 236U to 232Th and the natural depletion of 235U, but these sources have long since decayed and no longer contribute.
In the Earth's crust, thorium is much more abundant: with an abundance of 8.1 parts per million (ppm), it is one of the most abundant of the heavy elements, almost as abundant as lead (13 ppm) and more abundant than tin (2.1 ppm). This is because thorium is likely to form oxide minerals that do not sink into the core; it is classified as a lithophile. Common thorium compounds are also poorly soluble in water. Thus, even though the refractory elements have the same relative abundances in the Earth as in the Solar System as a whole, there is more accessible thorium than heavy platinum group metals in the crust.
Natural thorium is usually almost pure 232Th, which is the longest-lived and most stable isotope of thorium, having a half-life comparable to the age of the universe.Its radioactive decay is the largest single contributor to the Earth's internal heat; the other major contributors are the shorter-lived primordial radionuclides, which are 238U, 40K, and 235U in descending order of their contribution. (At the time of the Earth's formation, 40K and 235U contributed much more by virtue of their short half-lives, but they have decayed more quickly, leaving the contribution from 232Th and 238U predominant.) Its decay accounts for a gradual decrease of thorium content of the Earth: the planet currently has around 85% of the amount present at the formation of the Earth. The other natural thorium isotopes are much shorter-lived; of them, only 230Th is usually detectable, occurring in secular equilibrium with its parent 238U, and making up at most 0.04% of natural thorium.
Thorium only occurs as a minor constituent of most minerals, and was for this reason previously thought to be rare.Soil normally contains about 6 ppm of thorium.
In nature, thorium occurs in the +4 oxidation state, together with uranium(IV), zirconium(IV), hafnium(IV), and cerium(IV), and also with scandium, yttrium, and the trivalent lanthanides which have similar ionic radii.Because of thorium's radioactivity, minerals containing it are often metamict (amorphous), their crystal structure having been damaged by the alpha radiation produced by thorium. An extreme example is ekanite, (Ca,Fe,Pb)2(Th,U)Si8O20, which almost never occurs in nonmetamict form due to the thorium it contains.
Monazite (chiefly phosphates of various rare-earth elements) is the most important commercial source of thorium because it occurs in large deposits worldwide, principally in India, South Africa, Brazil, Australia, and Malaysia. It contains around 2.5% thorium on average, although some deposits may contain up to 20%.Monazite is a chemically unreactive mineral that is found as yellow or brown sand; its low reactivity makes it difficult to extract thorium from it. Allanite (chiefly silicates-hydroxides of various metals) can have 0.1–2% thorium and zircon (chiefly zirconium silicate, ZrSiO4) up to 0.4% thorium.
Thorium dioxide occurs as the rare mineral thorianite. Due to its being isotypic with uranium dioxide, these two common actinide dioxides can form solid-state solutions and the name of the mineral changes according to the ThO2 content. SiO4−
4 ions are often replaced with M3+ (where M= Sc, Y, or Ln) and phosphate (PO3−
4) ions respectively. Because of the great insolubility of thorium dioxide, thorium does not usually spread quickly through the environment when released. The Th4+ ion is soluble, especially in acidic soils, and in such conditions the thorium concentration can reach 40 ppm.
In 1815, the Swedish chemist Jöns Jacob Berzelius analysed an unusual sample of gadolinite from a copper mine in Falun, central Sweden. He noted impregnated traces of a white mineral, which he cautiously assumed to be an earth (oxide in modern chemical nomenclature) of an unknown element. Berzelius had already discovered two elements, cerium and selenium, but he had made a public mistake once, announcing a new element, gahnium, that turned out to be zinc oxide.Berzelius privately named the putative element "thorium" in 1817 and its supposed oxide "thorina" after Thor, the Norse god of thunder. In 1824, after more deposits of the same mineral in Vest-Agder, Norway, were discovered, he retracted his findings, as the mineral (later named xenotime) proved to be mostly yttrium orthophosphate.
In 1828, Morten Thrane Esmark found a black mineral on Løvøya island, Telemark county, Norway. He was a Norwegian priest and amateur mineralogist who studied the minerals in Telemark, where he served as vicar. He commonly sent the most interesting specimens, such as this one, to his father, Jens Esmark, a noted mineralogist and professor of mineralogy and geology at the Royal Frederick University in Christiania (today called Oslo).The elder Esmark determined that it was not a known mineral and sent a sample to Berzelius for examination. Berzelius determined that it contained a new element. He published his findings in 1829, having isolated an impure sample by reducing KThF5 with potassium metal. Berzelius reused the name of the previous supposed element discovery and named the source mineral thorite.
Berzelius made some initial characterizations of the new metal and its chemical compounds: he correctly determined that the thorium–oxygen mass ratio of thorium oxide was 7.5 (its actual value is close to that, ~7.3), but he assumed the new element was divalent rather than tetravalent, and so calculated that the atomic mass was 7.5 times that of oxygen (120 amu); it is actually 15 times as large.He determined that thorium was a very electropositive metal, ahead of cerium and behind zirconium in electropositivity. Metallic thorium was isolated for the first time in 1914 by Dutch entrepreneurs Dirk Lely Jr. and Lodewijk Hamburger.
In the periodic table published by Dmitri Mendeleev in 1869, thorium and the rare-earth elements were placed outside the main body of the table, at the end of each vertical period after the alkaline earth metals. This reflected the belief at that time that thorium and the rare-earth metals were divalent. With the later recognition that the rare earths were mostly trivalent and thorium was tetravalent, Mendeleev moved cerium and thorium to group IV in 1871, which also contained the modern carbon group (group 14) and titanium group (group 4), because their maximum oxidation state was +4.Cerium was soon removed from the main body of the table and placed in a separate lanthanide series; thorium was left with group 4 as it had similar properties to its supposed lighter congeners in that group, such as titanium and zirconium.
While thorium was discovered in 1828 its first application dates only from 1885, when Austrian chemist Carl Auer von Welsbach invented the gas mantle, a portable source of light which produces light from the incandescence of thorium oxide when heated by burning gaseous fuels.Many applications were subsequently found for thorium and its compounds, including ceramics, carbon arc lamps, heat-resistant crucibles, and as catalysts for industrial chemical reactions such as the oxidation of ammonia to nitric acid.
Thorium was first observed to be radioactive in 1898, by the German chemist Gerhard Carl Schmidt and later that year, independently, by the Polish-French physicist Marie Curie. It was the second element that was found to be radioactive, after the 1896 discovery of radioactivity in uranium by French physicist Henri Becquerel.Starting from 1899, the New Zealand physicist Ernest Rutherford and the American electrical engineer Robert Bowie Owens studied the radiation from thorium; initial observations showed that it varied significantly. It was determined that these variations came from a short-lived gaseous daughter of thorium, which they found to be a new element. This element is now named radon, the only one of the rare radioelements to be discovered in nature as a daughter of thorium rather than uranium.
After accounting for the contribution of radon, Rutherford, now working with the British physicist Frederick Soddy, showed how thorium decayed at a fixed rate over time into a series of other elements in work dating from 1900 to 1903. This observation led to the identification of the half-life as one of the outcomes of the alpha particle experiments that led to the disintegration theory of radioactivity.The biological effect of radiation was discovered in 1903. The newly discovered phenomenon of radioactivity excited scientists and the general public alike. In the 1920s, thorium's radioactivity was promoted as a cure for rheumatism, diabetes, and sexual impotence. In 1932, most of these uses were banned in the United States after a federal investigation into the health effects of radioactivity. 10,000 individuals in the United States had been injected with thorium during X-ray diagnosis; they were later found to suffer health issues such as leukaemia and abnormal chromosomes. Public interest in radioactivity had declined by the end of the 1930s.
Up to the late 19th century, chemists unanimously agreed that thorium and uranium were analogous to hafnium and tungsten; the existence of the lanthanides in the sixth row was considered to be a one-off fluke. In 1892, British chemist Henry Bassett postulated a second extra-long periodic table row to accommodate known and undiscovered elements, considering thorium and uranium to be analogous to the lanthanides. In 1913, Danish physicist Niels Bohr published a theoretical model of the atom and its electron orbitals, which soon gathered wide acceptance. The model indicated that the seventh row of the periodic table should also have f-shells filling before the d-shells that were filled in the transition elements, like the sixth row with the lanthanides preceding the 5d transition metals.The existence of a second inner transition series, in the form of the actinides, was not accepted until similarities with the electron structures of the lanthanides had been established; Bohr suggested that the filling of the 5f orbitals may be delayed to after uranium.
It was only with the discovery of the first transuranic elements, which from plutonium onward have dominant +3 and +4 oxidation states like the lanthanides, that it was realised that the actinides were indeed filling f-orbitals rather than d-orbitals, with the transition-metal-like chemistry of the early actinides being the exception and not the rule.In 1945, when American physicist Glenn T. Seaborg and his team had discovered the transuranic elements americium and curium, he realised that thorium was the second member of the actinide series and was filling an f-block row, instead of being the heavier congener of hafnium filling a fourth d-block row.
In the 1990s, most applications that do not depend on thorium's radioactivity declined quickly due to safety and environmental concerns as suitable safer replacements were found.Despite its radioactivity, the element has remained in use for applications where no suitable alternatives could be found. A 1981 study by the Oak Ridge National Laboratory in the United States estimated that using a thorium gas mantle every weekend would be safe for a person, but this was not the case for the dose received by people manufacturing the mantles or for the soils around some factory sites. Some manufacturers have changed to other materials, such as yttrium. As recently as 2007, some companies continued to manufacture and sell thorium mantles without giving adequate information about their radioactivity, with some even falsely claiming them to be non-radioactive.
Thorium has been used as a power source on a prototype scale. The earliest thorium-based reactor was built at the Indian Point Energy Center located in Buchanan, New York, United States in 1962. century, three reactors were built in India and twelve elsewhere. Large-scale research was begun in 1996 by the International Atomic Energy Agency to study the use of thorium reactors; a year later, the United States Department of Energy started their research. Alvin Radkowsky of Tel Aviv University in Israel was the head designer of Shippingport Atomic Power Station in Pennsylvania, the first American civilian reactor to breed thorium. He founded a consortium to develop thorium reactors, which included other laboratories: Raytheon Nuclear Inc. and Brookhaven National Laboratory in the United States, and the Kurchatov Institute in Russia. In the 21st century, thorium's potential for reducing nuclear proliferation and its waste characteristics led to renewed interest in the thorium fuel cycle.One of the largest supplies of thorium in the world is in the country of India, where there is not much uranium. In the 1950s India targeted achieving energy independence with their three-stage nuclear power programme. In most countries, uranium was relatively abundant and the progress of thorium-based reactors was slow; in the 20th
When gram quantities of plutonium were first produced in the Manhattan Project, it was discovered that a minor isotope (240Pu) underwent significant spontaneous fission, which brought into question the viability of a plutonium-fueled gun-type nuclear weapon. While the Los Alamos team began work on the implosion-type weapon to circumvent this issue, the Chicago team discussed reactor design solutions. Eugene Wigner proposed to use the 240Pu-contaminated plutonium to drive the conversion of thorium into 233U in a special converter reactor. It was hypothesized that the 233U would then be usable in a gun-type weapon, though concerns about contamination from 232U were voiced. Progress on the implosion weapon was sufficient, and this converter was not developed further, but the design had enormous influence on the development of nuclear energy. It was the first detailed description of a highly-enriched water-cooled, water-moderated reactor similar to future naval and power reactors.
During the Cold War the United States explored the possibility of using 232Th as a source of 233U to be used in a nuclear bomb; they fired a test bomb in 1955.They concluded that a 233U-fired bomb would be a very potent weapon, but it bore few sustainable "technical advantages" over the contemporary uranium–plutonium bombs, especially since 233U is difficult to produce in isotopically pure form.
Thorium metal was used in the radiation case of at least one nuclear weapon design deployed by the United States (the W71).
The low demand makes working mines for extraction of thorium alone not profitable, and it is almost always extracted with the rare earths, which themselves may be by-products of production of other minerals.The current reliance on monazite for production is due to thorium being largely produced as a by-product; other sources such as thorite contain more thorium and could easily be used for production if demand rose. Present knowledge of the distribution of thorium resources is poor, as low demand has led to exploration efforts being relatively minor. In 2014, world production of the monazite concentrate, from which thorium would be extracted, was 2,700 tonnes.
The common production route of thorium constitutes concentration of thorium minerals; extraction of thorium from the concentrate; purification of thorium; and (optionally) conversion to compounds, such as thorium dioxide.
There are two categories of thorium minerals for thorium extraction: primary and secondary. Primary deposits occur in acidic granitic magmas and pegmatites. They are concentrated, but of small size. Secondary deposits occur at the mouths of rivers in granitic mountain regions. In these deposits, thorium is enriched along with other heavy minerals.Initial concentration varies with the type of deposit.
For the primary deposits, the source pegmatites, which are usually obtained by mining, are divided into small parts and then undergo flotation. Alkaline earth metal carbonates may be removed after reaction with hydrogen chloride; then follow thickening, filtration, and calcination. The result is a concentrate with rare-earth content of up to 90%.Secondary materials (such as coastal sands) undergo gravity separation. Magnetic separation follows, with a series of magnets of increasing strength. Monazite obtained by this method can be as pure as 98%.
Industrial production in the 20th century relied on treatment with hot, concentrated sulfuric acid in cast iron vessels, followed by selective precipitation by dilution with water, as on the subsequent steps. This method relied on the specifics of the technique and the concentrate grain size; many alternatives have been proposed, but only one has proven effective economically: alkaline digestion with hot sodium hydroxide solution. This is more expensive than the original method but yields a higher purity of thorium; in particular, it removes phosphates from the concentrate.
Acid digestion is a two-stage process, involving the use of up to 93% sulfuric acid at 210–230 °C. First, 60% sulfuric acid is added, thickening the reaction mixture as products are formed. Then, fuming sulfuric acid is added and the mixture is kept at the same temperature for another five hours to reduce the volume of solution remaining after dilution. The concentration of the sulfuric acid is selected based on reaction rate and viscosity, which both increase with concentration, albeit with viscosity retarding the reaction. Increasing the temperature also speeds up the reaction, but temperatures of 300 °C and above must be avoided, because they cause insoluble thorium pyrophosphate to form. Since dissolution is very exothermic, the monazite sand cannot be added to the acid too quickly. Conversely, at temperatures below 200 °C the reaction does not go fast enough for the process to be practical. To ensure that no precipitates form to block the reactive monazite surface, the mass of acid used must be twice that of the sand, instead of the 60% that would be expected from stoichiometry. The mixture is then cooled to 70 °C and diluted with ten times its volume of cold water, so that any remaining monazite sinks to the bottom while the rare earths and thorium remain in solution. Thorium may then be separated by precipitating it as the phosphate at pH 1.3, since the rare earths do not precipitate until pH 2.
Alkaline digestion is carried out in 30–45% sodium hydroxide solution at about 140 °C for about three hours. Too high a temperature leads to the formation of poorly soluble thorium oxide and an excess of uranium in the filtrate, and too low a concentration of alkali leads to a very slow reaction. These reaction conditions are rather mild and require monazite sand with a particle size under 45 μm. Following filtration, the filter cake includes thorium and the rare earths as their hydroxides, uranium as sodium diuranate, and phosphate as trisodium phosphate. This crystallises trisodium phosphate decahydrate when cooled below 60 °C; uranium impurities in this product increase with the amount of silicon dioxide in the reaction mixture, necessitating recrystallisation before commercial use. The hydroxides are dissolved at 80 °C in 37% hydrochloric acid. Filtration of the remaining precipitates followed by addition of 47% sodium hydroxide results in the precipitation of thorium and uranium at about pH 5.8. Complete drying of the precipitate must be avoided, as air may oxidise cerium from the +3 to the +4 oxidation state, and the cerium(IV) formed can liberate free chlorine from the hydrochloric acid. The rare earths again precipitate out at higher pH. The precipitates are neutralised by the original sodium hydroxide solution, although most of the phosphate must first be removed to avoid precipitating rare-earth phosphates. Solvent extraction may also be used to separate out the thorium and uranium, by dissolving the resultant filter cake in nitric acid. The presence of titanium hydroxide is deleterious as it binds thorium and prevents it from dissolving fully.
High thorium concentrations are needed in nuclear applications. In particular, concentrations of atoms with high neutron capture cross-sections must be very low (for example, gadolinium concentrations must be lower than one part per million by weight). Previously, repeated dissolution and recrystallisation was used to achieve high purity. Today, liquid solvent extraction procedures involving selective complexation of Th4+ are used. For example, following alkaline digestion and the removal of phosphate, the resulting nitrato complexes of thorium, uranium, and the rare earths can be separated by extraction with tributyl phosphate in kerosene.
Non-radioactivity-related uses have been in decline since the 1950sdue to environmental concerns largely stemming from the radioactivity of thorium and its decay products.
Most thorium applications use its dioxide (sometimes called "thoria" in the industry), rather than the metal. This compound has a melting point of 3300 °C (6000 °F), the highest of all known oxides; only a few substances have higher melting points. This helps the compound remain solid in a flame, and it considerably increases the brightness of the flame; this is the main reason thorium is used in gas mantles. All substances emit energy (glow) at high temperatures, but the light emitted by thorium is nearly all in the visible spectrum, hence the brightness of thorium mantles. Energy, some of it in the form of visible light, is emitted when thorium is exposed to a source of energy itself, such as a cathode ray, heat or ultraviolet light. This effect is shared by cerium dioxide, which converts ultraviolet light into visible light more efficiently, but thorium dioxide gives a higher flame temperature, emitting less infrared light. Thorium in mantles, though still common, has been progressively replaced with yttrium since the late 1990s. According to the 2005 review by the United Kingdom's National Radiological Protection Board, "although [thoriated gas mantles] were widely available a few years ago, they are not any more."
During the production of incandescent filaments, recrystallisation of tungsten is significantly lowered by adding small amounts of thorium dioxide to the tungsten sintering powder before drawing the filaments.A small addition of thorium to tungsten thermocathodes considerably reduces the work function of electrons; as a result, electrons are emitted at considerably lower temperatures. Thorium forms a one-atom-thick layer on the surface of tungsten. The work function from a thorium surface is lowered possibly because of the electric field on the interface between thorium and tungsten formed due to thorium's greater electropositivity. Since the 1920s, thoriated tungsten wires have been used in electronic tubes and in the cathodes and anticathodes of X-ray tubes and rectifiers. Thanks to the reactivity of thorium with atmospheric oxygen and nitrogen, thorium also acts as a getter for impurities in the evacuated tubes. The introduction of transistors in the 1950s significantly diminished this use, but not entirely. Thorium dioxide is used in gas tungsten arc welding (GTAW) to increase the high-temperature strength of tungsten electrodes and improve arc stability. Thorium oxide is being replaced in this use with other oxides, such as those of zirconium, cerium, and lanthanum.
Thorium dioxide is found in heat-resistant ceramics, such as high-temperature laboratory crucibles,either as the primary ingredient or as an addition to zirconium dioxide. An alloy of 90% platinum and 10% thorium is an effective catalyst for oxidising ammonia to nitrogen oxides, but this has been replaced by an alloy of 95% platinum and 5% rhodium because of its better mechanical properties and greater durability.
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.The radiation from these lenses can darken them and turn them yellow over a period of years and it degrades 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 in this application, as they provide similar effects and are not radioactive.
Thorium tetrafluoride is used as an antireflection material in multilayered optical coatings. It is transparent to electromagnetic waves having wavelengths in the range of 0.35–12 µm, a range that includes near ultraviolet, visible and mid infrared light. Its radiation is primarily due to alpha particles, which can be easily stopped by a thin cover layer of another material. Replacements for thorium tetrafluoride are being developed as of the 2010s.
Mag-Thor alloys (also called thoriated magnesium) found use in some aerospace applications, though such uses have been phased out due to concerns over radioactivity.
The main nuclear power source in a reactor is the neutron-induced fission of a nuclide; the synthetic fissilenuclei 233U and 239Pu can be bred from neutron capture by the naturally occurring quantity nuclides 232Th and 238U. 235U occurs naturally and is also fissile. In the thorium fuel cycle, the fertile isotope 232Th is bombarded by slow neutrons, undergoing neutron capture to become 233Th, which undergoes two consecutive beta decays to become first 233Pa and then the fissile 233U:
|(Nuclides before a yellow background in italic have half-lives under 30 days;|
nuclides in bold have half-lives over 1,000,000 years;
nuclides in are fissile)
233U is fissile and can be used as a nuclear fuel in the same way as 235U or 239Pu. When 233U undergoes nuclear fission, the neutrons emitted can strike further 232Th nuclei, continuing the cycle.This parallels the uranium fuel cycle in fast breeder reactors where 238U undergoes neutron capture to become 239U, beta decaying to first 239Np and then fissile 239Pu.
Thorium is more abundant than uranium and can satisfy world energy demands for longer.
232Th absorbs neutrons more readily than 238U, and 233U has a higher probability of fission upon neutron capture (92.0%) than 235U (85.5%) or 239Pu (73.5%).It also releases more neutrons upon fission on average. A single neutron capture by 238U produces transuranic waste along with the fissile 239Pu, but 232Th only produces this waste after five captures, forming 237Np. This number of captures does not happen for 98–99% of the 232Th nuclei because the intermediate products 233U or 235U undergo fission, and fewer long-lived transuranics are produced. Because of this, thorium is a potentially attractive alternative to uranium in mixed oxide fuels to minimise the generation of transuranics and maximise the destruction of plutonium.
Thorium fuels also result in a safer and better-performing reactor corebecause thorium dioxide has a higher melting point, higher thermal conductivity, and a lower coefficient of thermal expansion and is more stable chemically than the now-common fuel uranium dioxide, which can further oxidise to triuranium octoxide (U3O8).
The used fuel is difficult and dangerous to reprocess because many of the daughters of 232Th and 233U are strong gamma emitters.All 233U production methods result in impurities of 232U, either from parasitic knock-out (n,2n) reactions on 232Th, 233Pa, or 233U that result in the loss of a neutron, or from double neutron capture of 230Th, an impurity in natural 232Th:
232U by itself is not particularly harmful, but quickly decays to produce the strong gamma emitter 208Tl. (232Th follows the same decay chain, but its much longer half-life means that the quantities of 208Tl produced are negligible.) days and a high cross section for neutron capture. Thus it is a neutron poison: instead of rapidly decaying to the useful 233U, a significant amount of 233Pa converts to 234U and consumes neutrons, degrading the reactor efficiency. To avoid this, 233Pa is extracted from the active zone of thorium molten salt reactors during their operation, so that it does not have a chance to capture a neutron and will only decay to 233U.These impurities of 232U make 233U easy to detect and dangerous to work on, and the impracticality of their separation limits the possibilities of nuclear proliferation using 233U as the fissile material. 233Pa has a relatively long half-life of 27
The irradiation of 232Th with neutrons, followed by its processing, need to be mastered before these advantages can be realised, and this requires more advanced technology than the uranium and plutonium fuel cycle; years and is a major contributor to the long-term radiotoxicity of spent nuclear fuel.research continues in this area. Others cite the low commercial viability of the thorium fuel cycle: the international Nuclear Energy Agency predicts that the thorium cycle will never be commercially viable while uranium is available in abundance—a situation which may persist "in the coming decades". The isotopes produced in the thorium fuel cycle are mostly not transuranic, but some of them are still very dangerous, such as 231Pa, which has a half-life of 32,760
Natural thorium decays very slowly compared to many other radioactive materials, and the emitted alpha radiation cannot penetrate human skin. As a result, handling small amounts of thorium, such as those in gas mantles, is considered safe, although the use of such items may pose some risks.Exposure to an aerosol of thorium, such as contaminated dust, can lead to increased risk of cancers of the lung, pancreas, and blood, as lungs and other internal organs can be penetrated by alpha radiation. Internal exposure to thorium leads to increased risk of liver diseases.
The decay products of 232Th include more dangerous radionuclides such as radium and radon. Although relatively little of those products are created as the result of the slow decay of thorium, a proper assessment of the radiological toxicity of 232Th must include the contribution of its daughters, some of which are dangerous gamma emitters, millisieverts per use, about a third of the dose sustained during a mammogram.and which are built up quickly following the initial decay of 232Th due to the absence of long-lived nuclides along the decay chain. As the dangerous daughters of thorium have much lower melting points than thorium dioxide, they are volatilised every time the mantle is heated for use. In the first hour of use large fractions of the thorium daughters 224Ra, 228Ra, 212Pb, and 212Bi are released. Most of the radiation dose by a normal user arises from inhaling the radium, resulting in a radiation dose of up to 0.2
Some nuclear safety agencies make recommendations about the use of thorium mantles and have raised safety concerns regarding their manufacture and disposal; the radiation dose from one mantle is not a serious problem, but that from many mantles gathered together in factories or landfills is.
Thorium is odourless and tasteless.The chemical toxicity of thorium is low because thorium and its most common compounds (mostly the dioxide) are poorly soluble in water, precipitating out before entering the body as the hydroxide. Some thorium compounds are chemically moderately toxic, especially in the presence of strong complex-forming ions such as citrate that carry the thorium into the body in soluble form. If a thorium-containing object has been chewed or sucked, it loses 0.4% of thorium and 90% of its dangerous daughters to the body. Three quarters of the thorium that has penetrated the body accumulates in the skeleton. Absorption through the skin is possible, but is not a likely means of exposure. Thorium's low solubility in water also means that excretion of thorium by the kidneys and faeces is rather slow.
Tests on the thorium uptake of workers involved in monazite processing showed thorium levels above recommended limits in their bodies, but no adverse effects on health were found at those moderately low concentrations. No chemical toxicity has yet been observed in the tracheobronchial tract and the lungs from exposure to thorium.People who work with thorium compounds are at a risk of dermatitis. It can take as much as thirty years after the ingestion of thorium for symptoms to manifest themselves. Thorium has no known biological role.
Powdered thorium metal is pyrophoric: it ignites spontaneously in air. °C (520 °F) for dust clouds and 280 °C (535 °F) for layers. Its minimum explosive concentration was listed as 0.075 oz/cu ft (0.075 kg/m3); the minimum igniting energy for (non-submicron) dust was listed as 5 mJ.In 1964, the United States Department of the Interior listed thorium as "severe" on a table entitled "Ignition and explosibility of metal powders". Its ignition temperature was given as 270
In 1956, the Sylvania Electric Products explosion occurred during reprocessing and burning of thorium sludge in New York City, United States. Nine people were injured; one died of complications caused by third-degree burns.
Thorium exists in very small quantities everywhere on Earth although larger amounts exist in certain parts: the average human contains about 40 micrograms of thorium and typically consumes three micrograms per day. Most thorium exposure occurs through dust inhalation; some thorium comes with food and water, but because of its low solubility, this exposure is negligible.
Exposure is raised for people who live near thorium deposits or radioactive waste disposal sites, those who live near or work in uranium, phosphate, or tin processing factories, and for those who work in gas mantle production.Thorium is especially common in the Tamil Nadu coastal areas of India, where residents may be exposed to a naturally occurring radiation dose ten times higher than the worldwide average. It is also common in northern Brazilian coastal areas, from south Bahia to Guarapari, a city with radioactive monazite sand beaches, with radiation levels up to 50 times higher than world average background radiation.
Another possible source of exposure is thorium dust produced at weapons testing ranges, as thorium is used in the guidance systems of some missiles. This has been blamed for a high incidence of birth defects and cancer at Salto di Quirra on the Italian island of Sardinia.
The actinide or actinoid series encompasses the 15 metallic chemical elements with atomic numbers from 89 to 103, actinium through lawrencium.
Berkelium is a transuranic radioactive chemical element with the symbol Bk and atomic number 97. It is a member of the actinide and transuranium element series. It is named after the city of Berkeley, California, the location of the Lawrence Berkeley National Laboratory where it was discovered in December 1949. Berkelium was the fifth transuranium element discovered after neptunium, plutonium, curium and americium.
Protactinium is a chemical element with the symbol Pa and atomic number 91. It is a dense, silvery-gray actinide metal which readily reacts with oxygen, water vapor and inorganic acids. It forms various chemical compounds in which protactinium is usually present in the oxidation state +5, but it can also assume +4 and even +3 or +2 states. Concentrations of protactinium in the Earth's crust are typically a few parts per trillion, but may reach up to a few parts per million in some uraninite ore deposits. Because of its scarcity, high radioactivity and high toxicity, there are currently no uses for protactinium outside scientific research, and for this purpose, protactinium is mostly extracted from spent nuclear fuel.
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.
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.
In nuclear science, the decay chain refers to a series of radioactive decays of different radioactive decay products as a sequential series of transformations. It is also known as a "radioactive cascade". Most radioisotopes do not decay directly to a stable state, but rather undergo a series of decays until eventually a stable isotope is reached.
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.
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. 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. All thorium compounds are radioactive because there are no stable isotopes of thorium.
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.
Uranium (92U) is a naturally occurring radioactive element that has no stable isotope. It has two primordial isotopes,, that have long half-lives and are found in appreciable quantity in the Earth's crust. The decay product uranium-234 is also found. Other isotopes such as uranium-232 have been produced in breeder reactors. In addition to isotopes found in nature or nuclear reactors, many isotopes with far shorter half-lives have been produced, ranging from 215U to 242U. The standard atomic weight of natural uranium is 238.02891(3).
Protactinium (91Pa) has no stable isotopes. The three naturally occurring isotopes allow a standard atomic weight to be given.
The thorium fuel cycle is a nuclear fuel cycle that uses an isotope of thorium, 232
, as the fertile material. In the reactor, 232
is transmuted into the fissile artificial uranium isotope 233
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
absorbs neutrons to produce 233
. This parallels the process in uranium breeder reactors whereby fertile 238
absorbs neutrons to form fissile 239
. Depending on the design of the reactor and fuel cycle, the generated 233
either fissions in situ or is chemically separated from the used nuclear fuel and formed into new nuclear fuel.
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.
Uranium-236 is an isotope of uranium that is neither fissile with thermal neutrons, nor very good fertile material, but is generally considered a nuisance and long-lived radioactive waste. It is found in spent nuclear fuel and in the reprocessed uranium made from spent nuclear fuel.
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.
Nuclear transmutation is the conversion of one chemical element or an isotope into another chemical element. Because any element is defined by its number of protons in its atoms, i.e. in the atomic nucleus, nuclear transmutation occurs in any process where the number of protons or neutrons in the nucleus is changed.
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.
Thorium is found in small amounts in most rocks and soils. Soil commonly contains an average of around 6 parts per million (ppm) of thorium. Thorium occurs in several minerals including thorite (ThSiO4), thorianite (ThO2 + UO2) and monazite. Thorianite is a rare mineral and may contain up to about 12% thorium oxide. Monazite contains 2.5% thorium, allanite has 0.1 to 2% thorium and zircon can have up to 0.4% thorium. Thorium-containing minerals occur on all continents. Thorium is several times more abundant in Earth's crust than all isotopes of uranium combined and thorium-232 is several hundred times more abundant than uranium-235.
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