Thorium

Thorium,  ₉₀Th

General properties
Pronunciation	/ˈθɔəriəm/ THAWR-ee-əm
Appearance	silvery, often with black tarnish
Standard atomic weight (Ar)	7002232037700000000♠232.0377(4)[1]
Thorium in the periodic table
Ce ↑ Th ↓ (Uqq) actinium ← thorium → protactinium
Atomic number (Z)	90
Group, period	group n/a, period 7
Block	f-block
Element category	actinide
Electron configuration	[Rn] 6d2 7s2
Electrons per shell	2, 8, 18, 32, 18, 10, 2
Physical properties
Spectral lines	​
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 P (Pa) 1 10 100 1 k 10 k 100 k at T (K) 2633 2907 3248 3683 4259 5055
Atomic properties
Oxidation states	4, 3, 2, 1 ​(a weakly basic oxide)
Electronegativity	Pauling scale: 1.3
Ionisation energies	1st: 587 kJ/mol 2nd: 1110 kJ/mol 3rd: 1930 kJ/mol
Atomic radius	empirical: 179.8 pm
Covalent radius	206±6 pm
Miscellanea
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 ordering	paramagnetic[2]
Magnetic susceptibility	132.0·10−6 cm3/mol (293 K)[3]
Young's modulus	79 GPa
Shear modulus	31 GPa
Bulk modulus	54 GPa
Poisson ratio	0.27
Mohs hardness	3.0
Vickers hardness	295–685 MPa
Brinell hardness	390–1500 MPa
CAS Number	7440-29-1
History
Naming	after Thor, the Norse god of thunder
Discovery	Jöns Jakob Berzelius (1829)
Main isotopes of thorium
Iso­tope Abun­dance Half-life (t1/2) Decay mode Pro­duct 227Th trace 18.68 d α 223Ra 228Th trace 1.9116 y α 224Ra 229Th trace 7917 y α 225Ra 230Th 0.02% 75400 y α 226Ra 231Th trace 25.5 h β− 231Pa 232Th 99.98% 1.405×1010 y α 228Ra 234Th trace 24.1 d β− 234Pa
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Thorium is a chemical element with symbol Th and atomic number 90. Thorium metal is silvery and tarnishes black when exposed to air, forming the 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, prone to ignition on air when finely divided.

Thorium is weakly radioactive: all of its known isotopes are unstable, the most stable isotope of thorium, 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 ²⁰⁸Pb. Thorium is one of only two significantly radioactive elements that still occur naturally in large quantities as a primordial element (the other being uranium).^[a] It is estimated to be about three to four times more abundant than uranium in the Earth's crust, and is chiefly refined from monazite sands as a by-product of extracting rare-earth metals.

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. However, its first applications were developed only over half a century later, in the late 19th century. Thorium's radioactivity was widely acknowledged during the first decades of the 20th century; in the second half of that century, thorium's uses have been diminished or annulled by concerns over its radioactivity and availability of non-radioactive replacements.

Uses in which thorium was once widely used but is only marginally used now include uses as an alloying element in TIG welding electrodes, as a material in high-end optics and scientific instrumentation, and as the light source in gas mantles. Thorium is predicted to be able to replace uranium as nuclear fuel in nuclear reactors, but only a few thorium reactors have yet been completed.

Bulk properties[edit]

Thorium is a moderately hard, paramagnetic, bright silvery radioactive actinide metal; in the periodic table, it is located to the right of the actinide actinium, to the left of the actinide protactinium, and below the lanthanide cerium. Pure thorium is very ductile and, as normal for metals, can be cold-rolled, swaged, and drawn.^[4] At room temperature, thorium metal has a face-centred cubic crystal structure; additionally, it has two other forms at exotic conditions, one at high temperature (over 1360 °C; body-centred cubic) and one at high pressure (around 100 GPa; body-centred tetragonal).^[4]

The properties of thorium vary widely depending on the amount of impurities in the sample: the major impurity is usually thorium dioxide (ThO₂). The purest thorium specimens usually contain about a tenth of a percent of the dioxide.^[4] Experimental measurements of its density give values between 11.5 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.^[4] These values lie intermediate between those of its neighbours actinium (10.1 g/cm³) and protactinium (15.4 g/cm³), showing the continuity of trends across the early actinides.^[4]

Thorium's melting point of 1750 °C is above both that of actinium (1227 °C) and that of protactinium (~1560 °C). In the beginning of period 7, from francium to thorium, the melting points of the elements increase (following the trend in the other periods): this is because the number of delocalised electrons that each atom contributes increases from one in francium to four in thorium, and there is a greater attraction between these electrons and the metal ions as their charge increases from one in francium to four in thorium. After thorium, there is a new smooth trend downward in the melting points of the early actinides from thorium to plutonium where the number of f electrons increases from about 0.4 to about 6, due to the itinerance of the f-orbitals, increasing hybridisation of the 5f and 6d orbitals and the formation of directional bonds in the metal resulting in increasingly complex crystal structures and weakened metallic bonding.^[5][6] (The f-electron count for thorium is listed as a non-integer due to a 5f–6d overlap.)^[6] Among the actinides, thorium has the highest melting and boiling points and second-lowest density (second only to actinium), its boiling point of 4788 °C is the fifth-highest among all the elements with known boiling points, behind only osmium, tantalum, tungsten, and rhenium.^[4]

Thorium metal has a bulk modulus (measure of resistance to compression of a material) of 54 GPa, about the same as that of tin (58.2 GPa). In comparison, that of aluminium is 75.2 GPa; copper 137.8 GPa; and mild steel 160–169 GPa.^[7] Thorium's hardness is similar to that of soft steel, so heated pure thorium can be rolled in sheets and pulled into wire.^[5] While thorium is nearly half as dense as uranium and plutonium, it is harder than either of them.^[5] Thorium becomes superconductive below 1.4 K.^[4]

Thorium can also form alloys with many other metals. Addition of small amounts of thorium improves the mechanical strength of magnesium, and thorium-aluminium alloys have been considered as a way to store thorium in proposed future thorium nuclear reactors, with chromium and uranium, it forms eutectic mixtures, and thorium is completely miscible in both solid and liquid states with its lighter congener cerium.^[4]

Isotopes[edit]

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). On the other hand, all the elements from polonium (element 84) onward are noticeably radioactive, the isotope 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 even slightly longer than the generally accepted age of the universe (about 13.8 billion years). As such, ²³²Th still occurs naturally today: four-fifths of the thorium present at Earth's formation has survived to the present.^[8][9][10] It is the only isotope of thorium occurring in significant quantities in nature today, and thus thorium is usually considered to be a mononuclidic element,^[8] its stability is attributed to its closed nuclear shell: it has one at 142 neutrons.^[11][12] Thorium has a characteristic terrestrial isotopic composition, with atomic weight 232.0377(4). Thorium is one of only three significantly radioactive elements (the others being protactinium and uranium) that occur in large enough quantities on Earth for this to be possible.^[1]

Thorium nuclei are susceptible to alpha decay because the strong nuclear force is not strong enough to overcome the electromagnetic repulsion between their protons,^[13] the alpha decay of ²³²Th decay initiates the so-called 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 stable ²⁰⁸Pb.^[8] Any sample of thorium or its compounds contains traces of these daughters, which are isotopes of thallium, lead, bismuth, polonium, radon, radium, and actinium.^[8] As such, natural thorium samples can be chemically purified to extract its useful daughter nuclides, such as ²¹²Pb, which is used in nuclear medicine for cancer therapy.^{[14][15] 232}Th also very occasionally undergoes spontaneous fission rather than alpha decay, and has left evidence in 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 years and hence alpha decay predominates.^[16][17]

The 4n decay chain of ²³²Th, commonly called the "thorium series"

Thirty radioisotopes have been characterised, which range in mass number from 209^[18] to 238,^[16] the most stable of them (after ²³²Th) are ²³⁰Th with a half-life of 75,380 years, ²²⁹Th with a half-life of 7,340 years, ²²⁸Th with a half-life of 1.92 years, ²³⁴Th with a half-life of 24.10 days, and ²²⁷Th with a half-life of 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 ²³⁷Np: the last of these is long extinct primordially 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.^[8]

In deep seawaters the isotope ²³⁰Th becomes significant enough that the International Union of Pure and Applied Chemistry reclassified thorium as a binuclidic element in 2013, as it can then make up to 0.04% of natural thorium.^[1] The reason for this is that while its parent ²³⁸U is soluble in water, ²³⁰Th is insoluble and thus precipitates to form part of the sediment, and may be observed doing so. 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.^[16]

Thorium also has three known nuclear isomers (or metastable states), ^216m1Th, ^216m2Th, and ^229mTh. ^229mTh has the lowest known excitation energy of any isomer,^[19] measured to be 7.6 ± 0.5 eV. This is so low that when it undergoes isomeric transition, the emitted gamma radiation is in the ultraviolet range.^[20][21][b]

Different isotopes of thorium behave identically chemically, but have slightly differing physical properties: for example, the densities of isotopically pure ²²⁸Th, ²²⁹Th, ²³⁰Th, and ²³²Th are respectively expected to be 11.5, 11.6, 11.6, and 11.7 g/cm³.^[23] 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.^[23][c] While ²³²Th is not fissionable, it is fertile as it can be converted to fissile ²³³U by neutron capture and subsequent beta decay.^[23][24]

Radiometric dating[edit]

Two radiometric dating methods involve thorium isotopes: uranium–thorium dating, involving the decay of ²³⁴U to ²³⁰Th, and ionium–thorium dating, which measures the ratio of ²³²Th to ²³⁰Th. (The name ionium for ²³⁰Th is a remnant from the early history of radioactivity, when different isotopes were not recognised to be the same element and were given different names.) 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.^[25] 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 while uranium is rather soluble in water, thorium and protactinium are not, and so they are selectively precipitated into ocean-floor sediments, from which their ratios are measured. The scheme has a range of several hundred thousand years.^[25][26] 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.^[27][28] Both of these dating methods assume that the proportion of ²³⁰Th to ²³²Th is a constant during the time 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 shift within the sediment layer.^[27][28]

Chemistry[edit]

Reactions of thorium metal

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,^[29] 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 destabilised. Such unusual behaviour is due to relativistic effects, which are increasingly 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 result in thorium almost always losing all four of its valence electrons and hence occurring in its highest possible oxidation state of +4. This behaviour is quite distinct from that of its lanthanide congener cerium, for whom +4 is the highest possible state but +3 also plays an important role and is more stable. Therefore, thorium is much more similar to the transition metals zirconium and hafnium than to its true lanthanide congener cerium in its properties such as ionisation 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.^[30][31]

Despite this anomalous electron configuration for gaseous thorium atoms, however, metallic thorium shows significant 5f involvement, this was first realised 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-centered cubic as it actually is. Indeed, the correct crystal structure can only be obtained when the 5f states are included, proving that thorium, and not protactinium, acts as the first actinide metallurgically with the clear influence of the 5f orbitals,^[6] 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.^[32]

Tetravalent thorium compounds are usually colourless or yellow, like those of silver or lead, as the Th⁴⁺ ion has no 5f or 6d electrons.^[5] 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.^[33][d] Thorium and uranium are the most investigated of the radioactive elements because their radioactivity is slight enough to not pose major problems of handling and accessibility and they may be safely handled in a normal laboratory.^[32]

Reactivity[edit]

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.^[34] Finely divided thorium metal can exhibit pyrophoricity, spontaneously igniting in the air.^[4] When heated in air, thorium turnings ignite and burn brilliantly with a white light to produce the dioxide; in bulk, the reaction of pure thorium with air is slow, although corrosion may eventually occur after several months; most thorium samples are contaminated with varying degrees of the dioxide, which greatly accelerates corrosion.^[4] Such samples slowly tarnish in air, becoming grey and finally black at the surface.^[4]

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 behind a black insoluble residue, ThO(OH,Cl)H.^[4][35] It dissolves in concentrated nitric acid containing a small amount of catalytic fluoride or fluorosilicate ions;^[4][36] if these are not present, passivation can occur, similarly to uranium and plutonium.^[4][37]

Inorganic compounds[edit]

Thorium dioxide has the fluorite structure. Th⁴⁺: __  /  O²⁻: __

Most binary compounds of thorium with nonmetals may simply be prepared by heating the elements together;^[38] in air, thorium burns to form the simple dioxide, ThO₂: this has the fluorite structure.^[39] Thorium dioxide, a refractory material, has the highest melting point (3390 °C) of all known oxides.^[40] It is somewhat hygroscopic and reacts readily with water and many gases,^[41] but dissolves easily in concentrated nitric acid in the presence of fluoride.^[42] When heated, it emits intense blue light through incandescence, which becomes white when mixed with its lighter homologue cerium dioxide (CeO₂, ceria): this is the basis for its previously common application in gas mantles.^[41] Several binary thorium chalcogenides and oxychalcogenides are also known with sulfur, selenium, and tellurium.^[43]

Crystal structure of thorium tetrafluoride. Th⁴⁺: __  /  F⁻: __

All four thorium tetrahalides are known, as are some low-valent bromides and iodides:^[44] the tetrahalides are all 8-coordinated hygroscopic compounds that dissolve easily in polar solvents such as water.^[45] Additionally, many related polyhalide ions are also known.^[44] Thorium tetrafluoride has a monoclinic crystal structure and is isotypic with zirconium tetrafluoride and hafnium tetrafluoride, where the Th⁴⁺ ions are coordinated with F⁻ ions in somewhat distorted square antiprisms.^[44] The other tetrahalides instead have dodecahedral geometry.^[45] Lower iodides ThI₃ (black) and ThI₂ (gold) can also be prepared by reducing the tetraiodide with thorium metal: These do not contain Th(III) and Th(II), but instead contain Th⁴⁺ and could be more clearly formulated as electride compounds.^[44] Many polynary halides with the alkali metals, barium, thallium, and ammonium are known for thorium fluorides, chlorides, and bromides,^[44] for example, when treated with potassium fluoride and hydrofluoric acid, Th⁴⁺ forms the complex anion ThF2−
6, which precipitates as an insoluble salt, K₂ThF₆.^[36]

Thorium borides, carbides, silicides, and nitrides are refractory materials, as are those of uranium and plutonium, and have thus received attention as possible nuclear fuels.^[38] All four heavier pnictogens (phosphorus, arsenic, antimony, and bismuth) also form binary thorium compounds. Thorium germanides are also known.^[46] Thorium reacts with hydrogen to form the thorium hydrides ThH₂ and Th₄H₁₅, the latter of which is superconducting below the transition temperature of 7.5–8 K; at standard temperature and pressure, it conducts electricity like a metal.^[47] They are thermally unstable and readily decompose upon exposure to air or moisture.^[38]

Coordination compounds[edit]

In acidic aqueous solution, thorium occurs as the tetrapositive aqua ion [Th(H₂O)₉]⁴⁺, which has tricapped trigonal prismatic molecular geometry:^[48][49] at pH < 3, the solutions of thorium salts are dominated by this cation.^[48] 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.^[48] 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 is formed and precipitates out (though equilibrium may take weeks to be reached, because the polymerisation usually slows down significantly just before the precipitation).^[50] 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.^[30]

Large 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,^[50] the distinctive ability of thorium salts is their high solubility, not only in water, but also in polar organic solvents.^[5]

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.^[51] They are important in thorium purification and the disposal of nuclear waste, but most of them have not yet been fully characterised, especially regarding their structural properties,^[51] 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.^[51] Thorium complexes with organic ligands, such as oxalate, citrate, and EDTA, are much stronger and tend to occur naturally in natural thorium-containing waters in concentrations orders of magnitude higher than the inorganic complexes.^[48]

Organothorium compounds[edit]

Sandwich structure of thorocene

Piano-stool structure of (η⁸-C₈H₈)ThCl₂(THF)₂

Most of the work on organothorium compounds has focused on the cyclopentadienyls and cyclooctatetraenyls. Like many of the early and middle actinides (up to americium, and also expected for curium), thorium forms the yellow cyclooctatetraenide complex Th(C₈H₈)₂, thorocene. It is isotypic with the better-known analogous uranium compound, uranocene,^[52] 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.^[52] It is an unstable compound in air and outright decomposes in water or at 190 °C.^[52] 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.^[30]

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;^[52][53] a formal +2 oxidation state even occurs in a derivative.^[54] 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 received attention due to the insight they give regarding the nature of the Th–C sigma bond.^[53]

Other organothorium compounds are not well-studied. Tetrabenzylthorium, Th(CH₂C₆H₅), and tetraallylthorium, Th(C₃H₅)₄, are known, but their structures have not yet been determined and 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.^[30]

Occurrence[edit]

Formation[edit]

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.^[55] 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,^[56] because of the abrupt loss of stability past ²⁰⁹Bi, the r-process is the only process of stellar nucleosynthesis that can create isotopes of thorium and uranium, because all other processes are too slow and the intermediate nuclei alpha decay before they capture enough neutrons to reach these elements.^[55][57][58]

Estimated abundances of the 83 primordial elements in the Solar system. Thorium is one of the rarest elements.

In the universe, thorium is among the rarest of the primordial elements: it achieves this position not only because it is one of the two elements that can be produced only in the r-process, but also because it has slowly been decaying away from the moment it formed, the only primordial elements rarer than thorium are uranium, the only other element produced only in the r-process, as well as thulium, lutetium, tantalum, and rhenium, the odd-numbered elements just before the third peak of r-process abundances around the heavy platinum group metals.^[55][56][e] Furthermore, neutron capture by nuclides beyond A = 209 often results in nuclear fission instead of neutron absorption, reducing the fraction of nuclei that cross the gap of instability past bismuth to become actinides such as thorium;^[56] in the distant past the abundances of thorium and uranium were still being enriched by the decay of extinct plutonium and curium isotopes, and thorium was enriched relative to uranium by the decay of extinct ²³⁶U to ²³²Th and the natural depletion of ²³⁵U, but these sources have long since decayed and no longer contribute.^[59]

On Earth, thorium is much more abundant: with an abundance of 8.1 parts per million (ppm) in the Earth's crust, it is one of the most abundant of the heavy elements, almost as abundant as lead (13 ppm) and significantly more abundant than tin (2.1 ppm).^[60] This is because thorium is likely to form oxide minerals that do not sink into the core; as such, it is classified as a lithophile. Furthermore, thorium compounds are also poorly soluble in water. Thus, even though the whole of the Earth contains the same abundances of the elements as the Solar System as a whole, there is significantly more accessible thorium than there are accessible heavy platinum group metals in the crust alone.^[61]

On Earth[edit]

The radiogenic heat from the decay of ²³²Th (violet) is a major contributor to the earth's internal heat budget. Of the four major nuclides providing this heat, ²³²Th has grown to be the most abundant as the other ones decayed faster than thorium.^{[62][63][64][65]}

Natural thorium is essentially isotopically pure ²³²Th, which is the longest-lived and most stable isotope of thorium, having a half-life comparable to the age of the universe,^[16] 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 size of contribution. (At the time of the Earth's formation, ⁴⁰K, and ²³⁵U contributed much more by virtue of their short half-lives, but by the same token they have also decayed more quickly, leaving the almost constant contribution from ²³²Th and ²³⁸U predominant.)^[66] 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.^[16][f]

On Earth, thorium is not a rare element as was previously thought, having a crustal abundance comparable to that of lead and molybdenum, twice that of arsenic, and thrice that of tin.^[68] Thorium only occurs as a minor constituent of most minerals.^[68] Soil normally contains about 6 ppm of thorium.^[69]

In nature, thorium occurs in the +4 oxidation state, together with uranium(IV), zirconium(IV), hafnium(IV), and cerium(IV), but also with scandium, yttrium, and the trivalent lanthanides which have similar ionic radii,^[68] because of thorium's radioactivity, minerals containing significant quantities of thorium are often metamict, their crystal structure having been partially or totally destroyed by the alpha radiation produced in the radioactive decay of thorium.^[70] An extreme example is ekanite, (Ca,Fe,Pb)₂(Th,U)Si₈O₂₀, which almost never occurs in nonmetamict form due to thorium being an essential part of its chemical composition.^[71]

Monazite 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% thorium.^[68][72] Monazite is a chemically unreactive phosphate mineral that is found as yellow or brown sand; its low reactivity makes it difficult to extract thorium from it.^[68] Allanite can have 0.1–2% thorium and zircon up to 0.4% thorium.^[68]

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.^[68][g] Thorite, or thorium silicate (ThSiO₄), also has a high thorium content and is the mineral in which thorium was first discovered.^[68] In thorium silicate minerals, the Th⁴⁺ and SiO4−
4 ions are often replaced with M³⁺ (M = Sc, Y, Ln) and phosphate (PO3−
4) ions respectively.^[68] Because of the great insolubility of thorium dioxide, thorium does not usually spread quickly through the environment when released in significant quantities. However, the Th⁴⁺ ion is soluble, especially in acidic soils, and in such conditions the thorium concentration can reach 40 ppm.^[73]

History[edit]

Tor's Fight with the Giants (1872) by Mårten Eskil Winge, depicting an artist's perception of Thor, the Norse god of thunder, raising his hammer in a battle against the giants.^[74]

Erroneous report[edit]

In 1815, the Swedish chemist Jöns Jakob 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. (By that time, 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 simply zinc oxide.)^[75] Berzelius privately named the supposed tentative element "thorium" in 1817^[76] and its supposed oxide "thorina" after Thor, the Norse god of thunder.^[77] In 1824, after more deposits of the same mineral in Vest-Agder, Norway, were discovered, he retracted his findings, as the mineral in question proved to actually be an yttrium mineral, primarily composed of yttrium orthophosphate.^{[24][75][78][79]} As the yttrium in this mineral was initially mistaken as being a new element, the mineral was named kenotime by the French mineralogist François Sulpice Beudant as a rebuke of Berzelius, from the Greek words κενός (kenos; "empty") and τιμή (timē; "honour"). This became "xenotime" as a misprint from the beginning, blunting the criticism.^[75][79][80] This misspelt form was later explained as being from ξένος (xenos; "alien") and τιμή (timē; "honour"), supposedly referencing the small, rare and easily overlooked crystals that xenotime occurs as.^[81]

Discovery[edit]

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 University of Oslo.^[82] The elder Esmark determined that it was not any known mineral and sent a sample to Berzelius for examination. Berzelius determined that it contained a new element,^[24] he published his findings in 1829, having isolated an impure sample for the first time by reducing KThF₅ with potassium metal.^[83][84][85] Berzelius reused the name of the previous supposed element discovery.^[83][86] Thus, he named the source mineral thorite, which has the chemical composition (Th,U)SiO₄.^[24]

Jöns Jacob Berzelius, the person who first identified thorium as a new element

Berzelius also made some initial characterisation of the new metal and its chemical compounds: he correctly determined that the thorium–oxygen mass ratio was 7.5 (its actual value is close to that, ~7.3), but he assumed the new element was divalent rather than tetravalent, and as such assumed that the atomic mass was 7.5 times that of oxygen (120 amu), while it is actually 15 times as large.^[h] He determined that thorium was a very electropositive metal, that he placed ahead of cerium and behind zirconium in electropositivity.^[87] Berzelius did not isolate the element in its metallic state; for the first time, thorium was isolated in 1914 by Dutch entrepreneurs Dirk Lely Jr. and Lodewijk Hamburger. They obtained 99% pure thorium metal by reducing thorium chloride with sodium metal.^[88][i] A simpler method leading to even higher purity was discovered in 1927 by American engineers John Marden and Harvey Rentschler, involving the reduction of thorium oxide with calcium when calcium chloride was present.^[88]

Initial chemical classification[edit]

In the periodic table published by Russian chemist 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 contained the modern carbon group (group 14), titanium group (group 4), cerium, and thorium, because their maximum oxidation state was +4.^[90][91] Cerium was soon removed from the main body of the table and placed in a separate lanthanide series, while thorium remained with group 4 as it had similar properties to its supposed lighter congeners in that group, such as titanium and zirconium.^[92][j]

First uses[edit]

Although thorium was discovered in 1828, it had no applications until 1885, when Austrian chemist Carl Auer von Welsbach invented the gas mantle, a portable source of light which produces light from the incandescence of very hot thorium oxide, heated to extremely high temperatures by burning gaseous fuels.^[24] After that, many applications were found for thorium and its compounds, such as in ceramics, carbon arc lamps, heat-resistant crucibles, and as catalysts for industrial chemical reactions such as the oxidation of ammonia to nitric acid.

World War II thorium dioxide gas mantle

Radioactivity[edit]

In the late 19th century onward, the atomic theory underwent significant improvements, which shaped the further history of thorium. Thorium was first observed to be radioactive in 1898, independently, by the German chemist Gerhard Carl Schmidt and later that year, 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.^[93][94][95] Between 1900 and 1903, British physicists Ernest Rutherford and Frederick Soddy showed how thorium decayed at a fixed rate over time into a series of other elements, this observation led to the identification of half-life as one of the outcomes of the alpha particle experiments that led to their disintegration theory of radioactivity.^[96] The biological effect of radiation was discovered in 1903;^[97] the danger presented by radioactivity to health and environment was the reason thorium was phased out of use in applications that did not explicitly use the radioactivity.^[24] Since the 1930s, it has been widely acknowledged that thorium possesses a minor threat to human organisms in large quantities.

Further classification[edit]

Glenn T. Seaborg, the person who settled thorium's location in the f-block

Up to late 19th century, chemists unanimously agreed that thorium and uranium were analogous to the 5d elements 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 1922, 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,^[90] 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,^[98] such that Bohr suggested that the filling of the 5f orbitals may be delayed to after uranium.^[90]

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;^[99] 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 and filling a fourth d-block row.^[92][k]

Phasing out[edit]

Despite thorium's radioactivity, the element has remained in use for a long time for applications not exploiting the effect as no suitable alternatives could be found. While a 1981 study by the Oak Ridge National Laboratory (Oak Ridge, Tennessee, United States) estimated that a dose from using a thorium mantle every weekend would be safe for a person,^[102][103] this was not the case for the dose received by people manufacturing the mantles (and thus contacting many) as well as soils around some factory sites.^[104] A major shift occurred in the 1990s, when most of these applications that do not depend on thorium's radioactivity declined quickly due to safety and environmental concerns as suitable safer replacements have been found.^[24][105] Due to concerns, some manufacturers have switched to other materials, such as yttrium, although these are usually either more expensive or less efficient. Other manufacturers continued to make thorium mantles, but moved their factories to developing countries,^[103] as recently as 2007, some companies continued to manufacture and sell thorium mantles without giving adequate information about their radioactivity, with some even fraudulently claiming them to be non-radioactive while in reality using significant quantities of thorium, up to 259 milligrams per mantle.^[105][106]

Nuclear power[edit]

The Indian Point Energy Center (Buchanan, New York, United States), home of the world's first thorium reactor

The United States explored the possibility to use ²³²Th as a source for ²³³U, which would be used in a nuclear bomb, in the wake of the Cold War; they fired a test bomb in 1955.^[107] However, they soon recognized that while a ²³³U-fired bomb would be a very potent weapon, it bore few sustainable "technical advantages" over the contemporary method of uranium–plutonium bombs;^[108] in particular, this nuclide is difficult to produce in an isotopically pure state; and the impurities, as well as its decay products, complicate handling it and make it more easily recognizable.^[107]

Usage of thorium as a power source has been explored; the earliest thorium-based reactor was made in the United States: the first core at the Indian Point Energy Center (Buchanan, New York) in 1962.^[109] India has one of the largest supplies of thorium in the world but does not have much uranium used elsewhere, and targeted in the 1950s at achieving energy independence for the country with their three-stage nuclear power programme.^[110][111] On the other hand, in most countries, the progress stalled because uranium was relatively abundant and the progress of thorium-based reactors was therefore slow (in the 20th century, 3 reactors were opened in India and 12 elsewhere^[112]). Large-scale research was begun in 1996 by the International Atomic Energy Agency (IAEA) to study the use of thorium reactors; a year later, the United States Department of Energy started their research on the matter. Nuclear scientist Alvin Radkowsky of Tel Aviv University in Israel, the head designer of the American first civilian nuclear power plant in Shippingport, Pennsylvania, whose third core bred thorium,^[113] founded a consortium to develop thorium reactors, which included other laboratories: Raytheon Nuclear Inc. (Cambridge, Massachusetts, United States), Brookhaven National Laboratory (Upton, New York, United States) and the Kurchatov Institute (Moscow, Russia).^[114] In the 21st century, thorium's potential for improving proliferation resistance and waste characteristics led to renewed interest in the thorium fuel cycle.^{[115][116][117]}

Production[edit]

Lower-bound estimates of thorium reserves in tonnes, 2014^[107]

Country	Reserves
India	846,000
Brazil	632,000
Australia	595,000
United States	595,000
Egypt	380,000
Turkey	374,000
Venezuela	300,000
Canada	172,000
Russia	155,000
South Africa	148,000
China	100,000
Norway	87,000
Greenland	86,000
Finland	60,500
Sweden	50,000
Kazakhstan	50,000
Other countries	1,725,000
World total	6,355,000

Worldwide production of thorium is low, at a few tens of tons per year,^[59] such low demands make working mines for extraction of thorium alone not profitable; as a result, it is almost always extracted with the rare earths, which themselves may be by-products of production of other minerals.^[118] 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.^[119] Present knowledge of the distribution of thorium resources is poor because of the relatively low-key exploration efforts arising out of insignificant demand.^[120]

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.^[121]

Concentration[edit]

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 a 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.^[34] Initial concentration varies with the type of deposit.^[121]

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 dissolution with by reaction with hydrogen chloride; then follow thickening, filtration, and calcination. The result is concentrate of a thorium with rare-earth content up to 90%.^[121] Secondary materials (such as coastal sands) undergo gravity separation. Then follows magnetic separation with a series of magnets of increasing strength. Monazite obtained by this method can be as pure as 98%.^[121]

Industrial production in the twentieth 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. However, this method heavily relied on the techique specifics and the concentrate grain size; while many alternatives have been proposed, only one has proven effective economically: alkaline digestion with hot sodium hydroxide solution. This is more expensive than the original method but yields higher purity of thorium; in particular, it removes phosphates from the concentrate.^[121]

Acid digestion[edit]

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 as it is so dense, 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.^[121]

Alkaline digestion[edit]

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, while too low a concentration of alkali leads to a very slow reaction, these reaction conditions are rather mild and consequently require finely grained monazite sand, with 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 then 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 then air may oxidise cerium from the +3 to the +4 oxidation state, and the cerium(IV) formed can then liberate free chlorine from the hydrochloric acid, the rare earths again precipitate out at higher pH. The precipitates are then neutralised by the original sodium hydroxide solution, although most of the phosphate must be removed beforehand 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.^[121]

Purification[edit]

High thorium concentrations are needed in nuclear applications; particularly, 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 these high purities. Today, liquid solvent extraction procedures involving selective complexation of Th⁴⁺ is 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.^[121]

Modern applications[edit]

Non-radioactivity-related uses have been on decline since the 1950s.^[122] Many applications of thorium are becoming obsolete due to environmental concerns largely stemming from the radioactivity of thorium and its decay products. Thorium is thus being phased out of many of its uses.^[24][105]

Most thorium applications use its dioxide (sometimes called "thoria" in the industry), rather than the metal. One particular characteristic of this compound is its high melting point, 3300 °C (6000 °F) – the highest of all known oxides; only a few substances have higher melting points.^[40] In particular, that helps the compound remain solid when introduced into a flame, and when it is, it considerably increases the luminacy of the flame; this is the main reason thorium is used in gas mantles.^[123] Although all substances emit energy (glow) when heated to high temperatures, light emitted by thorium is almost exclusively located in the visible spectrum, which explain the brightness of thorium mantles.^[124] Energy, some of it in the form of the visible light, is emitted when thorium is exposed to a source of energy itself, such as a cathode ray, heat or ultraviolet light. Generally, this effect is shared by cerium dioxide, which converts ultraviolet light into visible light more efficiently, but thorium dioxide gives a higher temperature of the flame, emitting less infrared light.^[123] Thorium in mantles, though still common, have been being replaced with a different rare-earth element, yttrium, since the late 1990s.^[125] According to the 2005 review by the United Kingdom's National Radiological Protection Board, "although they were widely available a few years ago, they are not any more."^[126]

During the production of incandescent filaments, recrystallization of tungsten is signifiantly lowered by adding small amounts of thorium dioxide to the tungsten sintering powder before drawing the filaments.^[122] A small addition of thorium to tungsten thermocathodes considerably reduced the work function of electrons; as the result, electrons are emitted at considerably lower temperatures.^[24] (Thorium forms a one-molecule-thin layer of tungsten. The work function from a thorium surface is lowered possibly because of the electric field on the surface between thorium and tungsten formed due to thorium's greater electropositivity.)^[127] non the suthorium monoxide dipole layer, which is constantly renewed from the interior of the electrode.) 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 atmospherial oxygen and nitrogen, thorium also marks impurities in the evacuated tubes. Introduction of transistors in the 1950s significantly diminished this use, though not entirely.^[122] Thorium dioxide is used in gas tungsten arc welding (GTAW) to increase the high-temperature strength of tungsten electrodes and improve arc stability.^[24] Nevertheless, because of safety concerns, thorium oxide is being replaced in this use with other oxides, such as those of zirconium, cerium, and lanthanum.^[128][129]

Thorium dioxide is a material for heat-resistant ceramics, as used in high-temperature laboratory crucibles,^[24] as a main material 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 likewise been replaced by an alloy of 95% platinum and 5% rhodium because of its better mechanical properties and greater durability.^[122]

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

When added to glass, thorium dioxide helps increase refractive index and decrease dispersion, such glass finds application in high-quality lenses for cameras and scientific instruments.^[35] 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.^[130] Yellowed lenses may be restored to their original colourless state with 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.^[122]

Thorium tetrafluoride is used as an antireflection material in multilayered optical coatings, it has an optical transparency in the range of 0.35–12 µm, and its radiation is primarily due to alpha particles, which can be easily stopped by a thin cover layer of another material.^[131] Replacements for thorium tetrafluoride are being developed as of the 2010s.^[132]

Potential use for nuclear energy[edit]

Thorium has been suggested as a potent nuclear power source and a possible replacement to the currently used uranium and plutonium. India, which has little uranium but much thorium, is a big proponent of development of thorium-based power technologies and has prioritised developing a thorium fuel cycle.^[111]

The main nuclear power source in a reactor is the spontaneous fission of a certain nuclide; of the synthetic fissile^[c] nuclei, ²³³U and ²³⁹Pu can be bred from neutron capture by the naturally occurring quantity nuclides ²³²Th and ²³⁸U (note that ²³⁵U occurs naturally and is also fissile).^{[133][134][l]} 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:^[24]

232
90Th
+ n → 233
90Th
+ γ β⁻→21.8 min 233
91Pa
β⁻→27.0 days 233
92U

²³³U is fissile and hence can be used as a nuclear fuel in much the same way as the more-commonly used ²³⁵U or ²³⁹Pu. When ²³³U undergoes nuclear fission, the neutrons emitted can strike further ²³²Th nuclei, restarting the cycle,^[24] this closely 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.^[135]

Advantages[edit]

Thorium is more abundant than uranium and hence can satisfy world energy demands for longer.

²³²Th also absorbs neutrons more readily than ²³⁸U, and not only does ²³³U have a higher probability of fission upon neutron capture (92.0%) than ²³⁵U (85.5%) or ²³⁹Pu (73.5%),^[136] it also releases more neutrons upon fission on average.^[137] While a single neutron capture by ²³⁸U would produce transuranic waste along with the fissile ²³⁹Pu, 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.^[138]

Thorium fuels also result in a safer and better-performing reactor core^[24] because thorium dioxide has a higher melting point, higher thermal conductivity, 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).^[139]

Disadvantages[edit]

The used fuel is difficult and dangerous to reprocess because many of the daughters of ²³²Th and ²³³U are strong gamma emitters.^[137] Additionally, all ²³³U production methods other than mercury fluorescence always result in significant impurities of the very dangerous 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:^[140]

230
90Th
+ n → 231
90Th
+ γ β⁻→25.5 h 231
91Pa
α→3.28 × 104
y ­ 231
91Pa
+ n → 232
91Pa
+ γ β⁻→1.3 d 232
92U

While ²³²U by itself is not particularly harmful, it quickly decays to produce significant quantities of the strong gamma emitter ²⁰⁸Tl. (While ²³²Th also follows the same decay chain, its much longer half-life means that the quantities of ²⁰⁸Tl produced by it are essentially negligible.)^[141] These impurities of ²³²U make ²³³U very easy to detect and very dangerous to work on, and the impracticality of their separation limits the possibilities of nuclear proliferation using ²³³U as the fissile material.^[140] Additionally, ²³³Pa has a relatively long half-life of 27 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 only decays to ²³³U.^[142]

The need to irradiate ²³²Th with neutrons and process it come before these advantages become real, and this requires more advanced technology than the presently used fuels based on uranium and plutonium; nevertheless, advances are being made in this area.^[24] Another common criticism centres around the low commercial viability of the thorium fuel cycle:^{[143][144][145]} some entities like the Nuclear Energy Agency go further and predict that the thorium cycle will never be commercially viable while uranium is available in abundance—a situation which Trevor Findlay predicts will persist "in the coming decades".^[146] Furthermore, though the isotopes produced in the thorium fuel cycle are mostly not transuranic, some of them are still very dangerous, such as ²³¹Pa, which has a long half-life of 32760 years and is a major contributor to the long-term radiotoxicity of spent nuclear fuel.^[142]

Hazards[edit]

Radiological[edit]

Experiment on the effect of radiation (from an unburned thorium gas mantle) on the germination and growth of timothy-grass seed

Natural thorium decays very slowly compared to many other radioactive materials, and the emitted alpha radiation cannot penetrate human skin, as a result, owning and handling small amounts of thorium, such as those in a gas mantle, is considered safe, although usage of such items may pose some risks.^[147] 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.^[147] Exposure to thorium internally leads to increased risk of liver diseases.^[148]

The decay products of ²³²Th include more dangerous radionuclides such as radium and radon, although relatively little of those products is created as the result of the faint 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,^[149] and which are built up quickly following the initial decay of ²³²Th due to the absence of long-lived nuclides along the decay chain,^[150] as the dangerous daughters of thorium have much lower melting points than thorium dioxide, they would be volatilised every time the mantle is heated for use. During burning, significant fractions of the thorium daughters ²²⁴Ra, ²²⁸Ra, ²¹²Pb, and ²¹²Bi are released in the first hour of use alone.^[151] Most of the radiation dose by a normal user arises from inhaling the radium, resulting in a radiation dose of up to 0.2 millisieverts per use, about a third of the dose sustained during a mammogram.^[152]

Some nuclear safety agencies make recommendations about use of thorium mantles and have raised some safety concerns regarding their manufacture and disposal, because while the radiation dose from one mantle is not a serious problem, that from many mantles gathered together in factories or landfills is.^[148]

Biological[edit]

Thorium is odourless and tasteless,^[153] the chemical toxicity of thorium is low because thorium and its most common compounds (mostly the dioxide) are poorly soluble in water,^[154] precipitating out before entering the body as the hydroxide.^[155] (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.)^[150] If thorium is ingested, 0.4% of it and 90% of its dangerous daughters are leached into the body.^[106] Out of the thorium that does remain in the body, three quarters of it accumulates in the skeleton. While absorption through the skin is possible, it is not a likely means of thorium exposure.^[147] Thorium's low solubility in water also means that excretion of thorium by the kidneys and faeces is rather slow.^[150]

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.^[155] 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.^[156]

Chemical[edit]

Powdered thorium metal is pyrophoric and often ignites spontaneously in air.^[4] U.S. Department of the Interior listed in 1964 thorium as "severe" on the table titled Ignition and explosibility of metal powders. Its ignition temperature was given as 270 °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); minimum igniting energy for (non-submicron) dust was 5 mJ.^[157]

In 1956, reprocessing and burning of thorium sludge at the Sylvania Electric Products' Metallurgical Laboratory in New York City, New York, U.S., resulted in a chemical explosion. Nine people were injured; one died of complications caused by third-degree burns.^{[158][159][160]}

Exposure routes[edit]

Thorium exists in very small quantities almost everywhere on Earth: the average human contains about 100 micrograms of thorium and typically consumes three micrograms per day.^[156] Most thorium exposure occurs through dust inhalation; some thorium comes with food and water, but because of its low solubility, this exposure is negligible.^[150]

Exposure is raised for people who live near thorium deposits, 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 industries.^[161] 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.^[162]

Notes[edit]

References[edit]

Bibliography[edit]

• Golub, A. M. (1971). Общая и неорганическая химия (General and Inorganic Chemistry). 2. 
• Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 0-08-037941-9. 
• Wickleder, Mathias S.; Fourest, Blandine; Dorhout, Peter K. (2006). "Thorium". In Morss, Lester R.; Edelstein, Norman M.; Fuger, Jean. The Chemistry of the Actinide and Transactinide Elements (PDF). 3 (3rd ed.). Dordrecht, the Netherlands: Springer. pp. 52–160. doi:10.1007/1-4020-3598-5_3. 
• Stoll, Wolfgang (2005). "Thorium and Thorium Compounds". Ullmann's Encyclopedia of Industrial Chemistry. Wiley-VCH. ISBN 978-3-527-31097-5. doi:10.1002/14356007.a27_001. 

Further reading[edit]

• Brett W. Jordan; Rod Eggert; Brent Dixon; Brett Carlsen (October 2014). "Thorium: Does Crustal Abundance Lead to Economic Availability?" (PDF). Colorado School of Mines Working Paper 2014-07. 

External links[edit]

Look up thorium in Wiktionary, the free dictionary.

Wikimedia Commons has media related to Thorium.

• International Thorium Energy Committee – iThEC
• International Thorium Energy Organisation – IThEO.org
• European Nuclear Society – Natural Decay Chains
• ATSDR CDC ToxFAQs: health questions about thorium
• FactSheet on Thorium, World Nuclear Association
• Thorium at The Periodic Table of Videos (University of Nottingham)