Thorium

Not to be confused with Thallium or Thulium.

232
90

Th

1.9
Years

228
89

Ac

Thorium

6.1
Minutes

228
88

Ra

5.7
Years

Actinium
224
88

Ra

3.6
Days

Radium

Francium
220
86

A thorium atom has 90 protons and therefore 90

electrons, of which four are valence electrons. Thorium
metal is silvery and tarnishes black when exposed to air.
Thorium is weakly radioactive: all its known isotopes are
unstable, with the six naturally occurring ones (thorium227, 228, 230, 231, 232, and 234) having half-lives between 25.52 hours and 14.05 billion years. Thorium-232,
which has 142 neutrons, is the most stable isotope of thorium and accounts for nearly all natural thorium, with
the other ve natural isotopes occurring only in traces:
it decays very slowly through alpha decay to radium-228,
starting a decay chain named the thorium series that ends
at lead208. Thorium is estimated to be about three to
four times more abundant than uranium in the Earths
crust, and is chiey rened from monazite sands as a byproduct of extracting rare earth metals.

Rn

55
Seconds

Radon

Astatine
216
84

Po

212
84

0.14
Seconds

Po

3e-07
Seconds

212
83

Bi

Actinides
Alkali Metals
Alkaline Earth Metals
Halogens
Metalloids
Noble Gases
Poor Metals
Transition Metals

212
82

Pb

Bismuth
208
82

10.6
Hours

Pb

Stable

208
81

Tl

3.1
Minutes

Polonium

61
Minutes

Lead

Thallium

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

Thorium was once commonly used as the light source in

gas mantles and as an alloying material, but these applications have declined due to concerns about its radioactivity. Thorium is also used as an alloying element in nonconsumable TIG welding electrodes. It remains popular
as a material in high-end optics and scientic instrumentation; thorium and uranium are the only radioactive elements with major commercial applications that do not
rely on their radioactivity. 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.

1.1

228
90

1.41e+10
Years

Thorium is a chemical element with symbol Th and

atomic number 90. A radioactive actinide metal, thorium
is one of only three radioactive elements that still occurs
in quantity in nature as a primordial element (the other
two being bismuth and uranium).[lower-alpha 1] It was discovered in 1828 by the Norwegian mineralogist Morten
Thrane Esmark and identied by the Swedish chemist
Jns Jakob Berzelius, who named it after Thor, the Norse
god of thunder.

Th

Pure thorium is soft, very ductile, and can be cold-rolled,

swaged, and drawn.[3]
The measured properties of thorium vary widely depending on the amount of impurities in the sample used: the
major impurity is usually thorium dioxide (ThO2 ). The
purest thorium specimens usually contain about a tenth
of a percent of the dioxide.[3] Its density has been calculated to be 11.724 g/cm3 , while experimental measurements give values between 11.5 and 11.66 g/cm3 :[3]
these values lie intermediate between those of its neighbours actinium (10.07 g/cm3 ) and protactinium (15.37
g/cm3 ), showing the continuity of trends across the actinide series.[3] However, thoriums melting point of 1750
C is above both that of actinium (1227 C) and that of
protactinium (156215 C): the melting points of the actinides do not have a clear dependence on their number
of f electrons, although there is a smooth trend downward from thorium to plutonium where the number of f

Characteristics
Physical

Thorium is a soft, 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.
1

electrons increases from zero to six.[4] Thorium is a soft

metal, having a bulk modulus of 54 GPa, comparable to
those of tin and scandium. The hardness of thorium is
similar to that of soft steel, so heated pure thorium can
be rolled in sheets and pulled into wire.[4] Thorium becomes superconductive below 1.40 K.[3][lower-alpha 2] Nevertheless, while thorium is nearly half as dense as uranium
and plutonium, it is harder than either of them.[4] Among
the actinides, thorium has the highest melting point and
second-lowest density (second only to actinium).[3] The
thermal expansion, electrical and thermal conductivities
of thorium, protactinium, and uranium are comparable
and are typical of post-transition metals.[5]

CHARACTERISTICS

tive charge is 3.82 and the second coordination sphere

contains 13.4 water molecules.[11] The Th4+ ion is relatively large and is the largest of the tetrapositive actinide
ions, and depending on the coordination number can have
a radius between 0.95 and 1.14 . As a result, thorium
salts have a weak tendency to hydrolyze, weaker than that
of many multiply charged ions such as Fe3+ .[11] The distinctive ability of thorium salts is their high solubility, not
only in water, but also in polar organic solvents.[4]

Thorium has been shown to activate carbonhydrogen

bonds, forming unusual compounds. Thorium atoms can
also bond to more atoms than any other element: for instance, in the compound thorium aminodiboranate, thoThorium can also form alloys with many other metals. rium has a coordination number of fteen.[13]
With chromium and uranium, it forms eutectic mixtures,
and thorium is completely miscible in both solid and liquid states with its lighter congener cerium.[3]
1.3 Atomic

1.2

Chemical

A thorium atom has 90 electrons, of which four are

valence electrons. Four atomic orbitals are theoretically
available for the valence electrons to occupy: 5f, 6d, 7s,
and 7p. However, the 7p orbital is greatly destabilized
and hence it is not occupied in the ground state of any
thorium ion.[14] Despite thoriums position in the f-block
of the periodic table, it has an anomalous [Rn]6d2 7s2
electron conguration in the ground state. However, in
metallic thorium, the [Rn]5f1 6d1 7s2 conguration is a
low-lying excited state and hence the 5f orbitals contribute, existing in a rather broad energy band.[14]

Thorium is a highly reactive metal. At standard temperature and pressure, thorium is slowly attacked by water, but does not readily dissolve in most common acids,
the exception being hydrochloric acid.[3][6] It dissolves
in concentrated nitric acid containing a small amount of
catalytic uoride or uorosilicate ions;[3][7] if these are
not present, passivation can occur.[3] At high temperatures, it is easily attacked by oxygen, hydrogen, nitrogen,
the halogens, and sulfur. It can also form binary comof thopounds with carbon and phosphorus.[3] When thorium The ground-state electron congurations
+
2 1
rium
ions
are
as
follows:
Th
,
[Rn]6d
7s
; Th2+ ,
dissolves in hydrochloric acid, a black residue, probably
1 1 [lower-alpha 3]
3+
1
4+
[Rn]5f 6d ;
Th , [Rn]5f ; Th , [Rn].
ThO(OH,Cl)H, is left behind.[3]
This shows the increasing stabilization of the 5f orbital
Finely divided thorium metal presents a re hazard as ion charge increases; however, this stabilization is
due to its pyrophoricity and must therefore be handled insucient to chemically stabilize Th3+ with its lone
carefully.[3] When heated in air, thorium turnings ignite 5f valence electron, and therefore the stable and most
and burn brilliantly with a white light to produce the diox- common form of thorium in chemicals is Th4+ with all
ide. In bulk, the reaction of pure thorium with air is four valence electrons lost, leaving behind an inert core
slow, although corrosion may eventually occur after sev- of inner electrons with the electron conguration of
eral months; most thorium samples are however contam- the noble gas radon.[14][15] The rst ionization potential
inated with varying degrees of the dioxide, which greatly of thorium was measured to be (6.08 0.12) eV in
accelerates corrosion.[3] Such samples slowly tarnish in 1974;[16] more recent measurements have rened this to
air, becoming gray and nally black.[3]
6.3067 eV.[17]
The most important oxidation state of thorium is +4, represented in compounds such as thorium dioxide (ThO2 )
and thorium tetrauoride (ThF4 ), although +3, +2, and 1.4 Isotopes
+1 states are also known, as in thorium tribromide
(ThBr3 ), thorium dihydride (ThH2 ), and thorium mono- Main article: Isotopes of thorium
bromide (ThBr).[8][9][10] Owing to thorium(IV)'s lack of
electrons on 6d and 5f orbitals, the tetravalent thorium Although thorium has 6 naturally occurring isotopes,
compounds are colorless.[4]
none of these isotopes are stable; however, one isotope,
In aqueous solution, thorium occurs exclusively as the
tetrapositive aqua ion [Th(H2 O)9 ]4+ , which has tricapped
trigonal prismatic molecular geometry:[11][12] at pH <
3, the solutions of thorium salts are dominated by this
cation.[11] The ThO bond distance is (245 1) pm, the
coordination number of Th4+ is (10.8 0.5), the eec-

232

Th, is relatively stable, with a half-life of 14.05 billion years, considerably longer than the age of the earth,
and even slightly longer than the generally accepted age
of the universe (about 13.8 billion years).[lower-alpha 4] This
isotope is the longest-lived of all isotopes with more
than 83 protons and makes up nearly all natural tho-

3
rium. As such, thorium is generally considered to be 2
mononuclidic.[18][19][20] However, in deep seawaters the
isotope 230 Th becomes more signicant, which led to
IUPAC reclassifying thorium as a binuclidic element in 2.1
2013.[21] In fact, uranium ores with low thorium concentrations can be puried to produce gram-sized thorium
samples of which over a quarter is the 230 Th isotope.[22]
Thorium has a characteristic terrestrial isotopic composition, consisting largely of 232 Th and a little 230 Th, and
thus an atomic mass can be given, which is 232.0377(4)
u.[21]

History
Discovery

232

Th is the longest-lived isotope in the 4n decay chain

which includes isotopes with a mass number divisible by 4, begins with the alpha decay of 232 Th to
228
Ra,[lower-alpha 5] and terminates at stable 208 Pb, and its
longevity means that the isotopes in its decay chain still
exist in nature as radiogenic nuclides despite their short
half-lives.[18][lower-alpha 6][lower-alpha 7] As such, natural thorium samples can be chemically puried to extract its useful daughter nuclides, such as lead-212 (212 Pb), which is
used in nuclear medicine for cancer therapy.[23][24]
Thirty radioisotopes have been characterized, which
range in mass number from 209[25] to 238.[22] The most
stable of them (after 232 Th) are 230 Th with a half-life
of 75,380 years, 229 Th with a half-life of 7,340 years,
228
Th with a half-life of 1.92 years, 234 Th with a halflife of 24.10 days, and 227 Th with a half-life of 18.68
days: all of these isotopes except 229 Th occur in nature
as trace radioisotopes due to their presence in the decay
chains of 232 Th, 235 U, and 238 U. 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. The isotope 229 Th has a nuclear isomer
(or metastable state) with a remarkably low excitation enThor, the namesake of thorium
ergy,[26] recently measured to be (7.6 0.5) eV.[27]
In the early history of the study of radioactivity, the different natural isotopes of thorium were given dierent
names. In this scheme, 227 Th was named radioactinium
(RdAc), 228 Th radiothorium (RdTh), 230 Th ionium (Io),
231
Th uranium Y (UY), 232 Th thorium (Th), and 234 Th
uranium X1 (UX1 ).[22] When it was realized that all of
these are isotopes of thorium, many of these names fell
out of use, and thorium came to refer to all isotopes,
not just 232 Th.[22] However, the name ionium is still encountered for 230 Th in the context of ionium-thorium
dating.[28][29]
Dierent isotopes of thorium behave identically chemically, but do have slightly diering physical properties:
for example, the densities of 228 Th, 229 Th, 230 Th, and
232
Th in gcm3 are respectively expected to be 11.524,
11.575, 11.626, and 11.727.[30] The isotope 229 Th is expected to be ssionable with a bare critical mass of 2839
kg, although with steel reectors this value could drop to
994 kg.[30] While 232 Th, the most common thorium isotope, is not ssionable, it is fertile as it can be converted
to ssile 233 U using neutron capture.[30][31]

In 1815, the Swedish chemist Jns Jakob Berzelius analyzed a mineral from a copper mine in Falun. Assuming that a new element was contained in the mineral, he
named the supposed element thorium after Thor, the
Norse god of thunder. However, the mineral later proved
to actually be an yttrium mineral, primarily composed of
yttrium orthophosphate.[31] As the yttrium in this mineral
was initially mistaken as being a new element, the mineral was named xenotime from the Greek words
(vain) and (honor).[32][33]
In 1828, Morten Thrane Esmark found a black mineral on
Lvya island, Norway, and gave a sample to his father,
Jens Esmark, a noted mineralogist. The elder Esmark was
not able to identify it and sent a sample to the Swedish
chemist Jns Jakob Berzelius for examination. Berzelius
determined that it contained a new element.[31] He published his ndings in 1829.[34][35][36] Berzelius reused the
name of the previous supposed element discovery.[34][37]
Thus, he named the source mineral thorite, which has the
chemical composition (Th,U)SiO4 .[31]

2.2

3 OCCURRENCE

Subsequent developments

In Dmitri Mendeleev's 1869 periodic table, 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 reected the belief
at that time that thorium and the rare earth metals were
divalent.[lower-alpha 8] 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,
titanium group, cerium, and thorium, because their maximum oxidation state was +4.[38][39] While cerium was
soon removed from the main body of the table and placed
in a separate lanthanide series, it was not until 1945 that The radiogenic heat from the decay of 232 Th is a major contribGlenn T. Seaborg realized that thorium was the second utor to the earths internal heat budget. The other major contrib235
238
40
member of the actinide series and was lling an f-block utors are U, U, and K.
row, instead of being the heavier congener of hafnium
and lling a fourth d-block row.[40][lower-alpha 9]
but still tiny traces of 234 Th and 230 Th from the decay
Thorium was rst observed to be radioactive in 1898, in- chain of uranium-238 (the uranium series).[22] Earlier in
dependently, by the Polish-French physicist Marie Curie the Earths history, 229 Th would also have been produced
and the German chemist Gerhard Carl Schmidt.[42][43][44] in the now extinct decay chain of 237 Np (the neptunium
Between 1900 and 1903, Ernest Rutherford and series): it is now only produced as a daughter of articial
Frederick Soddy showed how thorium decayed at a xed uranium-233, itself produced from neutron irradiation of
rate over time into a series of other elements. This ob- 232 Th.[22]
servation led to the identication of half-life as one of
the outcomes of the alpha particle experiments that led On Earth, thorium is not a rare element as was previously
thought, having an abundance comparable to that of lead
to their disintegration theory of radioactivity.[45]
and molybdenum, twice that of arsenic, and thrice that
Although thorium was discovered in 1828, it had no ap- of tin.[48] In nature, it occurs in the +4 oxidation state,
plications until 1885, when Carl Auer von Welsbach in- together with uranium(IV), zirconium(IV), hafnium(IV),
vented the gas mantle.[31] After 1885, many applications and cerium(IV), but also with the scandium, yttrium, and
were found for thorium and its compounds. In recent the trivalent lanthanides which have similar ionic radii.[48]
decades, however, most of these applications that do not However, thorium only occurs as a minor constituent of
depend on thoriums radioactivity have declined due to most minerals.[48]
safety and environmental concerns.[31]
Thorium minerals occur on all continents.[6][49][50] Thorium is several times more abundant in Earths crust than
all isotopes of uranium combined and thorium-232 is several hundred times more abundant than uranium-235.[48]
3 Occurrence
Because of thoriums radioactivity, minerals containing
signicant quantities of thorium are often metamict, their
Main article: Occurrence of thorium
Thorium-232 is a primordial nuclide, having existed in crystal structure having been partially or totally destroyed
by the alpha radiation produced in the radioactive deits current form for over 4.5 billion years, predating the
[51][lower-alpha 10]
An extreme example is
formation of the Earth; it was forged in the cores of dy- cay of thorium.
ekanite
((Ca,Fe,Pb)
2 (Th,U)Si8 O20 ), which almost never
ing stars through the r-process and scattered across the
being an esgalaxy by supernovae.[46] Its radioactive decay produces occurs in nonmetamict form due to thorium
[52]
sential
part
of
its
chemical
composition.
[47]
a signicant amount of the Earths internal heat.
Natural thorium is essentially monoisotopic 232 Th, which
is the longest-lived and most stable isotope of thorium,
having a half-life comparable to the age of the universe.
If the source contains no uranium, the only other thorium isotope present would be 228 Th, which occurs in the
decay chain of thorium-232 (the thorium series): the ratio of 228 Th to 232 Th would be under 1010 .[22] However,
if uranium is present, tiny traces of several other isotopes
will be present: 231 Th and 227 Th from the decay chain
of uranium-235 (the actinium series), and slightly larger

Monazite is the most important commercial source of

thorium because it occurs in large deposits worldwide
and contains 2.5% thorium. It is a chemically unreactive phosphate mineral that has a high specic gravity and
is found as yellow or brown monazite sand; its low reactivity makes it dicult to extract thorium from it.[48]
Allanite can have 0.12% thorium and zircon up to 0.4%
thorium.[48]
Thorium dioxide occurs as the rare mineral thorianite,
which usually contains up to 12% ThO2 . However,

5
due to its being isotypic with uranium dioxide, the
two actinide dioxides can form solid-state solutions and
the name of the mineral changes according to the
ThO2 content.[48][lower-alpha 11] Thorite, or thorium silicate (ThSiO4 ),[lower-alpha 12] also has a high thorium content and is the mineral in which thorium was rst
discovered.[48] 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.[48][lower-alpha 13]

Production

ThO2 + 2 Ca 2 CaO + Th
Sometimes thorium is extracted by electrolysis of a uoride in a mixture of sodium and potassium chloride at
700800 C in a graphite crucible. Highly pure thorium
can be extracted from its iodide with the crystal bar process.[55]

5 Compounds
5.1 Oxides and hydroxides
See also: Thorium dioxide
In air, thorium turnings burn to form the simple dioxide,

Monazite a major thorium mineral

Thorium is extracted mostly from monazite: thorium

diphosphate (Th(PO4 )2 ) is reacted with nitric acid, and
the produced thorium nitrate treated with tributyl phosphate. Rare-earth impurities are separated by increasing
the pH in sulfate solution.[53]

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

ThO2 , also called thoria or thorina.[56] Thoria, a refractory material, has the highest melting point (3390 C) of
all known oxides.[57] It is somewhat hygroscopic and reacts readily with water and many gases.[9] When heated,
it emits intense blue light, which becomes white when
mixed with its lighter homolog cerium dioxide (CeO2 ,
ceria): this is the basis for its previously common application in gas mantles.[9] Related to thoria is the oxoanion
ThO2
3, found in BaThO3 and K2 ThO3 .[9] Reports of thorium
peroxide, initially supposed to be Th2 O7 and be formed
from reacting thorium salts with hydrogen peroxide, were
later discovered to contain both peroxide anions and the
anions of the reacting thorium salt.[9] Thorium monoxide has recently been produced through laser ablation of
thorium in the presence of oxygen.[58] This highly polar
molecule has the largest known internal electric eld.[59]

In another extraction method, monazite is decomposed

with a 45% aqueous solution of sodium hydroxide at 140
C. Mixed metal hydroxides are extracted rst, ltered
at 80 C, washed with water and dissolved with concentrated hydrochloric acid. Next, the acidic solution is neutralized with hydroxides to pH = 5.8 that results in precipitation of thorium hydroxide (Th(OH)4 ) contaminated
with ~3% of rare-earth hydroxides; the remaining rareearth hydroxides remain in solution. Thorium hydroxide
is dissolved in an inorganic acid and then puried from
the rare earth elements. An ecient method is the dissolution of thorium hydroxide in nitric acid, because the
resulting solution can be puried by extraction with or- Thorium hydroxide, Th(OH)4 , can be prepared by adding
a hydroxide of ammonium or an alkali metal to a thoganic solvents:[53]
rium salt solution, where it appears as a gelatinous precipitate that will dissolve in dilute acids, among other
Th(OH)4 + 4 HNO3 Th(NO3 )4 + 4 H2 O
substances.[9] It can also be prepared by electrolysis of
thorium nitrates.[9] It is stable from 260450 C; at 470
Metallic thorium is separated from the anhydrous ox- C and above it continuously decomposes to become
ide or chloride by reacting it with calcium in an inert thoria.[9] It easily absorbs atmospheric carbon dioxide to
form the hydrated carbonate ThOCO3 xH2 O and, under
atmosphere:[54]

COMPOUNDS

high-pressure conditions in a carbon dioxide atmosphere, boiling points are 679 C and 857 C.[10] Like the tetraTh(CO3 )2 0.5H2 O or Th(OH)2 CO3 2H2 O.[9][60]
chloride, both an and a form exist and both are
isotypic to the tetrachloride forms, though the phase
transition here occurs at 426 C. There is also a low5.2 Halides
temperature form.[10] Incomplete reports of the lower
bromides ThBr3 , ThBr2 , and ThBr are known (the last
only known as a gas-phase molecular species): ThBr3 and
ThBr2 are known to be very reactive and at high temperatures disproportionate.[10]

Crystal structure of thorium tetrauoride. Th4+ : __ / F : __

All four thorium tetrahalides are known, as are some lowvalent bromides and iodides.[10] Additionally, many related polyhalide ions are also known.[10] Thorium tetrauoride (ThF4 ) is most easily produced by reacting various thorium salts, thoria, or thorium hydroxide with
hydrogen uoride: methods that involve steps in the aqueous phase are more dicult because they result in hydroxide and oxide uorides that have to be reduced with
hydrogen uoride or uorine gas.[10] It has a monoclinic
crystal structure and is isotypic with zirconium tetrauoride and hafnium tetrauoride, where the Th4+ ions are
coordinated with F ions in somewhat distorted square
antiprisms.[10] It is a white, hygroscopic powder: at temperatures above 500 C, it reacts with atmospheric moisture to produce the oxyuoride ThOF2 .[61]
Thorium tetrachloride (ThCl4 ) can be produced in many
ways. The usual method is crystallization from an aqueous solution and then heating the product above 100 C
to dehydrate it.[10] Further purication can be achieved
by subliming it. Its melting and boiling points are respectively 770 C and 921 C.[10] It undergoes a phase transition at 405 C, with a low-temperature phase and hightemperature phase. Nevertheless, the phase usually
persists below the transition temperature. Both phases
crystallize in the tetragonal crystal system and the structural dierences are small.[10] Below 203 C, a lowtemperature form exists with a complex structure.[10]

Thorium tetraiodide (ThI4 ) is prepared by direct reaction of the elements in a sealed silica ampoule. Water and oxygen must not be present, or else ThOI2 and
ThO2 can contaminate the product.[10] It has a dierent crystal structure from the other tetrahalides, being
monoclinic.[10] The lower iodides ThI3 and ThI2 can be
prepared by reducing the tetraiodide with thorium metal.
(ThI is also predicted to form as an intermediate in the
dissociation of ThI4 to thorium metal.)[10] These do not
contain Th(III) and Th(II), but instead contain Th4+ and
could be more clearly formulated as Th4+ (I )3 (e ) and
Th4+ (I )2 (e )2 respectively.[10] Depending on the amount
of time allowed for the reaction between ThI4 and thorium, two modications of ThI3 can be produced: shorter
times give thin lustrous rods of -ThI3 , while longer times
give small -ThI3 crystals with green to brass-colored
luster.[10] ThI2 also has two modications, which can be
produced by varying the reaction temperature: at 600 C,
-ThI2 is formed, while a reaction temperature of 700
850 C produces -ThI2 , which has a golden luster.[10]
Many polynary halides with the alkali metals, barium,
thallium, and ammonium are known for thorium uorides, chlorides, and bromides.[10] For example, when
treated with potassium uoride and hydrouoric acid,
Th4+ forms the complex anion ThF2
6, which precipitates as an insoluble salt, K2 ThF6 .[7]

5.3 Chalcogenides and pnictides

The heavier chalcogens sulfur, selenium, and tellurium
are known to form thorium chalcogenides, many of which
have more complex structure than the oxides. Apart from
several binary compounds, the oxychalcogenides ThOS
(yellow), ThOSe, and ThOTe are also known.[62] The ve
binary thorium suldes ThS (lustrous metallic), Th2 S3
(brown metallic), Th7 S12 (black), ThS2 (purple-brown),
and Th2 S5 (orange-brown) may be produced by reacting hydrogen sulde with thorium, its halides, or thoria
(the last if carbon is present): they all hydrolyze in acidic
solutions.[62] The six selenides are analogous to the suldes, with the addition of ThSe3 .[62] The ve tellurides
are also similar to the suldes and selenides (although
Th2 Te5 is unknown), but have slightly dierent crystal
structures: for example, ThS has the sodium chloride
structure, but ThTe has the caesium chloride structure.[62]

Thorium tetrabromide (ThBr4 ) can be produced either by

reacting thorium(IV) hydroxide with hydrobromic acid
(which has the disadvantage of often resulting in products contaminated with oxybromides) or by directly reacting bromine or hydrogen bromide with thorium metal
or compounds.[10] The product can then be puried by All ve chemically characterized pnictogens (nitrogen,
sublimation at 600 C in a vacuum.[10] The melting and phosphorus, arsenic, antimony, and bismuth) also form

5.5

Organometallic and other carbon-containing compounds

compounds with thorium.[63] Three thorium nitrides are

known: ThN, Th3 N4 , and Th2 N3 . The brass-colored
Th3 N4 is most easily produced by heating thorium metal
in a nitrogen atmosphere. Th3 N4 and Th2 N3 decompose to the golden-yellow ThN, and indeed ThN can
often be seen covering the surface of Th3 N4 samples
because Th3 N4 is hygroscopic and water vapor in the
air can decompose it: thin lms of ThN are metallic
in character and, like all other actinide mononitrides,
has the sodium chloride structure. ThN is also a lowtemperature superconductor. All three nitrides can react
with thorium halides to form halide nitrides ThNX (X =
F, Cl, Br, I).[63] The heavier pnictogens also form analogous monopnictides, except ThBi which has not yet been
structurally characterized. The other well-characterized
thorium pnictides are Th3 P4 , Th2 P11 , ThP7 , Th3 As4 ,
ThAs2 , Th3 Sb4 , ThSb2 , and ThBi2 .[63]

5.4

Other inorganic

Thorium reacts with hydrogen to form the thorium hydrides ThH2 and Th4 H15 , the latter of which is superconducting below the transition temperature of 7.58 K; at
standard temperature and pressure, it conducts electricity
like a metal.[8] Finely divided thorium metal reacts very
readily with hydrogen at standard conditions, but large
pieces may need to be heated to 300400 C for a reaction to take place.[8] Around 850 C, the reaction forming
rst ThH2 and then Th4 H15 occurs without breaking up
the structure of the thorium metal.[8] Thorium hydrides
react readily with oxygen or steam to form thoria, and
at 250350 C quickly react with hydrogen halides, suldes, phosphides, and nitrides to form the corresponding
thorium binary compounds.[8]
Three binary thorium borides are known: ThB6 , ThB4 ,
and ThB12 . The last is isotypic with UB12 . While reports
of ThB66 and ThB76 exist, they may simply be thoriumstabilized boron allotropes.[64] The three known binary
thorium carbides are ThC2 , Th2 C3 , and ThC: all are produced by reacting thorium or thoria with carbon. ThC
and ThC2 are refractory solids and have melting points
over 2600 C.[64]
Many other inorganic thorium compounds with polyatomic anions are known, such as the perchlorates,
sulfates, sultes, nitrates, carbonates, phosphates,
vanadates, molybdates, chromates, and other
oxometallates,[lower-alpha 14] many of which are known
in hydrated forms.[60] These are important in thorium
purication and the disposal of nuclear waste, but most
have not yet been fully characterized, especially on their
structural properties.[60] For example, thorium perchlorate is very water-soluble and crystallizes from acidic
solutions as the tetrahydrate Th(ClO4 )4 4H2 O, while
thorium nitrate forms tetra- and pentahydrates, is soluble
in water and alcohols, and is an important intermediate
in the purication of thorium and its compounds.[60]

Structure of thorocene

5.5 Organometallic and other carboncontaining compounds

Like many of the early and middle actinides (thorium through americium, and also expected for curium),
thorium forms the yellow cyclooctatetraenide complex
Th(C8 H8 ), thorocene. It is isotypic with the more wellknown analogous uranium compound, uranocene.[65] It
can be prepared by reacting K2 C8 H8 with thorium tetrachloride in tetrahydrofuran (THF) at the temperature
of dry ice, or by reacting thorium tetrauoride with
MgC8 H8 .[65] It is an unstable compound in air and
outright decomposes in water or at 190 C.[65] Many
other organothorium compounds are known, many involving the cyclopentadienyl anion.[65] Some coordination complexes with carboxylates and acetylacetonates
are also known, although these are not organothorium
compounds.[60]

6 Applications
6.1 Nuclear
Due to environmental concerns over thoriums radioactivity that cause its non-nuclear applications to sharply decrease in importance, the most important possible use of
thorium is now its possible use in the thorium fuel cycle as a nuclear fuel, as its applications in radiometric
dating (which depend on its radioactivity) are mostly
specialized.[31]

8
6.1.1

6 APPLICATIONS
Nuclear energy

Main article: Thorium fuel cycle

In thermal breeder reactors, the fertile isotope 232 Th, the
most common thorium isotope, is bombarded by slow
neutrons, undergoing neutron capture to become 233 Th,
which undergoes two consecutive beta decays to become
rst 233 Pa and then the ssile 233 U:[31]

232
90 Th

+ n 233
233
233
90 Th +
91 Pa
92 U

233

U is ssile and hence can be used as a nuclear fuel in

much the same way as the more-commonly used 235 U or
239
Pu. When 233 U undergoes nuclear ssion, the neutrons emitted can strike further 232 Th nuclei, restarting
the cycle.[31] This closely parallels the uranium fuel cycle
in fast breeder reactors where 238 U undergoes neutron
capture to become 239 U, beta decaying to rst 239 Np and
then ssile 239 Pu.[66] The main advantage of the thorium
fuel cycle is that thorium is more abundant than uranium
and hence can satisfy world energy demands for longer.
An added advantage 233 U and 239 Pu enjoy over all other
ssile nuclei (except the naturally occurring 235 U) is that
they can be bred from the naturally-occurring quantity
isotopes 232 Th and 238 U.[67][68][lower-alpha 15] Additionally,
233
U is easily detected, can be mixed with 238 U to prevent direct use in nuclear weapons and limit nuclear proliferation, and has a higher neutron yield than 239 Pu.
Thorium fuels also result in a safer and better-performing
reactor core[31] because thoria has a higher melting point,
higher thermal conductivity, and lower coecient of thermal expansion than the now-common fuel uranium dioxide (UO2 ): thoria also exhibits greater chemical stability
and, unlike uranium dioxide, does not further oxidize.[69]
A single neutron capture by 238 U would produce
transuranic waste, along with it ssile 239 Pu, whereas six
captures are generally necessary to do so from 232 Th. 98
99% of thorium-cycle fuel nuclei would ssion at either
233
U or 235 U, so fewer long-lived transuranics are produced. Because of this, thorium is a potentially attractive alternative to uranium in mixed oxide (MOX) fuels
to minimize the generation of transuranics and maximize
the destruction of plutonium.[70] The disadvantages of
the thorium fuel cycle include the need to neutron irradiate and process natural 232 Th 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
technology.[31]
In 1997, the U.S. Energy Department underwrote research into thorium fuel, and research also was begun
in 1996 by the International Atomic Energy Agency
(IAEA), to study the use of thorium reactors. Nuclear
scientist Alvin Radkowsky of Tel Aviv University in Israel founded a consortium to develop thorium reactors,

which included other companies: Raytheon Nuclear Inc.,

Brookhaven National Laboratory and the Kurchatov Institute in Moscow.[71] Radkowsky was chief scientist in
the U.S. nuclear submarine program directed by Admiral
Hyman Rickover and later headed the design team that
built the USAs rst civilian nuclear power plant at Shippingport, Pennsylvania, which was a scaled-up version of
the rst naval reactor.[71] The third Shippingport core, initiated in 1977, bred thorium.[72] Even earlier examples
of reactors using fuel with thorium exist, including the
rst core at the Indian Point Energy Center in 1962.[73]
However, in most countries uranium was relatively abundant and hence research into thorium fuel waned for a
while. A notable exception was Indias three-stage nuclear power programme.[74] In the twenty-rst century
thoriums potential for improving proliferation resistance
and waste characteristics led to renewed interest in the
thorium fuel cycle.[75][76][77] Currently, some countries
such as India are developing technology for thorium nuclear reactors.[78][79]

6.1.2 Radiometric dating

Two radiometric dating methods involve thorium isotopes: uranium-thorium dating, involving the decay of
234
U to 230 Th (ionium), and ionium-thorium dating,
which measures the ratio of 232 Th to 230 Th. These rely
on the fact that 232 Th is a primordial radioisotope, but
230
Th only occurs as an intermediate decay product in the
decay chain of 238 U.[80] Uranium-thorium dating is a relatively short-range process because of the short half-lives
of 234 U and 230 Th relative to the age of the Earth: it is
also accompanied by a sister process involving the alpha
decay of 235 U into 231 Th, which very quickly becomes
the longer-lived 231 Pa, and this process is often used to
check the results of uranium-thorium dating. Uraniumthorium 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-oor sediments, from which their ratios are measured. The scheme has a range of several
hundred thousand years.[80][81] Ionium-thorium dating is
a related process, which exploits the insolubility of thorium (both 232 Th and 230 Th) and thus its presence in
ocean sediments to date these sediments by measuring
the ratio of 232 Th to 230 Th.[28][29] Both of these dating
methods assume that the proportion of thorium-230 to
thorium-232 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.[28][29]

9
ements are found in the laments of vacuum tubes, e.g.
magnetron found in microwave oven. Thorium is added
because it lowers the eective work function with the result that the thoriated tungsten thermocathode emits electrons at considerably lower temperatures.[31] Thoria has
been used as a catalyst in the conversion of ammonia to
nitric acid,[31] in petroleum cracking and in producing
sulfuric acid.[31] It is the active ingredient of Thorotrast,
which was used as radiocontrast agent for X-ray diagnostics because of thoriums high opacity to X-rays. This use
has been abandoned due to its carcinogenic nature.[6]
Thorium tetrauoride is used as an antireection material
in multilayered optical coatings. It has excellent optical
Thorium oxide gas mantle
transparency in the range of 0.3512 m, and its radiation
is primarily due to alpha particles, which can be easily
6.2 Non-nuclear
stopped by a thin cover layer of another material.[87] Thorium tetrauoride was also used in manufacturing carbon
Many non-nuclear applications of thorium are becom- arc lamps, which provided high-intensity illumination for
ing obsolete due to environmental concerns largely stem- movie projectors and search lights.[82]
ming from the radioactivity of thorium and its decay
products.[31]
The melting point of thoria 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).[57] This
means that when heated to high temperatures, it does
not melt, but merely glows with an intense blue light;
addition of cerium dioxide gives a bright white light.[9]
This property of thoria means that thoria and thorium nitrate are used in mantles of portable gas lights, including natural gas lamps, oil lamps and camping lights.[82]
A study in 1981 estimated that the dose from using a
thorium mantle every weekend for a year would be 0.30.6 millirems (mrem), tiny in comparison to the normal
annual dose of a few hundred millirems (a person actually ingesting a mantle would receive a dose of 200
mrem (2 mSv)).[83][84] However, the radioactivity is a
major concern for people involved with the manufacture of mantles, and an issue with contamination of soil
around some former factory sites.[85] Due to these concerns, some manufacturers have switched to other materials, such as yttrium, although these are usually either more
expensive or less ecient. Other manufacturers continue
to make thorium mantles, but moved their factories to
developing countries.[84]
Thoria is a material for heat-resistant ceramics, as used
in high-temperature laboratory crucibles.[31] When added
to glass, it helps increase refractive index and decrease
dispersion. Such glass nds application in high-quality
lenses for cameras and scientic instruments.[6] The radiation from these lenses can darken them and turn them
yellow over a period of years and degrade lm, but the
health risks are minimal.[86] Yellowed lenses may be restored to their original colorless state with lengthy exposure to intense ultraviolet radiation.

7 Precautions

Experiment on the eect of radiation (from an unburned thorium

gas mantle) on the germination and growth of timothy-grass seed;
from Popular Science, 1909.

As thorium occurs naturally, it 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 of thorium.[88] This
exposure is raised for people who live near uranium,
phosphate, or tin processing factories, thorium deposits,
radioactive waste disposal sites, and for those who work
in uranium, thorium, tin, or phosphate mining or gas
mantle production industries.[89] When thorium is ingested, 99.98% does not remain in the body. 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.[90] Powdered thorium metal is pyrophoric and
often ignites spontaneously in air.[3]

Thoria was used to control the grain size of tungsten metal Natural thorium decays very slowly compared to many
used for spirals of electric lamps. Thoriated tungsten el- other radioactive materials, and the alpha radiation emit-

10

REFERENCES

ted cannot penetrate human skin meaning owning and

thorium and uranium are given values half of their actual
ones.
handling small amounts of thorium, such as a gas mantle, is considered safe.[90] Because 232 Th is only weakly
[9] A second extra-long periodic table row, to accommodate
radioactive, but decays to more dangerous radionuclides
known and undiscovered elements with an atomic weight
such as radium and radon, emitting alpha and gamma
greater than bismuth (thorium, protactinium and uranium,
radiation, a proper assessment of the radiological toxifor example), had been postulated as far back as 1892.
city of 232 Th must include the contribution of its daughMost investigators, however, considered that these eleters such as 228 Ra.[91] Exposure to an aerosol of thoments were analogous to the third-row transition elements
hafnium, tantalum and tungsten. The existence of a secrium, however, can lead to increased risk of cancers of
ond inner transition series, in the form of the actinides,
the lung, pancreas, and blood, as lungs and other internal
[90]
was not accepted until similarities with the electron strucorgans can be penetrated by alpha radiation. Exposure
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to thorium internally leads to increased risk of liver diseases. Thorium is radioactive and produces a radioactive [10] The same also applies to uranium minerals, and many thogas, radon220, as one of its decay products. Secondary
rium minerals also contain uranium.[51][52]
decay products of thorium include radium and actinium.
Because of this, there are concerns about the safety of [11] Thorianite refers to minerals with 75100 mol% ThO2 ;
uranothorianite, 2575 mol% ThO2 ; thorian uraninite,
thorium mantles. Some nuclear safety agencies make rec1525 mol% ThO2 ; uraninite, 015 mol% ThO2 .[48]
[92]
ommendations about their use. Production of gas mantles has led to some safety concerns during manufacture. [12] More specically, thorite refers to thorium silicate with
the tetragonal zircon structure; monoclinic thorium sili-

The chemical toxicity of thorium is low because thorium

cate is referred to as huttonite.[48]
and its most common compounds (mostly the dioxide) are
poorly soluble in water.[93] Nevertheless, some thorium [13] Hydroxide ions may also replace silicate ions to form
Th(SiO4 )x(OH)x, which as a mineral is named
compounds are chemically moderately toxic. People who
thorogummite.[48]
work with thorium compounds are at a risk of dermatitis.
It can take as much as thirty years after the ingestion of [14] Among the low number of other known thorium oxometthorium for symptoms to manifest themselves.[88]
allates are the arsenate, tungstate, germanate, silicate,

Notes

[1] Traces of primordial plutonium244 still exist in

nature,[2] but this does not occur in quantity, unlike bismuth, thorium, and uranium.
[2] The transition temperature is between 1.35 and 1.40 K.[3]
[3] [Rn]6d2 is a very low-lying excited state conguration of
Th2+ .[14]
[4]

[5]

232

Th is in fact the shortest-lived nuclide that still has a

half-life longer than the generally accepted age of the universe. It is the sixth-most unstable primordial nuclide:
among the primordial nuclides, only 238 U, 40 K, 235 U,
146
Sm, and 244 Pu have shorter half-lives.[18]
232

Th has the following extremely rare decay modes:

double beta decay to 232 U; spontaneous ssion; and
cluster decay to 182 Yb, expelling 26 Ne and 24 Ne
clusters.[18]

[6] The longest-lived intermediate decay product of 232 Th is

its immediate alpha daughter 228 Ra, which has a half-life
of only 5.7 years.[18]
[7] Technically, the 4n chain starts at primordial 244 Pu, which
decays successively to 240 U, 240 Np, 240 Pu, 236 U, and then
232
Th: however, the concentration of primordial 244 Pu is
now reduced to mere traces and hence these radioisotopes
are extinct for all practical purposes.[18]
[8] This is shown by the fact that the rare earths are there given
atomic weight values two-thirds of their actual ones, and

borate, and perrhenate. While thorium titanates and

tantalates are known, they are structurally more like double oxides than true oxometallates.[60]
[15] The thirteen ssile actinide isotopes with half-lives over
a year are 229 Th, 233 U, 235 U, 236 Np, 239 Pu, 241 Pu,
242m
Am, 243 Cm, 245 Cm, 247 Cm, 249 Cf, 251 Cf, and
252
Es. Of these, only 235 U is naturally occurring, and
only 233 U and 239 Pu can be bred from naturally occurring nuclei with single neutron capture.[67][68]

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13

[75] IAEA-TECDOC-1349 Potential of thorium-based fuel

cycles to constrain plutonium and to reduce the long-lived
waste toxicity. International Atomic Energy Agency.
2002. Retrieved 2009-03-24.
[76] Evans, Brett (April 14, 2006). Scientist urges switch to
thorium. ABC News. Archived from the original on
2010-03-28. Retrieved 2011-09-17.
[77] Martin, Richard (December 21, 2009). Uranium Is So
Last Century Enter Thorium, the New Green Nuke.
Wired. Retrieved 2010-06-19.
[78] Progress on Indias Thorium Nuclear Reactor and South
Africas Pebble Bed. Nextbigfuture.com (22 August
2008). Retrieved on 2011-05-01.

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 3 (3rd
ed.). Dordrecht, the Netherlands: Springer. pp. 52
160. doi:10.1007/1-4020-3598-5_3.

11 External links
International Thorium Energy Committee iThEC
International Thorium Energy Organisation
IThEO.org

[79] Nuclear Power in India|Indian Nuclear Energy. Worldnuclear.org. Retrieved on 1 May 2011.

European Nuclear Society Natural Decay Chains

[80] 3-6: Uranium Thorium Dating

ATSDR CDC ToxFAQs: health questions about

thorium

[81] Uranium-Thorium Dating

[82] McKetta, John J. (1996). Encyclopedia of Chemical Processing and Design: Thermoplastics to Trays, Separation,
Useful Capacity. CRC Press. p. 81. ISBN 0-8247-2609X.
[83] Stoves - Survival Unlimited
[84] The Straight Dope: Are camp lanterns radioactive?
[85] http://www.state.nj.us/health/eoh/hhazweb/hhw_no_3.
pdf
[86] Thoriated Camera Lens (ca. 1970s)
[87] Rancourt, James D. (1996). Optical thin lms: user handbook. SPIE Press. p. 196. ISBN 0-8194-2285-1.
[88] Emsley, John (2011). Natures Building Blocks.
[89] Thorium ToxFAQs Agency for Toxic Substances and
Disease Registry
[90] Thorium: Radiation Protection US EPA
[91] Natural Decay Series: Uranium, Radium, and Thorium.
Argonne National Laboratory, EVS: Human Health Fact
Sheet, August 2005]
[92] Radioactivity in Lantern Mantles. Australian Radiation
Protection and Nuclear Safety Agency
[93] B. Merkel, G. Dudel et al.: Untersuchungen zur radiologischen Emission des Uran-Tailings Schneckenstein, 1988
(PDF; 4,0 MB), TU Bergakademie Freiberg and TU Dresden.

10

Bibliography

Golub, A. M. (1971).
(General and Inorganic Chemistry) 2.
Greenwood, Norman N.; Earnshaw, Alan (1997).
Chemistry of the Elements (2nd ed.). ButterworthHeinemann. ISBN 0080379419.

FactSheet on Thorium, World Nuclear Association

Thorium at The Periodic Table of Videos (University
of Nottingham)

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12

12
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