Actinide Halides
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The actinide () or actinoid () series encompasses at least the 14 metallic
chemical element A chemical element is a chemical substance whose atoms all have the same number of protons. The number of protons is called the atomic number of that element. For example, oxygen has an atomic number of 8: each oxygen atom has 8 protons in its ...
s in the 5f series, with
atomic number The atomic number or nuclear charge number (symbol ''Z'') of a chemical element is the charge number of its atomic nucleus. For ordinary nuclei composed of protons and neutrons, this is equal to the proton number (''n''p) or the number of pro ...
s from 89 to 102,
actinium Actinium is a chemical element; it has chemical symbol, symbol Ac and atomic number 89. It was discovered by Friedrich Oskar Giesel in 1902, who gave it the name ''emanium''; the element got its name by being wrongly identified with a substa ...
through
nobelium Nobelium is a synthetic element, synthetic chemical element; it has Chemical symbol, symbol No and atomic number 102. It is named after Alfred Nobel, the inventor of dynamite and benefactor of science. A radioactive metal, it is the tenth transura ...
. Number 103,
lawrencium Lawrencium is a synthetic chemical element; it has symbol Lr (formerly Lw) and atomic number 103. It is named after Ernest Lawrence, inventor of the cyclotron, a device that was used to discover many artificial radioactive elements. A radioactiv ...
, is also generally included despite being part of the 6d transition series. The actinide series derives its name from the first element in the series, actinium. The informal chemical symbol An is used in general discussions of actinide chemistry to refer to any actinide. The 1985 IUPAC ''Red Book'' recommends that ''actinoid'' be used rather than ''actinide'', since the suffix ''-ide'' normally indicates a negative ion. However, owing to widespread current use, ''actinide'' is still allowed. Actinium through nobelium are
f-block A block of the periodic table is a set of elements unified by the atomic orbitals their valence electrons or vacancies lie in. The term seems to have been first used by Charles Janet. Each block is named after its characteristic orbital: s-bl ...
elements, while lawrencium is a d-block element and a
transition metal In chemistry, a transition metal (or transition element) is a chemical element in the d-block of the periodic table (groups 3 to 12), though the elements of group 12 (and less often group 3) are sometimes excluded. The lanthanide and actinid ...
. The series mostly corresponds to the filling of the 5f
electron shell In chemistry and atomic physics, an electron shell may be thought of as an orbit that electrons follow around an atom's nucleus. The closest shell to the nucleus is called the "1 shell" (also called the "K shell"), followed by the "2 shell" (o ...
, although as isolated atoms in the ground state many have anomalous configurations involving the filling of the 6d shell due to interelectronic repulsion. In comparison with the
lanthanide The lanthanide () or lanthanoid () series of chemical elements comprises at least the 14 metallic chemical elements with atomic numbers 57–70, from lanthanum through ytterbium. In the periodic table, they fill the 4f orbitals. Lutetium (el ...
s, also mostly f-block elements, the actinides show much more variable valence. They all have very large atomic and ionic radii and exhibit an unusually large range of physical properties. While actinium and the late actinides (from curium onwards) behave similarly to the lanthanides, the elements
thorium Thorium is a chemical element; it has symbol Th and atomic number 90. Thorium is a weakly radioactive light silver metal which tarnishes olive grey when it is exposed to air, forming thorium dioxide; it is moderately soft, malleable, and ha ...
,
protactinium Protactinium is a chemical element; it has symbol Pa and atomic number 91. It is a dense, radioactive, silvery-gray actinide metal which readily reacts with oxygen, water vapor, and inorganic acids. It forms various chemical compounds, in which p ...
, and
uranium Uranium is a chemical element; it has chemical symbol, symbol U and atomic number 92. It is a silvery-grey metal in the actinide series of the periodic table. A uranium atom has 92 protons and 92 electrons, of which 6 are valence electrons. Ura ...
are much more similar to
transition metal In chemistry, a transition metal (or transition element) is a chemical element in the d-block of the periodic table (groups 3 to 12), though the elements of group 12 (and less often group 3) are sometimes excluded. The lanthanide and actinid ...
s in their chemistry, with
neptunium Neptunium is a chemical element; it has chemical symbol, symbol Np and atomic number 93. A radioactivity, radioactive actinide metal, neptunium is the first transuranic element. It is named after Neptune, the planet beyond Uranus in the Solar Syste ...
,
plutonium Plutonium is a chemical element; it has symbol Pu and atomic number 94. It is a silvery-gray actinide metal that tarnishes when exposed to air, and forms a dull coating when oxidized. The element normally exhibits six allotropes and four ...
, and
americium Americium is a synthetic element, synthetic chemical element; it has Chemical symbol, symbol Am and atomic number 95. It is radioactive and a transuranic member of the actinide series in the periodic table, located under the lanthanide element e ...
occupying an intermediate position. All actinides are
radioactive Radioactive decay (also known as nuclear decay, radioactivity, radioactive disintegration, or nuclear disintegration) is the process by which an unstable atomic nucleus loses energy by radiation. A material containing unstable nuclei is conside ...
and release energy upon radioactive decay; naturally occurring uranium and thorium, and synthetically produced plutonium are the most abundant actinides on Earth. These have been used in
nuclear reactor A nuclear reactor is a device used to initiate and control a Nuclear fission, fission nuclear chain reaction. They are used for Nuclear power, commercial electricity, nuclear marine propulsion, marine propulsion, Weapons-grade plutonium, weapons ...
s, and uranium and plutonium are critical elements of
nuclear weapon A nuclear weapon is an explosive device that derives its destructive force from nuclear reactions, either fission (fission or atomic bomb) or a combination of fission and fusion reactions (thermonuclear weapon), producing a nuclear exp ...
s. Uranium and thorium also have diverse current or historical uses, and americium is used in the
ionization chamber The ionization chamber is the simplest type of gaseous ionisation detector, and is widely used for the detection and measurement of many types of ionizing radiation, including X-rays, gamma rays, alpha particles and beta particles. Conventionall ...
s of most modern
smoke detector A smoke detector is a device that senses smoke, typically as an indicator of fire. Smoke detectors/alarms are usually housed in plastic enclosures, typically shaped like a disk about in diameter and thick, but shape and size vary. Smoke can be ...
s. Due to their long half-lives, only thorium and uranium are found on Earth and astrophysically in substantial quantities. The radioactive decay of uranium produces transient amounts of actinium and protactinium, and atoms of neptunium and plutonium are occasionally produced from transmutation reactions in
uranium ore Uranium ore deposits are economically recoverable concentrations of uranium within Earth's crust. Uranium is one of the most common Chemical element, elements in Earth's crust, being 40 times more common than silver and 500 times more common than ...
s. The other actinides are purely
synthetic element A synthetic element is a known chemical element that does not occur naturally on Earth: it has been created by human manipulation of fundamental particles in a nuclear reactor, a particle accelerator, or the explosion of an atomic bomb; thus, it i ...
s.Greenwood, p. 1250 Nuclear weapons tests have released at least six actinides heavier than plutonium into the environment; analysis of debris from the 1952 first test of a
hydrogen bomb A thermonuclear weapon, fusion weapon or hydrogen bomb (H-bomb) is a second-generation nuclear weapon design. Its greater sophistication affords it vastly greater destructive power than first-generation nuclear bombs, a more compact size, a lo ...
showed the presence of americium, curium,
berkelium Berkelium is a synthetic chemical element; it has symbol Bk and atomic number 97. It is a member of the actinide and transuranium element series. It is named after the city of Berkeley, California, the location of the Lawrence Berkeley National ...
,
californium Californium is a synthetic chemical element; it has symbol Cf and atomic number 98. It was first synthesized in 1950 at Lawrence Berkeley National Laboratory (then the University of California Radiation Laboratory) by bombarding curium with al ...
, and the discovery of einsteinium and fermium. In presentations of the
periodic table The periodic table, also known as the periodic table of the elements, is an ordered arrangement of the chemical elements into rows (" periods") and columns (" groups"). It is an icon of chemistry and is widely used in physics and other s ...
, the f-block elements are customarily shown as two additional rows below the main body of the table. This convention is entirely a matter of aesthetics and formatting practicality; a rarely used wide-formatted periodic table inserts the 4f and 5f series in their proper places, as parts of the table's sixth and seventh rows (periods).
Actinides


Discovery, isolation and synthesis

Like the
lanthanide The lanthanide () or lanthanoid () series of chemical elements comprises at least the 14 metallic chemical elements with atomic numbers 57–70, from lanthanum through ytterbium. In the periodic table, they fill the 4f orbitals. Lutetium (el ...
s, the actinides form a family of elements with similar properties. Within the actinides, there are two overlapping groups:
transuranium element The transuranium (or transuranic) elements are the chemical elements with atomic number greater than 92, which is the atomic number of uranium. All of them are radioactively unstable and decay into other elements. Except for neptunium and pluton ...
s, which follow uranium in the
periodic table The periodic table, also known as the periodic table of the elements, is an ordered arrangement of the chemical elements into rows (" periods") and columns (" groups"). It is an icon of chemistry and is widely used in physics and other s ...
; and transplutonium elements, which follow plutonium. Compared to the lanthanides, which (except for
promethium Promethium is a chemical element; it has Symbol (chemistry), symbol Pm and atomic number 61. All of its isotopes are Radioactive decay, radioactive; it is extremely rare, with only about 500–600 grams naturally occurring in the Earth's crust a ...
) are found in nature in appreciable quantities, most actinides are rare. Most do not occur in nature, and of those that do, only thorium and uranium do so in more than trace quantities. The most abundant or easily synthesized actinides are uranium and thorium, followed by plutonium, americium, actinium, protactinium, neptunium, and curium. The existence of transuranium elements was suggested in 1934 by
Enrico Fermi Enrico Fermi (; 29 September 1901 – 28 November 1954) was an Italian and naturalized American physicist, renowned for being the creator of the world's first artificial nuclear reactor, the Chicago Pile-1, and a member of the Manhattan Project ...
, based on his experiments. However, even though four actinides were known by that time, it was not yet understood that they formed a family similar to lanthanides. The prevailing view that dominated early research into transuranics was that they were regular elements in the 7th period, with thorium, protactinium and uranium corresponding to 6th-period
hafnium Hafnium is a chemical element; it has symbol Hf and atomic number 72. A lustrous, silvery gray, tetravalent transition metal, hafnium chemically resembles zirconium and is found in many zirconium minerals. Its existence was predicted by Dm ...
,
tantalum Tantalum is a chemical element; it has Symbol (chemistry), symbol Ta and atomic number 73. It is named after Tantalus, a figure in Greek mythology. Tantalum is a very hard, ductility, ductile, lustre (mineralogy), lustrous, blue-gray transition ...
and
tungsten Tungsten (also called wolfram) is a chemical element; it has symbol W and atomic number 74. It is a metal found naturally on Earth almost exclusively in compounds with other elements. It was identified as a distinct element in 1781 and first ...
, respectively. Synthesis of transuranics gradually undermined this point of view. By 1944, an observation that curium failed to exhibit oxidation states above 4 (whereas its supposed 6th period homolog,
platinum Platinum is a chemical element; it has Symbol (chemistry), symbol Pt and atomic number 78. It is a density, dense, malleable, ductility, ductile, highly unreactive, precious metal, precious, silverish-white transition metal. Its name origina ...
, can reach oxidation state of 6) prompted Glenn Seaborg to formulate an " actinide hypothesis". Studies of known actinides and discoveries of further transuranic elements provided more data in support of this position, but the phrase "actinide hypothesis" (the implication being that a "hypothesis" is something that has not been decisively proven) remained in active use by scientists through the late 1950s. At present, there are two major methods of producing
isotope Isotopes are distinct nuclear species (or ''nuclides'') of the same chemical element. They have the same atomic number (number of protons in their Atomic nucleus, nuclei) and position in the periodic table (and hence belong to the same chemica ...
s of transplutonium elements: (1) irradiation of the lighter elements with
neutron The neutron is a subatomic particle, symbol or , that has no electric charge, and a mass slightly greater than that of a proton. The Discovery of the neutron, neutron was discovered by James Chadwick in 1932, leading to the discovery of nucle ...
s; (2) irradiation with accelerated charged particles. The first method is more important for applications, as only neutron irradiation using nuclear reactors allows the production of sizeable amounts of synthetic actinides; however, it is limited to relatively light elements. The advantage of the second method is that elements heavier than plutonium, as well as neutron-deficient isotopes, can be obtained, which are not formed during neutron irradiation. In 1962–1966, there were attempts in the United States to produce transplutonium isotopes using a series of six underground nuclear explosions. Small samples of rock were extracted from the blast area immediately after the test to study the explosion products, but no isotopes with
mass number The mass number (symbol ''A'', from the German word: ''Atomgewicht'', "atomic weight"), also called atomic mass number or nucleon number, is the total number of protons and neutrons (together known as nucleons) in an atomic nucleus. It is appro ...
greater than 257 could be detected, despite predictions that such isotopes would have relatively long
half-lives Half-life is a mathematical and scientific description of exponential or gradual decay. Half-life, half life or halflife may also refer to: Film * ''Half-Life'' (film), a 2008 independent film by Jennifer Phang * '' Half Life: A Parable for t ...
of α-decay. This non-observation was attributed to
spontaneous fission Spontaneous fission (SF) is a form of radioactive decay in which a heavy atomic nucleus splits into two or more lighter nuclei. In contrast to induced fission, there is no inciting particle to trigger the decay; it is a purely probabilistic proc ...
owing to the large speed of the products and to other decay channels, such as neutron emission and
nuclear fission Nuclear fission is a reaction in which the nucleus of an atom splits into two or more smaller nuclei. The fission process often produces gamma photons, and releases a very large amount of energy even by the energetic standards of radioactiv ...
.


From actinium to uranium

Uranium Uranium is a chemical element; it has chemical symbol, symbol U and atomic number 92. It is a silvery-grey metal in the actinide series of the periodic table. A uranium atom has 92 protons and 92 electrons, of which 6 are valence electrons. Ura ...
and
thorium Thorium is a chemical element; it has symbol Th and atomic number 90. Thorium is a weakly radioactive light silver metal which tarnishes olive grey when it is exposed to air, forming thorium dioxide; it is moderately soft, malleable, and ha ...
were the first actinides discovered. Uranium was identified in 1789 by the German chemist
Martin Heinrich Klaproth Martin Heinrich Klaproth (1 December 1743 – 1 January 1817) was a German chemist. He trained and worked for much of his life as an apothecary, moving in later life to the university. His shop became the second-largest apothecary in Berlin, and ...
in
pitchblende Uraninite, also known as pitchblende, is a radioactive, uranium-rich mineral and ore with a chemical composition that is largely UO2 but because of oxidation typically contains variable proportions of U3O8. Radioactive decay of the urani ...
ore. He named it after the planet
Uranus Uranus is the seventh planet from the Sun. It is a gaseous cyan-coloured ice giant. Most of the planet is made of water, ammonia, and methane in a Supercritical fluid, supercritical phase of matter, which astronomy calls "ice" or Volatile ( ...
, which had been discovered eight years earlier. Klaproth was able to precipitate a yellow compound (likely sodium diuranate) by dissolving
pitchblende Uraninite, also known as pitchblende, is a radioactive, uranium-rich mineral and ore with a chemical composition that is largely UO2 but because of oxidation typically contains variable proportions of U3O8. Radioactive decay of the urani ...
in
nitric acid Nitric acid is an inorganic compound with the formula . It is a highly corrosive mineral acid. The compound is colorless, but samples tend to acquire a yellow cast over time due to decomposition into nitrogen oxide, oxides of nitrogen. Most com ...
and neutralizing the solution with
sodium hydroxide Sodium hydroxide, also known as lye and caustic soda, is an inorganic compound with the formula . It is a white solid ionic compound consisting of sodium cations and hydroxide anions . Sodium hydroxide is a highly corrosive base (chemistry), ...
. He then reduced the obtained yellow powder with charcoal, and extracted a black substance that he mistook for metal. Sixty years later, the French scientist
Eugène-Melchior Péligot Eugène-Melchior Péligot (24 March 1811 – 15 April 1890), also known as Eugène Péligot, was a French chemist who isolated the first sample of uranium metal in 1841. Péligot proved that the black powder of Martin Heinrich Klaproth was not ...
identified it as uranium oxide. He also isolated the first sample of uranium metal by heating uranium tetrachloride with metallic
potassium Potassium is a chemical element; it has Symbol (chemistry), symbol K (from Neo-Latin ) and atomic number19. It is a silvery white metal that is soft enough to easily cut with a knife. Potassium metal reacts rapidly with atmospheric oxygen to ...
. The
atomic mass Atomic mass ( or ) is the mass of a single atom. The atomic mass mostly comes from the combined mass of the protons and neutrons in the nucleus, with minor contributions from the electrons and nuclear binding energy. The atomic mass of atoms, ...
of uranium was then calculated as 120, but
Dmitri Mendeleev Dmitri Ivanovich Mendeleev ( ; ) was a Russian chemist known for formulating the periodic law and creating a version of the periodic table of elements. He used the periodic law not only to correct the then-accepted properties of some known ele ...
in 1872 corrected it to 240 using his periodicity laws. This value was confirmed experimentally in 1882 by K. Zimmerman. Thorium oxide was discovered by
Friedrich Wöhler Friedrich Wöhler Royal Society of London, FRS(For) HonFRSE (; 31 July 180023 September 1882) was a German chemist known for his work in both organic chemistry, organic and inorganic chemistry, being the first to isolate the chemical elements be ...
in the mineral thorianite, which was found in Norway (1827).
Jöns Jacob Berzelius Baron Jöns Jacob Berzelius (; 20 August 1779 – 7 August 1848) was a Swedish chemist. Berzelius is considered, along with Robert Boyle, John Dalton, and Antoine Lavoisier, to be one of the founders of modern chemistry. Berzelius became a memb ...
characterized this material in more detail in 1828. By reduction of thorium tetrachloride with potassium, he isolated the metal and named it thorium after the Norse god of thunder and lightning
Thor Thor (from ) is a prominent list of thunder gods, god in Germanic paganism. In Norse mythology, he is a hammer-wielding æsir, god associated with lightning, thunder, storms, sacred trees and groves in Germanic paganism and mythology, sacred g ...
. The same isolation method was later used by Péligot for uranium.
Actinium Actinium is a chemical element; it has chemical symbol, symbol Ac and atomic number 89. It was discovered by Friedrich Oskar Giesel in 1902, who gave it the name ''emanium''; the element got its name by being wrongly identified with a substa ...
was discovered in 1899 by André-Louis Debierne, an assistant of
Marie Curie Maria Salomea Skłodowska-Curie (; ; 7 November 1867 – 4 July 1934), known simply as Marie Curie ( ; ), was a Polish and naturalised-French physicist and chemist who conducted pioneering research on radioactivity. She was List of female ...
, in the pitchblende waste left after removal of radium and polonium. He described the substance (in 1899) as similar to
titanium Titanium is a chemical element; it has symbol Ti and atomic number 22. Found in nature only as an oxide, it can be reduced to produce a lustrous transition metal with a silver color, low density, and high strength, resistant to corrosion in ...
and (in 1900) as similar to thorium. The discovery of actinium by Debierne was however questioned in 1971 and 2000, arguing that Debierne's publications in 1904 contradicted his earlier work of 1899–1900. This view instead credits the 1902 work of Friedrich Oskar Giesel, who discovered a radioactive element named ''emanium'' that behaved similarly to lanthanum. The name actinium comes from the , meaning beam or ray. This metal was discovered not by its own radiation but by the radiation of the daughter products. Owing to the close similarity of actinium and lanthanum and low abundance, pure actinium could only be produced in 1950. The term actinide was probably introduced by
Victor Goldschmidt Victor Moritz Goldschmidt (27 January 1888 – 20 March 1947) was a Norwegian mineralogist considered (together with Vladimir Vernadsky) to be the founder of modern geochemistry and crystal chemistry, developer of the Goldschmidt Classificatio ...
in 1937.
Protactinium Protactinium is a chemical element; it has symbol Pa and atomic number 91. It is a dense, radioactive, silvery-gray actinide metal which readily reacts with oxygen, water vapor, and inorganic acids. It forms various chemical compounds, in which p ...
was possibly isolated in 1900 by
William Crookes Sir William Crookes (; 17 June 1832 – 4 April 1919) was an English chemist and physicist who attended the Royal College of Chemistry, now part of Imperial College London, and worked on spectroscopy. He was a pioneer of vacuum tubes, inventing ...
. It was first identified in 1913, when Kasimir Fajans and Oswald Helmuth Göhring encountered the short-lived isotope 234mPa (half-life 1.17 minutes) during their studies of the 238U decay chain. They named the new element ''brevium'' (from Latin ''brevis'' meaning brief); the name was changed to ''protoactinium'' (from
Greek Greek may refer to: Anything of, from, or related to Greece, a country in Southern Europe: *Greeks, an ethnic group *Greek language, a branch of the Indo-European language family **Proto-Greek language, the assumed last common ancestor of all kno ...
πρῶτος + ἀκτίς meaning "first beam element") in 1918 when two groups of scientists, led by the Austrian
Lise Meitner Elise Lise Meitner ( ; ; 7 November 1878 – 27 October 1968) was an Austrian-Swedish nuclear physicist who was instrumental in the discovery of nuclear fission. After completing her doctoral research in 1906, Meitner became the second woman ...
and
Otto Hahn Otto Hahn (; 8 March 1879 – 28 July 1968) was a German chemist who was a pioneer in the field of radiochemistry. He is referred to as the father of nuclear chemistry and discoverer of nuclear fission, the science behind nuclear reactors and ...
of Germany and Frederick Soddy and John Arnold Cranston of Great Britain, independently discovered the much longer-lived 231Pa. The name was shortened to ''protactinium'' in 1949. This element was little characterized until 1960, when Alfred Maddock and his co-workers in the U.K. isolated 130 grams of protactinium from 60 tonnes of waste left after extraction of uranium from its ore.Greenwood, p. 1251


Neptunium and above

Neptunium (named for the planet
Neptune Neptune is the eighth and farthest known planet from the Sun. It is the List of Solar System objects by size, fourth-largest planet in the Solar System by diameter, the third-most-massive planet, and the densest giant planet. It is 17 t ...
, the next
planet A planet is a large, Hydrostatic equilibrium, rounded Astronomical object, astronomical body that is generally required to be in orbit around a star, stellar remnant, or brown dwarf, and is not one itself. The Solar System has eight planets b ...
out from Uranus, after which uranium was named) was discovered by Edwin McMillan and Philip H. Abelson in 1940 in
Berkeley, California Berkeley ( ) is a city on the eastern shore of San Francisco Bay in northern Alameda County, California, United States. It is named after the 18th-century Anglo-Irish bishop and philosopher George Berkeley. It borders the cities of Oakland, Cali ...
. They produced the 239Np isotope (half-life 2.4 days) by bombarding uranium with slow
neutron The neutron is a subatomic particle, symbol or , that has no electric charge, and a mass slightly greater than that of a proton. The Discovery of the neutron, neutron was discovered by James Chadwick in 1932, leading to the discovery of nucle ...
s. It was the first
transuranium element The transuranium (or transuranic) elements are the chemical elements with atomic number greater than 92, which is the atomic number of uranium. All of them are radioactively unstable and decay into other elements. Except for neptunium and pluton ...
produced synthetically. Transuranium elements do not occur in sizeable quantities in nature and are commonly synthesized via
nuclear reaction In nuclear physics and nuclear chemistry, a nuclear reaction is a process in which two atomic nucleus, nuclei, or a nucleus and an external subatomic particle, collide to produce one or more new nuclides. Thus, a nuclear reaction must cause a t ...
s conducted with nuclear reactors. For example, under irradiation with reactor neutrons,
uranium-238 Uranium-238 ( or U-238) is the most common isotope of uranium found in nature, with a relative abundance of 99%. Unlike uranium-235, it is non-fissile, which means it cannot sustain a chain reaction in a thermal-neutron reactor. However, it i ...
partially converts to
plutonium-239 Plutonium-239 ( or Pu-239) is an isotope of plutonium. Plutonium-239 is the primary fissile isotope used for the production of nuclear weapons, although uranium-235 is also used for that purpose. Plutonium-239 is also one of the three main iso ...
: : \ce \left( \ce \right) \ce This synthesis reaction was used by Fermi and his collaborators in their design of the reactors located at the Hanford Site, which produced significant amounts of plutonium-239 for the nuclear weapons of the
Manhattan Project The Manhattan Project was a research and development program undertaken during World War II to produce the first nuclear weapons. It was led by the United States in collaboration with the United Kingdom and Canada. From 1942 to 1946, the ...
and the United States' post-war nuclear arsenal. Actinides with the highest mass numbers are synthesized by bombarding uranium, plutonium, curium and californium with ions of nitrogen, oxygen, carbon, neon or boron in a
particle accelerator A particle accelerator is a machine that uses electromagnetic fields to propel electric charge, charged particles to very high speeds and energies to contain them in well-defined particle beam, beams. Small accelerators are used for fundamental ...
. Thus
nobelium Nobelium is a synthetic element, synthetic chemical element; it has Chemical symbol, symbol No and atomic number 102. It is named after Alfred Nobel, the inventor of dynamite and benefactor of science. A radioactive metal, it is the tenth transura ...
was produced by bombarding uranium-238 with neon-22 as : _^U + _^Ne -> _^No + 4_0^1n. The first isotopes of transplutonium elements,
americium-241 Americium-241 (Am, Am-241) is an isotope of americium. Like all isotopes of americium, it is radioactive, with a half-life of . Am is the most common isotope of americium as well as the most prevalent isotope of americium in nuclear waste. It ...
and curium-242, were synthesized in 1944 by Glenn T. Seaborg, Ralph A. James and
Albert Ghiorso Albert Ghiorso (July 15, 1915 – December 26, 2010) was an American nuclear scientist and co-discoverer of a record 12 chemical elements on the periodic table. His research career spanned six decades, from the early 1940s to the late 1990s. Biog ...
. Curium-242 was obtained by bombarding plutonium-239 with 32-MeV α-particles: : _^Pu + _2^4He -> _^Cm + _0^1n. The americium-241 and curium-242 isotopes also were produced by irradiating plutonium in a nuclear reactor. The latter element was named after
Marie Curie Maria Salomea Skłodowska-Curie (; ; 7 November 1867 – 4 July 1934), known simply as Marie Curie ( ; ), was a Polish and naturalised-French physicist and chemist who conducted pioneering research on radioactivity. She was List of female ...
and her husband Pierre who are noted for discovering
radium Radium is a chemical element; it has chemical symbol, symbol Ra and atomic number 88. It is the sixth element in alkaline earth metal, group 2 of the periodic table, also known as the alkaline earth metals. Pure radium is silvery-white, ...
and for their work in
radioactivity Radioactive decay (also known as nuclear decay, radioactivity, radioactive disintegration, or nuclear disintegration) is the process by which an unstable atomic nucleus loses energy by radiation. A material containing unstable nuclei is conside ...
. Bombarding curium-242 with α-particles resulted in an isotope of californium 245Cf in 1950, and a similar procedure yielded berkelium-243 from americium-241 in 1949. The new elements were named after
Berkeley, California Berkeley ( ) is a city on the eastern shore of San Francisco Bay in northern Alameda County, California, United States. It is named after the 18th-century Anglo-Irish bishop and philosopher George Berkeley. It borders the cities of Oakland, Cali ...
, by analogy with its
lanthanide The lanthanide () or lanthanoid () series of chemical elements comprises at least the 14 metallic chemical elements with atomic numbers 57–70, from lanthanum through ytterbium. In the periodic table, they fill the 4f orbitals. Lutetium (el ...
homologue
terbium Terbium is a chemical element; it has Symbol (chemistry), symbol Tb and atomic number 65. It is a silvery-white, rare earth element, rare earth metal that is malleable and ductile. The ninth member of the lanthanide series, terbium is a fairly ele ...
, which was named after the village of
Ytterby Ytterby () is a village on the Swedish island of Resarö, in Vaxholm Municipality in the Stockholm archipelago. Today the residential area is dominated by suburban homes. The name of the village translates to "outer village". Ytterby is the ...
in Sweden. In 1945, B. B. Cunningham obtained the first bulk chemical compound of a transplutonium element, namely americium hydroxide. Over the few years, milligram quantities of americium and microgram amounts of curium were accumulated that allowed production of isotopes of berkelium and californium. Sizeable amounts of these elements were produced in 1958, and the first californium compound (0.3 μg of CfOCl) was obtained in 1960 by B. B. Cunningham and J. C. Wallmann. Einsteinium and fermium were identified in 1952–1953 in the fallout from the "
Ivy Mike Ivy Mike was the code name, codename given to the first full-scale test of a Thermonuclear weapon, thermonuclear device, in which a significant fraction of the explosive nuclear weapon yield, yield comes from nuclear fusion. Ivy Mike was detona ...
" nuclear test (1 November 1952), the first successful test of a hydrogen bomb. Instantaneous exposure of uranium-238 to a large neutron flux resulting from the explosion produced heavy isotopes of uranium, which underwent a series of
beta decay In nuclear physics, beta decay (β-decay) is a type of radioactive decay in which an atomic nucleus emits a beta particle (fast energetic electron or positron), transforming into an isobar of that nuclide. For example, beta decay of a neutron ...
s to nuclides such as einsteinium-253 and fermium-255. The discovery of the new elements and the new data on neutron capture were initially kept secret on the orders of the US military until 1955 due to
Cold War The Cold War was a period of global Geopolitics, geopolitical rivalry between the United States (US) and the Soviet Union (USSR) and their respective allies, the capitalist Western Bloc and communist Eastern Bloc, which lasted from 1947 unt ...
tensions. Nevertheless, the Berkeley team were able to prepare einsteinium and fermium by civilian means, through the neutron bombardment of plutonium-239, and published this work in 1954 with the disclaimer that it was not the first studies that had been carried out on those elements. The "Ivy Mike" studies were declassified and published in 1955. The first significant (submicrogram) amounts of einsteinium were produced in 1961 by Cunningham and colleagues, but this has not been done for fermium yet. The first isotope of mendelevium, 256Md (half-life 87 min), was synthesized by Albert Ghiorso, Glenn T. Seaborg,
Gregory Robert Choppin Gregory Robert Choppin (November 9, 1927, Texas, United States – October 21, 2015, Tallahassee, Florida) was an American nuclear chemist and co-discoverer of the element mendelevium, atomic number 101. Others in the discovery group were Albert G ...
, Bernard G. Harvey and Stanley Gerald Thompson when they bombarded an 253Es target with
alpha particle Alpha particles, also called alpha rays or alpha radiation, consist of two protons and two neutrons bound together into a particle identical to a helium-4 nucleus. They are generally produced in the process of alpha decay but may also be produce ...
s in the 60-inch
cyclotron A cyclotron is a type of particle accelerator invented by Ernest Lawrence in 1929–1930 at the University of California, Berkeley, and patented in 1932. Lawrence, Ernest O. ''Method and apparatus for the acceleration of ions'', filed: Januar ...
of Berkeley Radiation Laboratory; this was the first isotope of any element to be synthesized one atom at a time. There were several attempts to obtain isotopes of nobelium by Swedish (1957) and American (1958) groups, but the first reliable result was the synthesis of 256No by the Russian group of
Georgy Flyorov Georgii Nikolayevich Flyorov (also spelled Flerov, rus, Гео́ргий Никола́евич Флёров, p=gʲɪˈorgʲɪj nʲɪkɐˈlajɪvʲɪtɕ ˈflʲɵrəf; 2 March 1913 – 19 November 1990) was a Soviet physicist who is known for h ...
in 1965, as acknowledged by the
IUPAC The International Union of Pure and Applied Chemistry (IUPAC ) is an international federation of National Adhering Organizations working for the advancement of the chemical sciences, especially by developing nomenclature and terminology. It is ...
in 1992. In their experiments, Flyorov et al. bombarded uranium-238 with neon-22. In 1961, Ghiorso et al. obtained the first isotope of lawrencium by irradiating californium (mostly californium-252) with boron-10 and boron-11 ions. The
mass number The mass number (symbol ''A'', from the German word: ''Atomgewicht'', "atomic weight"), also called atomic mass number or nucleon number, is the total number of protons and neutrons (together known as nucleons) in an atomic nucleus. It is appro ...
of this isotope was not clearly established (possibly 258 or 259) at the time. In 1965, 256Lr was synthesized by Flyorov et al. from 243Am and 18O. Thus IUPAC recognized the nuclear physics teams at Dubna and Berkeley as the co-discoverers of lawrencium.


Isotopes

Thirty-four isotopes of actinium and eight excited isomeric states of some of its
nuclide Nuclides (or nucleides, from nucleus, also known as nuclear species) are a class of atoms characterized by their number of protons, ''Z'', their number of neutrons, ''N'', and their nuclear energy state. The word ''nuclide'' was coined by the A ...
s are known, ranging in mass number from 203 to 236. Three isotopes, 225Ac, 227Ac and 228Ac, were found in nature and the others were produced in the laboratory; only the three natural isotopes are used in applications. Actinium-225 is a member of the radioactive
neptunium series In nuclear science a decay chain refers to the predictable series of radioactive decay, radioactive disintegrations undergone by the nuclei of certain unstable chemical elements. Radionuclide, Radioactive isotopes do not usually decay directly ...
;Greenwood, p. 1254 it was first discovered in 1947 as a decay product of
uranium-233 Uranium-233 ( or U-233) is a fissile isotope of uranium that is bred from thorium-232 as part of the thorium fuel cycle. Uranium-233 was investigated for use in nuclear weapons and as a Nuclear fuel, reactor fuel. It has been used successfully ...
and it is an α-emitter with a half-life of 10 days. Actinium-225 is less available than actinium-228, but is more promising in radiotracer applications. Actinium-227 (half-life 21.77 years) occurs in all uranium ores, but in small quantities. One gram of uranium (in radioactive equilibrium) contains only 2 gram of 227Ac. Actinium-228 is a member of the radioactive thorium series formed by the decay of 228Ra; it is a β emitter with a half-life of 6.15 hours. In one tonne of thorium there is 5 gram of 228Ac. It was discovered by
Otto Hahn Otto Hahn (; 8 March 1879 – 28 July 1968) was a German chemist who was a pioneer in the field of radiochemistry. He is referred to as the father of nuclear chemistry and discoverer of nuclear fission, the science behind nuclear reactors and ...
in 1906. There are 32 known
isotopes of thorium Thorium (90Th) has seven naturally occurring isotopes but none are stable. One isotope, 232Th, is ''relatively'' stable, with a half-life of 1.405×1010 years, considerably longer than the age of the Earth, and even slightly longer than the gen ...
ranging in mass number from 207 to 238. Of these, the longest-lived is 232Th, whose half-life of means that it still exists in nature as a
primordial nuclide In geochemistry, geophysics and nuclear physics, primordial nuclides, also known as primordial isotopes, are nuclides found on Earth that have existed in their current form since before Earth was formed. Primordial nuclides were present in the ...
. The next longest-lived is 230Th, an intermediate decay product of 238U with a half-life of 75,400 years. Several other thorium isotopes have half-lives over a day; all of these are also transient in the decay chains of 232Th, 235U, and 238U. Twenty-nine
isotopes of protactinium Protactinium (91Pa) has no stable isotopes. The four naturally occurring isotopes allow a standard atomic weight to be given. Thirty radioisotopes of protactinium have been characterized, ranging from 210Pa to 239Pa. The most stable isotope is 2 ...
are known with mass numbers 211–239 as well as three excited isomeric states. Only 231Pa and 234Pa have been found in nature. All the isotopes have short lifetimes, except for protactinium-231 (half-life 32,760 years). The most important isotopes are 231Pa and 233Pa, which is an intermediate product in obtaining uranium-233 and is the most affordable among artificial isotopes of protactinium. 233Pa has convenient half-life and energy of γ-radiation, and thus was used in most studies of protactinium chemistry. Protactinium-233 is a β-emitter with a half-life of 26.97 days. There are 27 known
isotopes of uranium Uranium (U) is a naturally occurring radioactive element (radioelement) with no stable isotopes. It has two primordial isotopes, uranium-238 and uranium-235, that have long half-lives and are found in appreciable quantity in Earth's crust. The d ...
, having mass numbers 215–242 (except 220). Three of them, 234U, 235U and 238U, are present in appreciable quantities in nature. Among others, the most important is 233U, which is a final product of transformation of 232Th irradiated by slow neutrons. 233U has a much higher fission efficiency by low-energy (thermal) neutrons, compared e.g. with 235U. Most uranium chemistry studies were carried out on uranium-238 owing to its long half-life of 4.4 years. There are 25
isotopes of neptunium Neptunium (93Np) is usually considered an artificial element, although trace quantities are found in nature, so a standard atomic weight cannot be given. Like all trace or artificial elements, it has no stable isotopes. The first isotope to be ...
with mass numbers 219–244 (except 221); they are all highly radioactive. The most popular among scientists are long-lived 237Np (t1/2 = 2.20 years) and short-lived 239Np, 238Np (t1/2 ~ 2 days). There are 21 known isotopes of plutonium, having mass numbers 227–247. The most stable isotope of plutonium is 244Pu with half-life of 8.13 years. Eighteen
isotopes of americium Americium (95Am) is an artificial element, and thus a standard atomic weight cannot be given. Like all artificial elements, it has no known stable isotopes. The first isotope to be synthesized was 241Am in 1944. The artificial element decays by e ...
are known with mass numbers from 229 to 247 (with the exception of 231). The most important are 241Am and 243Am, which are alpha-emitters and also emit soft, but intense γ-rays; both of them can be obtained in an isotopically pure form. Chemical properties of americium were first studied with 241Am, but later shifted to 243Am, which is almost 20 times less radioactive. The disadvantage of 243Am is production of the short-lived daughter isotope 239Np, which has to be considered in the data analysis.Myasoedov, p. 18 Among 19 isotopes of curium, ranging in mass number from 233 to 251, the most accessible are 242Cm and 244Cm; they are α-emitters, but with much shorter lifetime than the americium isotopes. These isotopes emit almost no γ-radiation, but undergo
spontaneous fission Spontaneous fission (SF) is a form of radioactive decay in which a heavy atomic nucleus splits into two or more lighter nuclei. In contrast to induced fission, there is no inciting particle to trigger the decay; it is a purely probabilistic proc ...
with the associated emission of neutrons. More long-lived isotopes of curium (245–248Cm, all α-emitters) are formed as a mixture during neutron irradiation of plutonium or americium. Upon short irradiation, this mixture is dominated by 246Cm, and then 248Cm begins to accumulate. Both of these isotopes, especially 248Cm, have a longer half-life (3.48 years) and are much more convenient for carrying out chemical research than 242Cm and 244Cm, but they also have a rather high rate of spontaneous fission. 247Cm has the longest lifetime among isotopes of curium (1.56 years), but is not formed in large quantities because of the strong fission induced by thermal neutrons. Seventeen isotopes of berkelium have been identified with mass numbers 233, 234, 236, 238, and 240–252. Only 249Bk is available in large quantities; it has a relatively short half-life of 330 days and emits mostly soft β-particles, which are inconvenient for detection. Its
alpha radiation Alpha decay or α-decay is a type of radioactive decay in which an atomic nucleus emits an alpha particle (helium nucleus). The parent nucleus transforms or "decays" into a daughter product, with a mass number that is reduced by four and an atom ...
is rather weak (1.45% with respect to β-radiation), but is sometimes used to detect this isotope. 247Bk is an alpha-emitter with a long half-life of 1,380 years, but it is hard to obtain in appreciable quantities; it is not formed upon neutron irradiation of plutonium because β-decay of curium isotopes with mass number below 248 is not known. (247Cm would actually release energy by β-decaying to 247Bk, but this has never been seen.) The 20 isotopes of californium with mass numbers 237–256 are formed in nuclear reactors; californium-253 is a β-emitter and the rest are α-emitters. The isotopes with even mass numbers (250Cf, 252Cf and 254Cf) have a high rate of spontaneous fission, especially 254Cf of which 99.7% decays by spontaneous fission. Californium-249 has a relatively long half-life (352 years), weak spontaneous fission and strong γ-emission that facilitates its identification. 249Cf is not formed in large quantities in a nuclear reactor because of the slow β-decay of the parent isotope 249Bk and a large cross section of interaction with neutrons, but it can be accumulated in the isotopically pure form as the β-decay product of (pre-selected) 249Bk. Californium produced by reactor-irradiation of plutonium mostly consists of 250Cf and 252Cf, the latter being predominant for large neutron fluences, and its study is hindered by the strong neutron radiation.Myasoedov, p. 22 Among the 18 known isotopes of einsteinium with mass numbers from 240 to 257, the most affordable is 253Es. It is an α-emitter with a half-life of 20.47 days, a relatively weak γ-emission and small spontaneous fission rate as compared with the isotopes of californium. Prolonged neutron irradiation also produces a long-lived isotope 254Es (t1/2 = 275.5 days). Twenty
isotopes of fermium Fermium (100Fm) is a synthetic element, and thus a standard atomic weight cannot be given. Like all artificial elements, it has no stable isotopes. The first isotope to be discovered (in fallout from nuclear testing) was 255Fm in 1952. 250Fm w ...
are known with mass numbers of 241–260. 254Fm, 255Fm and 256Fm are α-emitters with a short half-life (hours), which can be isolated in significant amounts. 257Fm (t1/2 = 100 days) can accumulate upon prolonged and strong irradiation. All these isotopes are characterized by high rates of spontaneous fission. Among the 17 known isotopes of mendelevium (mass numbers from 244 to 260), the most studied is 256Md, which mainly decays through electron capture (α-radiation is ≈10%) with a half-life of 77 minutes. Another alpha emitter, 258Md, has a half-life of 53 days. Both these isotopes are produced from rare einsteinium (253Es and 255Es respectively), that therefore limits their availability. Long-lived
isotopes of nobelium Nobelium (102No) is a synthetic element, and thus a standard atomic weight cannot be given. Like all synthetic elements, it has no stable isotopes. The first isotope to be synthesized (and correctly identified) was 254No in 1966. There are fourtee ...
and isotopes of lawrencium (and of heavier elements) have relatively short half-lives. For nobelium, 13 isotopes are known, with mass numbers 249–260 and 262. The chemical properties of nobelium and lawrencium were studied with 255No (t1/2 = 3 min) and 256Lr (t1/2 = 35 s). The longest-lived nobelium isotope, 259No, has a half-life of approximately 1 hour. Lawrencium has 14 known isotopes with mass numbers 251–262, 264, and 266. The most stable of them is 266Lr with a half life of 11 hours. Among all of these, the only isotopes that occur in sufficient quantities in nature to be detected in anything more than traces and have a measurable contribution to the atomic weights of the actinides are the primordial 232Th, 235U, and 238U, and three long-lived decay products of natural uranium, 230Th, 231Pa, and 234U. Natural thorium consists of 0.02(2)% 230Th and 99.98(2)% 232Th; natural protactinium consists of 100% 231Pa; and natural uranium consists of 0.0054(5)% 234U, 0.7204(6)% 235U, and 99.2742(10)% 238U.


Formation in nuclear reactors

The figure ''buildup of actinides'' is a table of nuclides with the number of neutrons on the horizontal axis (isotopes) and the number of protons on the vertical axis (elements). The red dot divides the nuclides in two groups, so the figure is more compact. Each nuclide is represented by a square with the mass number of the element and its half-life. Naturally existing actinide isotopes (Th, U) are marked with a bold border, alpha emitters have a yellow colour, and beta emitters have a blue colour. Pink indicates electron capture (236Np), whereas white stands for a long-lasting metastable state (242Am). The formation of actinide nuclides is primarily characterised by: *
Neutron capture Neutron capture is a nuclear reaction in which an atomic nucleus and one or more neutrons collide and merge to form a heavier nucleus. Since neutrons have no electric charge, they can enter a nucleus more easily than positively charged protons, wh ...
reactions (n,γ), which are represented in the figure by a short right arrow. * The (n,2n) reactions and the less frequently occurring (γ,n) reactions are also taken into account, both of which are marked by a short left arrow. * Even more rarely and only triggered by fast neutrons, the (n,3n) reaction occurs, which is represented in the figure with one example, marked by a long left arrow. In addition to these neutron- or gamma-induced
nuclear reaction In nuclear physics and nuclear chemistry, a nuclear reaction is a process in which two atomic nucleus, nuclei, or a nucleus and an external subatomic particle, collide to produce one or more new nuclides. Thus, a nuclear reaction must cause a t ...
s, the radioactive conversion of actinide nuclides also affects the nuclide inventory in a reactor. These decay types are marked in the figure by diagonal arrows. The beta-minus decay, marked with an arrow pointing up-left, plays a major role for the balance of the particle densities of the nuclides. Nuclides decaying by
positron emission Positron emission, beta plus decay, or β+ decay is a subtype of radioactive decay called beta decay, in which a proton inside a radionuclide nucleus is converted into a neutron while releasing a positron and an electron neutrino (). Positron emi ...
(beta-plus decay) or
electron capture Electron capture (K-electron capture, also K-capture, or L-electron capture, L-capture) is a process in which the proton-rich nucleus of an electrically neutral atom absorbs an inner atomic electron, usually from the K or L electron shells. Th ...
(ϵ) do not occur in a nuclear reactor except as products of knockout reactions; their decays are marked with arrows pointing down-right. Due to the long half-lives of the given nuclides,
alpha decay Alpha decay or α-decay is a type of radioactive decay in which an atomic nucleus emits an alpha particle (helium nucleus). The parent nucleus transforms or "decays" into a daughter product, with a mass number that is reduced by four and an a ...
plays almost no role in the formation and decay of the actinides in a power reactor, as the residence time of the nuclear fuel in the reactor core is rather short (a few years). Exceptions are the two relatively short-lived nuclides 242Cm (T1/2 = 163 d) and 236Pu (T1/2 = 2.9 y). Only for these two cases, the α decay is marked on the nuclide map by a long arrow pointing down-left. A few long-lived actinide isotopes, such as 244Pu and 250Cm, cannot be produced in reactors because neutron capture does not happen quickly enough to bypass the short-lived beta-decaying nuclides 243Pu and 249Cm; they can however be generated in nuclear explosions, which have much higher neutron fluxes.


Distribution in nature

Thorium and uranium are the most abundant actinides in nature with the respective mass concentrations of 16 ppm and 4 ppm. Uranium mostly occurs in the Earth's crust as a mixture of its oxides in the mineral
uraninite Uraninite, also known as pitchblende, is a radioactive, uranium-rich mineral and ore with a chemical composition that is largely UO2 but because of oxidation typically contains variable proportions of U3O8. Radioactive decay of the uranium c ...
, which is also called pitchblende because of its black color. There are several dozens of other uranium minerals such as carnotite (KUO2VO4·3H2O) and autunite (Ca(UO2)2(PO4)2·nH2O). The isotopic composition of natural uranium is 238U (relative abundance 99.2742%), 235U (0.7204%) and 234U (0.0054%); of these 238U has the largest half-life of 4.51 years. The worldwide production of uranium in 2009 amounted to 50,572
tonne The tonne ( or ; symbol: t) is a unit of mass equal to 1,000  kilograms. It is a non-SI unit accepted for use with SI. It is also referred to as a metric ton in the United States to distinguish it from the non-metric units of the s ...
s, of which 27.3% was mined in
Kazakhstan Kazakhstan, officially the Republic of Kazakhstan, is a landlocked country primarily in Central Asia, with a European Kazakhstan, small portion in Eastern Europe. It borders Russia to the Kazakhstan–Russia border, north and west, China to th ...
. Other important uranium mining countries are Canada (20.1%), Australia (15.7%),
Namibia Namibia, officially the Republic of Namibia, is a country on the west coast of Southern Africa. Its borders include the Atlantic Ocean to the west, Angola and Zambia to the north, Botswana to the east and South Africa to the south; in the no ...
(9.1%),
Russia Russia, or the Russian Federation, is a country spanning Eastern Europe and North Asia. It is the list of countries and dependencies by area, largest country in the world, and extends across Time in Russia, eleven time zones, sharing Borders ...
(7.0%), and
Niger Niger, officially the Republic of the Niger, is a landlocked country in West Africa. It is a unitary state Geography of Niger#Political geography, bordered by Libya to the Libya–Niger border, north-east, Chad to the Chad–Niger border, east ...
(6.4%). The most abundant thorium minerals are thorianite (), thorite () and monazite, (). Most thorium minerals contain uranium and vice versa; and they all have significant fraction of lanthanides. Rich deposits of thorium minerals are located in the United States (440,000 tonnes), Australia and India (~300,000 tonnes each) and Canada (~100,000 tonnes). The abundance of actinium in the Earth's crust is only about 5%. Actinium is mostly present in uranium-containing, but also in other minerals, though in much smaller quantities. The content of actinium in most natural objects corresponds to the isotopic equilibrium of parent isotope 235U, and it is not affected by the weak Ac migration. Protactinium is more abundant (10−12%) in the Earth's crust than actinium. It was discovered in uranium ore in 1913 by Fajans and Göhring. As actinium, the distribution of protactinium follows that of 235U. The half-life of the longest-lived isotope of neptunium, 237Np, is negligible compared to the age of the Earth. Thus neptunium is present in nature in negligible amounts produced as intermediate decay products of other isotopes. Traces of plutonium in uranium minerals were first found in 1942, and the more systematic results on 239Pu are summarized in the table (no other plutonium isotopes could be detected in those samples). The upper limit of abundance of the longest-living isotope of plutonium, 244Pu, is 3%. Plutonium could not be detected in samples of lunar soil. Owing to its scarcity in nature, most plutonium is produced synthetically.


Extraction

Owing to the low abundance of actinides, their extraction is a complex, multistep process.
Fluoride Fluoride (). According to this source, is a possible pronunciation in British English. is an Inorganic chemistry, inorganic, Monatomic ion, monatomic Ion#Anions and cations, anion of fluorine, with the chemical formula (also written ), whose ...
s of actinides are usually used because they are insoluble in water and can be easily separated with
redox Redox ( , , reduction–oxidation or oxidation–reduction) is a type of chemical reaction in which the oxidation states of the reactants change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is t ...
reactions. Fluorides are reduced with
calcium Calcium is a chemical element; it has symbol Ca and atomic number 20. As an alkaline earth metal, calcium is a reactive metal that forms a dark oxide-nitride layer when exposed to air. Its physical and chemical properties are most similar to it ...
,
magnesium Magnesium is a chemical element; it has Symbol (chemistry), symbol Mg and atomic number 12. It is a shiny gray metal having a low density, low melting point and high chemical reactivity. Like the other alkaline earth metals (group 2 ...
or
barium Barium is a chemical element; it has symbol Ba and atomic number 56. It is the fifth element in group 2 and is a soft, silvery alkaline earth metal. Because of its high chemical reactivity, barium is never found in nature as a free element. Th ...
:Golub, pp. 215–217 : \begin\\ \ce\\ \ce\\ \ce\\ \end Among the actinides, thorium and uranium are the easiest to isolate. Thorium is extracted mostly from monazite: thorium
pyrophosphate In chemistry, pyrophosphates are phosphorus oxyanions that contain two phosphorus atoms in a linkage. A number of pyrophosphate salts exist, such as disodium pyrophosphate () and tetrasodium pyrophosphate (), among others. Often pyrophosphates a ...
(ThP2O7) is reacted with
nitric acid Nitric acid is an inorganic compound with the formula . It is a highly corrosive mineral acid. The compound is colorless, but samples tend to acquire a yellow cast over time due to decomposition into nitrogen oxide, oxides of nitrogen. Most com ...
, and the produced thorium nitrate treated with tributyl phosphate. Rare-earth impurities are separated by increasing the pH in sulfate solution. In another extraction method, monazite is decomposed with a 45% aqueous solution of
sodium hydroxide Sodium hydroxide, also known as lye and caustic soda, is an inorganic compound with the formula . It is a white solid ionic compound consisting of sodium cations and hydroxide anions . Sodium hydroxide is a highly corrosive base (chemistry), ...
at 140 °C. Mixed metal hydroxides are extracted first, filtered at 80 °C, washed with water and dissolved with concentrated
hydrochloric acid Hydrochloric acid, also known as muriatic acid or spirits of salt, is an aqueous solution of hydrogen chloride (HCl). It is a colorless solution with a distinctive pungency, pungent smell. It is classified as a acid strength, strong acid. It is ...
. 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 rest of rare-earth hydroxides remains in solution. Thorium hydroxide is dissolved in an inorganic acid and then purified from the
rare earth element The rare-earth elements (REE), also called the rare-earth metals or rare earths, and sometimes the lanthanides or lanthanoids (although scandium and yttrium, which do not belong to this series, are usually included as rare earths), are a set o ...
s. An efficient method is the dissolution of thorium hydroxide in nitric acid, because the resulting solution can be purified by extraction with organic solvents: :Th(OH)4 + 4 HNO3 → Th(NO3)4 + 4 H2O Metallic thorium is separated from the anhydrous
oxide An oxide () is a chemical compound containing at least one oxygen atom and one other element in its chemical formula. "Oxide" itself is the dianion (anion bearing a net charge of −2) of oxygen, an O2− ion with oxygen in the oxidation st ...
,
chloride The term chloride refers to a compound or molecule that contains either a chlorine anion (), which is a negatively charged chlorine atom, or a non-charged chlorine atom covalently bonded to the rest of the molecule by a single bond (). The pr ...
or
fluoride Fluoride (). According to this source, is a possible pronunciation in British English. is an Inorganic chemistry, inorganic, Monatomic ion, monatomic Ion#Anions and cations, anion of fluorine, with the chemical formula (also written ), whose ...
by reacting it with calcium in an inert atmosphere: :ThO2 + 2 Ca → 2 CaO + Th Sometimes thorium is extracted by
electrolysis In chemistry and manufacturing, electrolysis is a technique that uses Direct current, direct electric current (DC) to drive an otherwise non-spontaneous chemical reaction. Electrolysis is commercially important as a stage in the separation of c ...
of a fluoride in a mixture of sodium and potassium chloride at 700–800 °C in a
graphite Graphite () is a Crystallinity, crystalline allotrope (form) of the element carbon. It consists of many stacked Layered materials, layers of graphene, typically in excess of hundreds of layers. Graphite occurs naturally and is the most stable ...
crucible. Highly pure thorium can be extracted from its iodide with the crystal bar process. Uranium is extracted from its ores in various ways. In one method, the ore is burned and then reacted with nitric acid to convert uranium into a dissolved state. Treating the solution with a solution of tributyl phosphate (TBP) in
kerosene Kerosene, or paraffin, is a combustibility, combustible hydrocarbon liquid which is derived from petroleum. It is widely used as a fuel in Aviation fuel, aviation as well as households. Its name derives from the Greek (''kērós'') meaning " ...
transforms uranium into an organic form UO2(NO3)2(TBP)2. The insoluble impurities are filtered and the uranium is extracted by reaction with hydroxides as (NH4)2U2O7 or with
hydrogen peroxide Hydrogen peroxide is a chemical compound with the formula . In its pure form, it is a very pale blue liquid that is slightly more viscosity, viscous than Properties of water, water. It is used as an oxidizer, bleaching agent, and antiseptic, usua ...
as UO4·2H2O. When the uranium ore is rich in such minerals as dolomite,
magnesite Magnesite is a mineral with the chemical formula ( magnesium carbonate). Iron, manganese, cobalt, and nickel may occur as admixtures, but only in small amounts. Occurrence Magnesite occurs as veins in and an alteration product of ultramafic r ...
, etc., those minerals consume much acid. In this case, the carbonate method is used for uranium extraction. Its main component is an aqueous solution of
sodium carbonate Sodium carbonate (also known as washing soda, soda ash, sal soda, and soda crystals) is the inorganic compound with the formula and its various hydrates. All forms are white, odourless, water-soluble salts that yield alkaline solutions in water ...
, which converts uranium into a complex O2(CO3)3sup>4−, which is stable in aqueous solutions at low concentrations of hydroxide ions. The advantages of the sodium carbonate method are that the chemicals have low corrosivity (compared to nitrates) and that most non-uranium metals precipitate from the solution. The disadvantage is that tetravalent uranium compounds precipitate as well. Therefore, the uranium ore is treated with sodium carbonate at elevated temperature and under oxygen pressure: :2 UO2 + O2 + 6 → 2 O2(CO3)3sup>4− This equation suggests that the best solvent for the uranyl carbonate processing is a mixture of carbonate with bicarbonate. At high pH, this results in precipitation of diuranate, which is treated with
hydrogen Hydrogen is a chemical element; it has chemical symbol, symbol H and atomic number 1. It is the lightest and abundance of the chemical elements, most abundant chemical element in the universe, constituting about 75% of all baryon, normal matter ...
in the presence of nickel yielding an insoluble uranium tetracarbonate. Another separation method uses polymeric resins as a
polyelectrolyte Polyelectrolytes are polymers whose repeating units bear an electrolyte group. Polycations and polyanions are polyelectrolytes. These groups dissociate in aqueous solutions (water), making the polymers charged. Polyelectrolyte properties are t ...
. Ion exchange processes in the resins result in separation of uranium. Uranium from resins is washed with a solution of
ammonium nitrate Ammonium nitrate is a chemical compound with the formula . It is a white crystalline salt consisting of ions of ammonium and nitrate. It is highly soluble in water and hygroscopic as a solid, but does not form hydrates. It is predominantly us ...
or nitric acid that yields
uranyl nitrate Uranyl nitrate is a water-soluble yellow uranium salt with the formula . The hexa-, tri-, and dihydrates are known. The compound is mainly of interest because it is an intermediate in the preparation of nuclear fuels. In the nuclear industry, it ...
, UO2(NO3)2·6H2O. When heated, it turns into UO3, which is converted to UO2 with hydrogen: : UO3 + H2 → UO2 + H2O Reacting uranium dioxide with
hydrofluoric acid Hydrofluoric acid is a solution of hydrogen fluoride (HF) in water. Solutions of HF are colorless, acidic and highly corrosive. A common concentration is 49% (48–52%) but there are also stronger solutions (e.g. 70%) and pure HF has a boiling p ...
changes it to uranium tetrafluoride, which yields uranium metal upon reaction with magnesium metal: : 4 HF + UO2 → UF4 + 2 H2O To extract plutonium, neutron-irradiated uranium is dissolved in nitric acid, and a reducing agent ( FeSO4, or H2O2) is added to the resulting solution. This addition changes the oxidation state of plutonium from +6 to +4, while uranium remains in the form of uranyl nitrate (UO2(NO3)2). The solution is treated with a reducing agent and neutralized with ammonium carbonate to pH = 8 that results in precipitation of Pu4+ compounds. In another method, Pu4+ and are first extracted with tributyl phosphate, then reacted with
hydrazine Hydrazine is an inorganic compound with the chemical formula . It is a simple pnictogen hydride, and is a colourless flammable liquid with an ammonia-like odour. Hydrazine is highly hazardous unless handled in solution as, for example, hydraz ...
washing out the recovered plutonium. The major difficulty in separation of actinium is the similarity of its properties with those of lanthanum. Thus actinium is either synthesized in nuclear reactions from isotopes of radium or separated using ion-exchange procedures.


Properties

Actinides have similar properties to lanthanides. Just as the 4f electron shells are filled in the lanthanides, the 5f electron shells are filled in the actinides. Because the 5f, 6d, 7s, and 7p shells are close in energy, many irregular configurations arise; thus, in gas-phase atoms, just as the first 4f electron only appears in cerium, so the first 5f electron appears even later, in protactinium. However, just as lanthanum is the first element to use the 4f shell in compounds, so actinium is the first element to use the 5f shell in compounds. The f-shells complete their filling together, at ytterbium and nobelium. The first experimental evidence for the filling of the 5f shell in actinides was obtained by McMillan and Abelson in 1940. As in lanthanides (see
lanthanide contraction The lanthanide contraction is the greater-than-expected decrease in atomic radii and ionic radii of the elements in the lanthanide series, from left to right. It is caused by the poor shielding effect of nuclear charge by the 4f electrons alo ...
), the
ionic radius Ionic radius, ''r''ion, is the radius of a monatomic ion in an ionic crystal structure. Although neither atoms nor ions have sharp boundaries, they are treated as if they were hard spheres with radii such that the sum of ionic radii of the cati ...
of actinides monotonically decreases with atomic number (see also actinoid contraction). The shift of electron configurations in the gas phase does not always match the chemical behaviour. For example, the early-transition-metal-like prominence of the highest oxidation state, corresponding to removal of all valence electrons, extends up to uranium even though the 5f shells begin filling before that. On the other hand, electron configurations resembling the lanthanide congeners already begin at plutonium, even though lanthanide-like behaviour does not become dominant until the second half of the series begins at curium. The elements between uranium and curium form a transition between these two kinds of behaviour, where higher oxidation states continue to exist, but lose stability with respect to the +3 state. The +2 state becomes more important near the end of the series, and is the most stable oxidation state for nobelium, the last 5f element. Oxidation states rise again only after nobelium, showing that a new series of 6d transition metals has begun:
lawrencium Lawrencium is a synthetic chemical element; it has symbol Lr (formerly Lw) and atomic number 103. It is named after Ernest Lawrence, inventor of the cyclotron, a device that was used to discover many artificial radioactive elements. A radioactiv ...
shows only the +3 oxidation state, and
rutherfordium Rutherfordium is a synthetic element, synthetic chemical element; it has Chemical symbol, symbol Rf and atomic number 104. It is named after physicist Ernest Rutherford. As a synthetic element, it is not found in nature and can only be made in a p ...
only the +4 state, making them respectively congeners of lutetium and hafnium in the 5d row.


Physical properties

Actinides are typical metals. All of them are soft and have a silvery color (but tarnish in air),Greenwood, p. 1264 relatively high
density Density (volumetric mass density or specific mass) is the ratio of a substance's mass to its volume. The symbol most often used for density is ''ρ'' (the lower case Greek letter rho), although the Latin letter ''D'' (or ''d'') can also be u ...
and plasticity. Some of them can be cut with a knife. Their
electrical resistivity Electricity is the set of physical phenomena associated with the presence and motion of matter possessing an electric charge. Electricity is related to magnetism, both being part of the phenomenon of electromagnetism, as described by ...
varies between 15 and 150 μΩ·cm. The hardness of thorium is similar to that of soft steel, so heated pure thorium can be rolled in sheets and pulled into wire. Thorium is nearly half as dense as uranium and plutonium, but is harder than either of them. All actinides are radioactive,
paramagnetic Paramagnetism is a form of magnetism whereby some materials are weakly attracted by an externally applied magnetic field, and form internal, induced magnetic fields in the direction of the applied magnetic field. In contrast with this behavior, ...
, and, with the exception of actinium, have several crystalline phases: plutonium has seven, and uranium, neptunium and californium three. The
crystal structure In crystallography, crystal structure is a description of ordered arrangement of atoms, ions, or molecules in a crystalline material. Ordered structures occur from intrinsic nature of constituent particles to form symmetric patterns that repeat ...
s of protactinium, uranium, neptunium and plutonium do not have clear analogs among the lanthanides and are more similar to those of the 3''d''-
transition metal In chemistry, a transition metal (or transition element) is a chemical element in the d-block of the periodic table (groups 3 to 12), though the elements of group 12 (and less often group 3) are sometimes excluded. The lanthanide and actinid ...
s. All actinides are
pyrophoric A substance is pyrophoric (from , , 'fire-bearing') if it ignites spontaneously in air at or below (for gases) or within 5 minutes after coming into contact with air (for liquids and solids). Examples are organolithium compounds and triethylb ...
, especially when finely divided, that is, they spontaneously ignite upon reaction with air at room temperature. The
melting point The melting point (or, rarely, liquefaction point) of a substance is the temperature at which it changes state of matter, state from solid to liquid. At the melting point the solid and liquid phase (matter), phase exist in Thermodynamic equilib ...
of actinides does not have a clear dependence on the number of ''f''-electrons. The unusually low melting point of neptunium and plutonium (~640 °C) is explained by hybridization of 5''f'' and 6''d'' orbitals and the formation of directional bonds in these metals.


Chemical properties

Like the lanthanides, all actinides are highly reactive with
halogen The halogens () are a group in the periodic table consisting of six chemically related elements: fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and the radioactive elements astatine (At) and tennessine (Ts), though some authors would ...
s and
chalcogen The chalcogens (ore forming) ( ) are the chemical elements in group 16 of the periodic table. This group is also known as the oxygen family. Group 16 consists of the elements oxygen (O), sulfur (S), selenium (Se), tellurium (Te), and the rad ...
s; however, the actinides react more easily. Actinides, especially those with a small number of 5''f''-electrons, are prone to hybridization. This is explained by the similarity of the electron energies at the 5''f'', 7''s'' and 6''d'' shells. Most actinides exhibit a larger variety of valence states, and the most stable are +6 for uranium, +5 for protactinium and neptunium, +4 for thorium and plutonium and +3 for actinium and other actinides.Golub, pp. 222–227 Actinium is chemically similar to lanthanum, which is explained by their similar ionic radii and electronic structures. Like lanthanum, actinium almost always has an oxidation state of +3 in compounds, but it is less reactive and has more pronounced
basic Basic or BASIC may refer to: Science and technology * BASIC, a computer programming language * Basic (chemistry), having the properties of a base * Basic access authentication, in HTTP Entertainment * Basic (film), ''Basic'' (film), a 2003 film ...
properties. Among other trivalent actinides Ac3+ is least acidic, i.e. has the weakest tendency to hydrolyze in aqueous solutions. Thorium is rather active chemically. Owing to lack of
electron The electron (, or in nuclear reactions) is a subatomic particle with a negative one elementary charge, elementary electric charge. It is a fundamental particle that comprises the ordinary matter that makes up the universe, along with up qua ...
s on 6''d'' and 5''f'' orbitals, tetravalent thorium compounds are colorless. At pH < 3, solutions of thorium salts are dominated by the cations h(H2O)8sup>4+. The Th4+ ion is relatively large, and depending on the
coordination number In chemistry, crystallography, and materials science, the coordination number, also called ligancy, of a central atom in a molecule or crystal is the number of atoms, molecules or ions bonded to it. The ion/molecule/atom surrounding the central ion ...
can have a radius between 0.95 and 1.14 Å. As a result, thorium salts have a weak tendency to hydrolyse. The distinctive ability of thorium salts is their high solubility both in water and polar organic solvents. Protactinium exhibits two valence states; the +5 is stable, and the +4 state easily oxidizes to protactinium(V). Thus tetravalent protactinium in solutions is obtained by the action of strong reducing agents in a hydrogen atmosphere. Tetravalent protactinium is chemically similar to uranium(IV) and thorium(IV).
Fluoride Fluoride (). According to this source, is a possible pronunciation in British English. is an Inorganic chemistry, inorganic, Monatomic ion, monatomic Ion#Anions and cations, anion of fluorine, with the chemical formula (also written ), whose ...
s,
phosphate Phosphates are the naturally occurring form of the element phosphorus. In chemistry, a phosphate is an anion, salt, functional group or ester derived from a phosphoric acid. It most commonly means orthophosphate, a derivative of orthop ...
s, hypophosphates, iodates and phenylarsonates of protactinium(IV) are insoluble in water and dilute acids. Protactinium forms soluble
carbonate A carbonate is a salt of carbonic acid, (), characterized by the presence of the carbonate ion, a polyatomic ion with the formula . The word "carbonate" may also refer to a carbonate ester, an organic compound containing the carbonate group ...
s. The hydrolytic properties of pentavalent protactinium are close to those of
tantalum Tantalum is a chemical element; it has Symbol (chemistry), symbol Ta and atomic number 73. It is named after Tantalus, a figure in Greek mythology. Tantalum is a very hard, ductility, ductile, lustre (mineralogy), lustrous, blue-gray transition ...
(V) and
niobium Niobium is a chemical element; it has chemical symbol, symbol Nb (formerly columbium, Cb) and atomic number 41. It is a light grey, crystalline, and Ductility, ductile transition metal. Pure niobium has a Mohs scale of mineral hardness, Mohs h ...
(V). The complex chemical behavior of protactinium is a consequence of the start of the filling of the 5''f'' shell in this element. Uranium has a valence from 3 to 6, the last being most stable. In the hexavalent state, uranium is very similar to the
group 6 element Group 6, numbered by IUPAC style, is a group of elements in the periodic table. Its members are chromium (Cr), molybdenum (Mo), tungsten (W), and seaborgium (Sg). These are all transition metals and chromium, molybdenum and tungsten are refract ...
s. Many compounds of uranium(IV) and uranium(VI) are
non-stoichiometric Non-stoichiometric compounds are chemical compounds, almost always solid inorganic compounds, having chemical element, elemental composition whose proportions cannot be represented by a ratio of small natural numbers (i.e. an empirical formula); ...
, i.e. have variable composition. For example, the actual chemical formula of uranium dioxide is UO2+x, where ''x'' varies between −0.4 and 0.32. Uranium(VI) compounds are weak oxidants. Most of them contain the linear "
uranyl The uranyl ion with the chemical formula has a linear structure with short U–O bonds, indicative of the presence of multiple bonds between uranium and oxygen, with uranium in the oxidation state +6. Four or more ligands may be bound to the u ...
" group, . Between 4 and 6 ligands can be accommodated in an equatorial plane perpendicular to the uranyl group. The uranyl group acts as a hard acid and forms stronger complexes with oxygen-donor ligands than with nitrogen-donor ligands. and are also the common form of Np and Pu in the +6 oxidation state. Uranium(IV) compounds exhibit reducing properties, e.g., they are easily oxidized by atmospheric oxygen. Uranium(III) is a very strong reducing agent. Owing to the presence of d-shell, uranium (as well as many other actinides) forms organometallic compounds, such as UIII(C5H5)3 and UIV(C5H5)4.Greenwood, p. 1278 Neptunium has valence states from 3 to 7, which can be simultaneously observed in solutions. The most stable state in solution is +5, but the valence +4 is preferred in solid neptunium compounds. Neptunium metal is very reactive. Ions of neptunium are prone to hydrolysis and formation of
coordination compound A coordination complex is a chemical compound consisting of a central atom or ion, which is usually metallic and is called the ''coordination centre'', and a surrounding array of chemical bond, bound molecules or ions, that are in turn known as ' ...
s. Plutonium also exhibits valence states between 3 and 7 inclusive, and thus is chemically similar to neptunium and uranium. It is highly reactive, and quickly forms an oxide film in air. Plutonium reacts with
hydrogen Hydrogen is a chemical element; it has chemical symbol, symbol H and atomic number 1. It is the lightest and abundance of the chemical elements, most abundant chemical element in the universe, constituting about 75% of all baryon, normal matter ...
even at temperatures as low as 25–50 °C; it also easily forms halides and intermetallic compounds. Hydrolysis reactions of plutonium ions of different oxidation states are quite diverse. Plutonium(V) can enter
polymerization In polymer chemistry, polymerization (American English), or polymerisation (British English), is a process of reacting monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks. There are many fo ...
reactions. The largest chemical diversity among actinides is observed in americium, which can have valence between 2 and 6. Divalent americium is obtained only in dry compounds and non-aqueous solutions (
acetonitrile Acetonitrile, often abbreviated MeCN (methyl cyanide), is the chemical compound with the formula and structure . This colourless liquid is the simplest organic nitrile (hydrogen cyanide is a simpler nitrile, but the cyanide anion is not class ...
). Oxidation states +3, +5 and +6 are typical for aqueous solutions, but also in the solid state. Tetravalent americium forms stable solid compounds ( dioxide,
fluoride Fluoride (). According to this source, is a possible pronunciation in British English. is an Inorganic chemistry, inorganic, Monatomic ion, monatomic Ion#Anions and cations, anion of fluorine, with the chemical formula (also written ), whose ...
and
hydroxide Hydroxide is a diatomic anion with chemical formula OH−. It consists of an oxygen and hydrogen atom held together by a single covalent bond, and carries a negative electric charge. It is an important but usually minor constituent of water. It ...
) as well as complexes in aqueous solutions. It was reported that in alkaline solution americium can be oxidized to the heptavalent state, but these data proved erroneous. The most stable valence of americium is 3 in aqueous solution and 3 or 4 in solid compounds.Myasoedov, pp. 25–29 Valence 3 is dominant in all subsequent elements up to lawrencium (with the exception of nobelium). Curium can be tetravalent in solids (
fluoride Fluoride (). According to this source, is a possible pronunciation in British English. is an Inorganic chemistry, inorganic, Monatomic ion, monatomic Ion#Anions and cations, anion of fluorine, with the chemical formula (also written ), whose ...
, dioxide). Berkelium, along with a valence of +3, also shows the valence of +4, more stable than that of curium; the valence 4 is observed in solid
fluoride Fluoride (). According to this source, is a possible pronunciation in British English. is an Inorganic chemistry, inorganic, Monatomic ion, monatomic Ion#Anions and cations, anion of fluorine, with the chemical formula (also written ), whose ...
and dioxide. The stability of Bk4+ in aqueous solution is close to that of Ce4+. Only valence 3 was observed for californium, einsteinium and fermium. The divalent state is proven for mendelevium and nobelium, and in nobelium it is more stable than the trivalent state. Lawrencium shows valence 3 both in solutions and solids. The redox potential \mathit E_\frac increases from −0.32 V in uranium, through 0.34 V (Np) and 1.04 V (Pu) to 1.34 V in americium revealing the increasing reduction ability of the An4+ ion from americium to uranium. All actinides form AnH3 hydrides of black color with salt-like properties. Actinides also produce
carbide In chemistry, a carbide usually describes a compound composed of carbon and a metal. In metallurgy, carbiding or carburizing is the process for producing carbide coatings on a metal piece. Interstitial / Metallic carbides The carbides of th ...
s with the general formula of AnC or AnC2 ( U2C3 for uranium) as well as sulfides An2S3 and AnS2. File:Uranylnitrate_crystals.jpg,
Uranyl nitrate Uranyl nitrate is a water-soluble yellow uranium salt with the formula . The hexa-, tri-, and dihydrates are known. The compound is mainly of interest because it is an intermediate in the preparation of nuclear fuels. In the nuclear industry, it ...
(UO2(NO3)2) File:U Oxstufen.jpg, Aqueous solutions of uranium III, IV, V, VI salts File:Np ox st .jpg, Aqueous solutions of neptunium III, IV, V, VI, VII salts File:Plutonium in solution.jpg, Aqueous solutions of plutonium III, IV, V, VI, VII salts File:UCl4.jpg, Uranium tetrachloride File:Uranium hexafluoride crystals sealed in an ampoule.jpg, Uranium hexafluoride File:Yellowcake.jpg, U3O8 ( yellowcake)


Compounds


Oxides and hydroxides

: An – actinide
**Depending on the isotopes
Some actinides can exist in several oxide forms such as An2O3, AnO2, An2O5 and AnO3. For all actinides, oxides AnO3 are amphoteric and An2O3, AnO2 and An2O5 are basic, they easily react with water, forming bases: : An2O3 + 3 H2O → 2 An(OH)3. These bases are poorly soluble in water and by their activity are close to the
hydroxide Hydroxide is a diatomic anion with chemical formula OH−. It consists of an oxygen and hydrogen atom held together by a single covalent bond, and carries a negative electric charge. It is an important but usually minor constituent of water. It ...
s of rare-earth metals. Np(OH)3 has not yet been synthesized, Pu(OH)3 has a blue color while Am(OH)3 is pink and Cm(OH)3 is colorless. Bk(OH)3 and Cf(OH)3 are also known, as are tetravalent hydroxides for Np, Pu and Am and pentavalent for Np and Am. The strongest base is of actinium. All compounds of actinium are colorless, except for black actinium sulfide (Ac2S3). Dioxides of tetravalent actinides crystallize in the cubic system, same as in calcium fluoride. Thorium reacting with oxygen exclusively forms the dioxide: : Th + O2 -> ce\overbrace^ Thorium dioxide is a refractory material with the highest melting point among any known oxide (3390 °C). Adding 0.8–1% ThO2 to tungsten stabilizes its structure, so the doped filaments have better mechanical stability to vibrations. To dissolve ThO2 in acids, it is heated to 500–600 °C; heating above 600 °C produces a very resistant to acids and other reagents form of ThO2. Small addition of fluoride ions catalyses dissolution of thorium dioxide in acids. Two protactinium oxides have been obtained: PaO2 (black) and Pa2O5 (white); the former is isomorphic with ThO2 and the latter is easier to obtain. Both oxides are basic, and Pa(OH)5 is a weak, poorly soluble base. Decomposition of certain salts of uranium, for example UO2(NO3)·6H2O in air at 400 °C, yields orange or yellow UO3. This oxide is amphoteric and forms several hydroxides, the most stable being uranyl hydroxide UO2(OH)2. Reaction of uranium(VI) oxide with hydrogen results in uranium dioxide, which is similar in its properties with ThO2. This oxide is also basic and corresponds to the uranium hydroxide U(OH)4. Plutonium, neptunium and americium form two basic oxides: An2O3 and AnO2. Neptunium trioxide is unstable; thus, only Np3O8 could be obtained so far. However, the oxides of plutonium and neptunium with the chemical formula AnO2 and An2O3 are well characterized.


Salts

: *An – actinide
**Depending on the isotopes
Actinides easily react with halogens forming salts with the formulas MX3 and MX4 (X =
halogen The halogens () are a group in the periodic table consisting of six chemically related elements: fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and the radioactive elements astatine (At) and tennessine (Ts), though some authors would ...
). So the first berkelium compound, BkCl3, was synthesized in 1962 with an amount of 3 nanograms. Like the halogens of rare earth elements, actinide
chloride The term chloride refers to a compound or molecule that contains either a chlorine anion (), which is a negatively charged chlorine atom, or a non-charged chlorine atom covalently bonded to the rest of the molecule by a single bond (). The pr ...
s, bromides, and iodides are water-soluble, and
fluoride Fluoride (). According to this source, is a possible pronunciation in British English. is an Inorganic chemistry, inorganic, Monatomic ion, monatomic Ion#Anions and cations, anion of fluorine, with the chemical formula (also written ), whose ...
s are insoluble. Uranium easily yields a colorless hexafluoride, which sublimates at a temperature of 56.5 °C; because of its volatility, it is used in the separation of uranium isotopes with
gas centrifuge A gas centrifuge is a device that performs isotope separation of gases. A centrifuge relies on the principles of centrifugal force accelerating molecules so that particles of different masses are physically separated in a gradient along the radiu ...
or gaseous diffusion. Actinide hexafluorides have properties close to
anhydride An acid anhydride is a type of chemical compound derived by the removal of water molecules from an acid (chemistry), acid. In organic chemistry, organic acid anhydrides contain the functional group . Organic acid anhydrides often form when one ...
s. They are very sensitive to moisture and hydrolyze forming AnO2F2.Greenwood, p.1269 The pentachloride and black hexachloride of uranium were synthesized, but they are both unstable. Action of acids on actinides yields salts, and if the acids are non-oxidizing then the actinide in the salt is in low-valence state: : U + 2 H2SO4U(SO4)2 + 2 H2 : 2 Pu + 6 HCl → 2 PuCl3 + 3 H2 However, in these reactions the regenerating hydrogen can react with the metal, forming the corresponding hydride. Uranium reacts with acids and water much more easily than thorium. Actinide salts can also be obtained by dissolving the corresponding hydroxides in acids. Nitrates, chlorides, sulfates and perchlorates of actinides are water-soluble. When crystallizing from aqueous solutions, these salts form hydrates, such as Th(NO3)4·6H2O, Th(SO4)2·9H2O and Pu2(SO4)3·7H2O. Salts of high-valence actinides easily hydrolyze. So, colorless sulfate, chloride, perchlorate and nitrate of thorium transform into basic salts with formulas Th(OH)2SO4 and Th(OH)3NO3. The solubility and insolubility of trivalent and tetravalent actinides is like that of lanthanide salts. So
phosphate Phosphates are the naturally occurring form of the element phosphorus. In chemistry, a phosphate is an anion, salt, functional group or ester derived from a phosphoric acid. It most commonly means orthophosphate, a derivative of orthop ...
s,
fluoride Fluoride (). According to this source, is a possible pronunciation in British English. is an Inorganic chemistry, inorganic, Monatomic ion, monatomic Ion#Anions and cations, anion of fluorine, with the chemical formula (also written ), whose ...
s,
oxalate Oxalate (systematic IUPAC name: ethanedioate) is an anion with the chemical formula . This dianion is colorless. It occurs naturally, including in some foods. It forms a variety of salts, for example sodium oxalate (), and several esters such as ...
s, iodates and
carbonate A carbonate is a salt of carbonic acid, (), characterized by the presence of the carbonate ion, a polyatomic ion with the formula . The word "carbonate" may also refer to a carbonate ester, an organic compound containing the carbonate group ...
s of actinides are weakly soluble in water; they precipitate as hydrates, such as ThF4·3H2O and Th(CrO4)2·3H2O. Actinides with oxidation state +6, except for the AnO22+-type cations, form nO4sup>2−, n2O7sup>2− and other complex anions. For example, uranium, neptunium and plutonium form salts of the Na2UO4 ( uranate) and (NH4)2U2O7 (diuranate) types. In comparison with lanthanides, actinides more easily form
coordination compound A coordination complex is a chemical compound consisting of a central atom or ion, which is usually metallic and is called the ''coordination centre'', and a surrounding array of chemical bond, bound molecules or ions, that are in turn known as ' ...
s, and this ability increases with the actinide valence. Trivalent actinides do not form fluoride coordination compounds, whereas tetravalent thorium forms K2ThF6, KThF5, and even K5ThF9 complexes. Thorium also forms the corresponding
sulfate The sulfate or sulphate ion is a polyatomic anion with the empirical formula . Salts, acid derivatives, and peroxides of sulfate are widely used in industry. Sulfates occur widely in everyday life. Sulfates are salts of sulfuric acid and many ...
s (for example Na2SO4·Th(SO4)2·5H2O),
nitrate Nitrate is a polyatomic ion with the chemical formula . salt (chemistry), Salts containing this ion are called nitrates. Nitrates are common components of fertilizers and explosives. Almost all inorganic nitrates are solubility, soluble in wa ...
s and thiocyanates. Salts with the general formula An2Th(NO3)6·''n''H2O are of coordination nature, with the
coordination number In chemistry, crystallography, and materials science, the coordination number, also called ligancy, of a central atom in a molecule or crystal is the number of atoms, molecules or ions bonded to it. The ion/molecule/atom surrounding the central ion ...
of thorium equal to 12. Even easier is to produce complex salts of pentavalent and hexavalent actinides. The most stable coordination compounds of actinides – tetravalent thorium and uranium – are obtained in reactions with diketones, e.g. acetylacetone.


Applications

While actinides have some established daily-life applications, such as in smoke detectors (americium)Greenwood, p. 1262 and gas mantles (thorium),Greenwood, p. 1255 they are mostly used in
nuclear weapon A nuclear weapon is an explosive device that derives its destructive force from nuclear reactions, either fission (fission or atomic bomb) or a combination of fission and fusion reactions (thermonuclear weapon), producing a nuclear exp ...
s and as
fuel A fuel is any material that can be made to react with other substances so that it releases energy as thermal energy or to be used for work (physics), work. The concept was originally applied solely to those materials capable of releasing chem ...
in nuclear reactors. The last two areas exploit the property of actinides to release enormous energy in nuclear reactions, which under certain conditions may become self-sustaining chain reactions. The most important isotope for
nuclear power Nuclear power is the use of nuclear reactions to produce electricity. Nuclear power can be obtained from nuclear fission, nuclear decay and nuclear fusion reactions. Presently, the vast majority of electricity from nuclear power is produced by ...
applications is
uranium-235 Uranium-235 ( or U-235) is an isotope of uranium making up about 0.72% of natural uranium. Unlike the predominant isotope uranium-238, it is fissile, i.e., it can sustain a nuclear chain reaction. It is the only fissile isotope that exists in nat ...
. It is used in the thermal reactor, and its concentration in natural uranium does not exceed 0.72%. This isotope strongly absorbs
thermal neutron The neutron detection temperature, also called the neutron energy, indicates a free neutron's kinetic energy, usually given in electron volts. The term ''temperature'' is used, since hot, thermal and cold neutrons are moderated in a medium wit ...
s releasing much energy. One fission act of 1 gram of 235U converts into about 1 MW·day. Of importance, is that emits more neutrons than it absorbs;Golub, pp. 220–221 upon reaching the
critical mass In nuclear engineering, critical mass is the minimum mass of the fissile material needed for a sustained nuclear chain reaction in a particular setup. The critical mass of a fissionable material depends upon its nuclear properties (specific ...
, enters into a self-sustaining chain reaction. Typically, uranium nucleus is divided into two fragments with the release of 2–3 neutrons, for example: : + ⟶ + + 3 Other promising actinide isotopes for nuclear power are
thorium-232 Thorium-232 () is the main naturally occurring isotope of thorium, with a relative abundance of 99.98%. It has a half life of 14.05 billion years, which makes it the longest-lived isotope of thorium. It decays by alpha decay to radium-228; its de ...
and its product from the
thorium fuel cycle The thorium fuel cycle is a nuclear fuel cycle that uses an isotope of thorium, , as the fertile material. In the reactor, is transmuted into the fissile artificial uranium isotope which is the nuclear fuel. Unlike natural uranium, natural ...
,
uranium-233 Uranium-233 ( or U-233) is a fissile isotope of uranium that is bred from thorium-232 as part of the thorium fuel cycle. Uranium-233 was investigated for use in nuclear weapons and as a Nuclear fuel, reactor fuel. It has been used successfully ...
. Emission of neutrons during the fission of uranium is important not only for maintaining the nuclear chain reaction, but also for the synthesis of the heavier actinides.
Uranium-239 Uranium (U) is a naturally occurring radioactive element (radioelement) with no stable isotopes. It has two primordial isotopes, uranium-238 and uranium-235, that have long half-lives and are found in appreciable quantity in Earth's crust. Th ...
converts via β-decay into plutonium-239, which, like uranium-235, is capable of spontaneous fission. The world's first nuclear reactors were built not for energy, but for producing plutonium-239 for nuclear weapons. About half of produced thorium is used as the light-emitting material of gas mantles. Thorium is also added into multicomponent
alloy An alloy is a mixture of chemical elements of which in most cases at least one is a metal, metallic element, although it is also sometimes used for mixtures of elements; herein only metallic alloys are described. Metallic alloys often have prop ...
s of
magnesium Magnesium is a chemical element; it has Symbol (chemistry), symbol Mg and atomic number 12. It is a shiny gray metal having a low density, low melting point and high chemical reactivity. Like the other alkaline earth metals (group 2 ...
and
zinc Zinc is a chemical element; it has symbol Zn and atomic number 30. It is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 (IIB) of the periodic tabl ...
. Mg-Th alloys are light and strong, but also have high melting point and ductility and thus are widely used in the aviation industry and in the production of
missile A missile is an airborne ranged weapon capable of self-propelled flight aided usually by a propellant, jet engine or rocket motor. Historically, 'missile' referred to any projectile that is thrown, shot or propelled towards a target; this ...
s. Thorium also has good electron emission properties, with long lifetime and low potential barrier for the emission. The relative content of thorium and uranium isotopes is widely used to estimate the age of various objects, including stars (see
radiometric dating Radiometric dating, radioactive dating or radioisotope dating is a technique which is used to Chronological dating, date materials such as Rock (geology), rocks or carbon, in which trace radioactive impurity, impurities were selectively incorporat ...
). The major application of plutonium has been in
nuclear weapon A nuclear weapon is an explosive device that derives its destructive force from nuclear reactions, either fission (fission or atomic bomb) or a combination of fission and fusion reactions (thermonuclear weapon), producing a nuclear exp ...
s, where the isotope plutonium-239 was a key component due to its ease of fission and availability. Plutonium-based designs allow reducing the
critical mass In nuclear engineering, critical mass is the minimum mass of the fissile material needed for a sustained nuclear chain reaction in a particular setup. The critical mass of a fissionable material depends upon its nuclear properties (specific ...
to about a third of that for uranium-235. The "
Fat Man "Fat Man" (also known as Mark III) was the design of the nuclear weapon the United States used for seven of the first eight nuclear weapons ever detonated in history. It is also the most powerful design to ever be used in warfare. A Fat Man ...
"-type plutonium bombs produced during the
Manhattan Project The Manhattan Project was a research and development program undertaken during World War II to produce the first nuclear weapons. It was led by the United States in collaboration with the United Kingdom and Canada. From 1942 to 1946, the ...
used explosive compression of plutonium to obtain significantly higher densities than normal, combined with a central neutron source to begin the reaction and increase efficiency. Thus only 6.2 kg of plutonium was needed for an explosive yield equivalent to 20 kilotons of TNT. (See also
Nuclear weapon design Nuclear weapons design are physical, chemical, and engineering arrangements that cause the physics package of a nuclear weapon to detonate. There are three existing basic design types: # Pure fission weapons are the simplest, least technically de ...
.) Hypothetically, as little as 4 kg of plutonium—and maybe even less—could be used to make a single atomic bomb using very sophisticated assembly designs.
Plutonium-238 Plutonium-238 ( or Pu-238) is a radioactive isotope of plutonium that has a half-life of 87.7 years. Plutonium-238 is a very powerful alpha emitter; as alpha particles are easily blocked, this makes the plutonium-238 isotope suitable for usage ...
is potentially more efficient isotope for nuclear reactors, since it has smaller critical mass than uranium-235, but it continues to release much thermal energy (0.56 W/g) by decay even when the fission chain reaction is stopped by control rods. Its application is limited by its high price (about US$1000/g). This isotope has been used in
thermopile A thermopile is an electronic device that converts thermal energy into electrical energy. It is composed of several thermocouples connected usually in series or, less commonly, in parallel. Such a device works on the principle of the thermoel ...
s and water
distillation Distillation, also classical distillation, is the process of separating the component substances of a liquid mixture of two or more chemically discrete substances; the separation process is realized by way of the selective boiling of the mixt ...
systems of some space satellites and stations. The
Galileo Galileo di Vincenzo Bonaiuti de' Galilei (15 February 1564 – 8 January 1642), commonly referred to as Galileo Galilei ( , , ) or mononymously as Galileo, was an Italian astronomer, physicist and engineer, sometimes described as a poly ...
and
Apollo Apollo is one of the Twelve Olympians, Olympian deities in Ancient Greek religion, ancient Greek and Ancient Roman religion, Roman religion and Greek mythology, Greek and Roman mythology. Apollo has been recognized as a god of archery, mu ...
spacecraft (e.g. Apollo 14) had heaters powered by kilogram quantities of plutonium-238 oxide; this heat is also transformed into electricity with thermopiles. The decay of plutonium-238 produces relatively harmless alpha particles and is not accompanied by gamma rays. Therefore, this isotope (~160 mg) is used as the energy source in heart pacemakers where it lasts about 5 times longer than conventional batteries. Actinium-227 is used as a neutron source. Its high specific energy (14.5 W/g) and the possibility of obtaining significant quantities of thermally stable compounds are attractive for use in long-lasting thermoelectric generators for remote use. 228Ac is used as an indicator of
radioactivity Radioactive decay (also known as nuclear decay, radioactivity, radioactive disintegration, or nuclear disintegration) is the process by which an unstable atomic nucleus loses energy by radiation. A material containing unstable nuclei is conside ...
in chemical research, as it emits high-energy electrons (2.18 MeV) that can be easily detected. 228Ac- 228Ra mixtures are widely used as an intense gamma-source in industry and medicine. Development of self-glowing actinide-doped materials with durable crystalline matrices is a new area of actinide utilization as the addition of alpha-emitting radionuclides to some glasses and crystals may confer luminescence.


Toxicity

Radioactive substances can harm human health via (i) local skin contamination, (ii) internal exposure due to ingestion of radioactive isotopes, and (iii) external overexposure by Beta particle, β-activity and Gamma ray, γ-radiation. Together with radium and transuranium elements, actinium is one of the most dangerous radioactive poisons with high specific Alpha radiation, α-activity. The most important feature of actinium is its ability to accumulate and remain in the surface layer of skeletons. At the initial stage of poisoning, actinium accumulates in the liver. Another danger of actinium is that it undergoes radioactive decay faster than being excreted. Adsorption from the digestive tract is much smaller (~0.05%) for actinium than radium. Protactinium in the body tends to accumulate in the kidneys and bones. The maximum safe dose of protactinium in the human body is 0.03 Curie (unit), μCi that corresponds to 0.5 micrograms of 231Pa. This isotope, which might be present in the air as aerosol, is 2.5 times more toxic than hydrocyanic acid. Plutonium, when entering the body through air, food or blood (e.g. a wound), mostly settles in the lungs, liver and bones with only about 10% going to other organs, and remains there for decades. The long residence time of plutonium in the body is partly explained by its poor solubility in water. Some isotopes of plutonium emit ionizing α-radiation, which damages the surrounding cells. The median lethal dose (LD50) for 30 days in dogs after intravenous injection of plutonium is 0.32 milligram per kg of body mass, and thus the lethal dose for humans is approximately 22 mg for a person weighing 70 kg; the amount for respiratory exposure should be approximately four times greater. Another estimate assumes that plutonium is 50 times less toxic than
radium Radium is a chemical element; it has chemical symbol, symbol Ra and atomic number 88. It is the sixth element in alkaline earth metal, group 2 of the periodic table, also known as the alkaline earth metals. Pure radium is silvery-white, ...
, and thus permissible content of plutonium in the body should be 5 μg or 0.3 μCi. Such amount is nearly invisible under microscope. After trials on animals, this maximum permissible dose was reduced to 0.65 μg or 0.04 μCi. Studies on animals also revealed that the most dangerous plutonium exposure route is through inhalation, after which 5–25% of inhaled substances is retained in the body. Depending on the particle size and solubility of the plutonium compounds, plutonium is localized either in the lungs or in the lymphatic system, or is absorbed in the blood and then transported to the liver and bones. Contamination via food is the least likely way. In this case, only about 0.05% of soluble and 0.01% of insoluble compounds of plutonium absorbs into blood, and the rest is excreted. Exposure of damaged skin to plutonium would retain nearly 100% of it. Using actinides in nuclear fuel, sealed radioactive sources or advanced materials such as self-glowing crystals has many potential benefits. However, a serious concern is the extremely high radiotoxicity of actinides and their migration in the environment. Use of chemically unstable forms of actinides in MOX and sealed radioactive sources is not appropriate by modern safety standards. There is a challenge to develop stable and durable actinide-bearing materials, which provide safe storage, use and final disposal. A key need is application of actinide solid solutions in durable crystalline host phases.


See also

* Actinides in the environment * Lanthanides * Major actinides * Minor actinides * transuranium, Transuranics


Notes


References


Bibliography

* * *


External links


Lawrence Berkeley Laboratory image of historic periodic table by Seaborg showing actinide series for the first time

Lawrence Livermore National Laboratory, ''Uncovering the Secrets of the Actinides''

Los Alamos National Laboratory, ''Actinide Research Quarterly''
{{Authority control Actinides, Periodic table