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Samarium
Samarium
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Samarium, 62Sm
Samarium
Pronunciation/səˈmɛəriəm/ (sə-MAIR-ee-əm)
Appearancesilvery white
Standard atomic weight Ar°(Sm)
Samarium in the periodic table
Hydrogen Helium
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon
Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine Argon
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
Caesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury (element) Thallium Lead Bismuth Polonium Astatine Radon
Francium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson


Sm

Pu
promethiumsamariumeuropium
Atomic number (Z)62
Groupf-block groups (no number)
Periodperiod 6
Block  f-block
Electron configuration[Xe] 4f6 6s2
Electrons per shell2, 8, 18, 24, 8, 2
Physical properties
Phase at STPsolid
Melting point1345 K ​(1072 °C, ​1962 °F)
Boiling point2173 K ​(1900 °C, ​3452 °F)
Density (at 20° C)7.518 g/cm3[3]
when liquid (at m.p.)7.16 g/cm3
Heat of fusion8.62 kJ/mol
Heat of vaporization192 kJ/mol
Molar heat capacity29.54 J/(mol·K)
Vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 1001 1106 1240 (1421) (1675) (2061)
Atomic properties
Oxidation statescommon: +3
0,[4] +1,[5] +2[6]
ElectronegativityPauling scale: 1.17
Ionization energies
  • 1st: 544.5 kJ/mol
  • 2nd: 1070 kJ/mol
  • 3rd: 2260 kJ/mol
Atomic radiusempirical: 180 pm
Covalent radius198±8 pm
Color lines in a spectral range
Spectral lines of samarium
Other properties
Natural occurrenceprimordial
Crystal structurerhombohedral (hR3)
Lattice constants
Rhombohedral crystal structure for samarium
ar = 0.89834 nm
α = 23.307°
ah = 0.36291 nm
ch = 2.6207 nm (at 20 °C)[3]
Thermal expansionpoly: 12.7 (at r.t.) µm/(m⋅K)
Thermal conductivity13.3 W/(m⋅K)
Electrical resistivityα, poly: 0.940 (at r.t.) µΩ⋅m
Magnetic orderingparamagnetic[7]
Molar magnetic susceptibility+1860.0×10−6 cm3/mol (291 K)[8]
Young's modulus49.7 GPa
Shear modulus19.5 GPa
Bulk modulus37.8 GPa
Speed of sound thin rod2130 m/s (at 20 °C)
Poisson ratio0.274
Vickers hardness410–440 MPa
Brinell hardness440–600 MPa
CAS Number7440-19-9
History
Namingafter the mineral samarskite (itself named after Vassili Samarsky-Bykhovets)
DiscoveryLecoq de Boisbaudran (1879)
First isolationWilhelm Muthmann (1903)
Isotopes of samarium
Main isotopes[9] Decay
Isotope abun­dance half-life (t1/2) mode pro­duct
144Sm 3.08% stable
145Sm synth 340 d ε 145Pm
146Sm trace 9.20×107 y[10] α 142Nd
147Sm 15% 1.066×1011 y α 143Nd
148Sm 11.3% 6.3×1015 y α 144Nd
149Sm 13.8% stable
150Sm 7.37% stable
151Sm synth 94.6 y β 151Eu
152Sm 26.7% stable
153Sm synth 46.285 h β 153Eu
154Sm 22.7% stable
 Category: Samarium
| references

Samarium is a chemical element; it has symbol Sm and atomic number 62. It is a moderately hard silvery metal that slowly oxidizes in air. Being a typical member of the lanthanide series, samarium usually has the oxidation state +3. Compounds of samarium(II) are also known, most notably the monoxide SmO, monochalcogenides SmS, SmSe and SmTe, as well as samarium(II) iodide.

Discovered in 1879 by French chemist Paul-Émile Lecoq de Boisbaudran, samarium was named after the mineral samarskite from which it was isolated. The mineral itself was named after a Russian mine official, Colonel Vassili Samarsky-Bykhovets, who thus became the first person to have a chemical element named after him, though the name was indirect.

Samarium occurs in concentration up to 2.8% in several minerals including cerite, gadolinite, samarskite, monazite and bastnäsite, the last two being the most common commercial sources of the element. These minerals are mostly found in China, the United States, Brazil, India, Sri Lanka and Australia; China is by far the world leader in samarium mining and production.

The main commercial use of samarium is in samarium–cobalt magnets, which have permanent magnetization second only to neodymium magnets; however, samarium compounds can withstand significantly higher temperatures, above 700 °C (1,292 °F), without losing their permanent magnetic properties. The radioisotope samarium-153 is the active component of the drug samarium (153Sm) lexidronam (Quadramet), which kills cancer cells in lung cancer, prostate cancer, breast cancer and osteosarcoma. Another isotope, samarium-149, is a strong neutron absorber and so is added to control rods of nuclear reactors. It also forms as a decay product during reactor operation and is one of the important factors considered in reactor design and operation. Other uses of samarium include catalysis of chemical reactions, radioactive dating and X-ray lasers. Samarium(II) iodide, in particular, is a common reducing agent in chemical synthesis.

Samarium has no biological role; some samarium salts are slightly toxic.[11]

Physical properties

[edit]

Samarium is a rare earth element with a hardness and density similar to zinc. With a boiling point of 1,794 °C (3,261 °F), samarium is the third most volatile lanthanide after ytterbium and europium and comparable in this respect to lead and barium; this helps separation of samarium from its ores.[12][13] When freshly prepared, samarium has a silvery lustre, and takes on a duller appearance when oxidized in air. Samarium is calculated to have one of the largest atomic radii of the elements; with a radius of 238 pm, only potassium, praseodymium, barium, rubidium and caesium are larger.[14]

In ambient conditions, samarium has a rhombohedral structure (α form). Upon heating to 731 °C (1,348 °F), its crystal symmetry changes to hexagonal close-packed (hcp),; it has actual transition temperature depending on metal purity. Further heating to 922 °C (1,692 °F) transforms the metal into a body-centered cubic (bcc) phase. Heating to 300 °C (572 °F) plus compression to 40 kbar results in a double-hexagonally close-packed structure (dhcp). Higher pressure of the order of hundreds or thousands of kilobars induces a series of phase transformations, in particular with a tetragonal phase appearing at about 900 kbar.[15] In one study, the dhcp phase could be produced without compression, using a nonequilibrium annealing regime with a rapid temperature change between about 400 °C (752 °F) and 700 °C (1,292 °F), confirming the transient character of this samarium phase. Thin films of samarium obtained by vapor deposition may contain the hcp or dhcp phases in ambient conditions.[15]

Samarium and its sesquioxide are paramagnetic at room temperature. Their corresponding effective magnetic moments, below 2 bohr magnetons, are the third-lowest among lanthanides (and their oxides) after lanthanum and lutetium. The metal transforms to an antiferromagnetic state upon cooling to 14.8 K.[16][17] Individual samarium atoms can be isolated by encapsulating them into fullerene molecules.[18] They can also be intercalated into the interstices of the bulk C60 to form a solid solution of nominal composition Sm3C60, which is superconductive at a temperature of 8 K.[19] Samarium doping of iron-based superconductors – a class of high-temperature superconductor – increases their transition to normal conductivity temperature up to 56 K, the highest value achieved so far in this series.[20]

Chemical properties

[edit]

In air, samarium slowly oxidizes at room temperature and spontaneously ignites at 150 °C (302 °F).[11][13] Even when stored under mineral oil, samarium gradually oxidizes and develops a grayish-yellow powder of the oxide-hydroxide mixture at the surface. The metallic appearance of a sample can be preserved by sealing it under an inert gas such as argon.

Samarium is quite electropositive and reacts slowly with cold water and rapidly with hot water to form samarium hydroxide:[21]

2Sm(s) + 6H2O(l) → 2Sm(OH)3(aq) + 3H2(g)

Samarium dissolves readily in dilute sulfuric acid to form solutions containing the yellow[22] to pale green Sm(III) ions, which exist as [Sm(OH2)9]3+ complexes:[21]

2Sm(s) + 3H2SO4(aq) → 2Sm3+(aq) + 3SO2−4(aq) + 3H2(g)

Samarium is one of the few lanthanides with a relatively accessible +2 oxidation state, alongside Eu and Yb.[23] Sm2+ ions are blood-red in aqueous solution.[24]

Compounds

[edit]
Formula Color Symmetry Space group No. Pearson symbol a (pm) b (pm) c (pm) Z Density,
g/cm3
Sm silvery trigonal[15] R3m 166 hR9 362.9 362.9 2621.3 9 7.52
Sm silvery hexagonal[15] P63/mmc 194 hP4 362 362 1168 4 7.54
Sm silvery tetragonal[25] I4/mmm 139 tI2 240.2 240.2 423.1 2 20.46
SmO golden cubic[26] Fm3m 225 cF8 494.3 494.3 494.3 4 9.15
Sm2O3 trigonal[27] P3m1 164 hP5 377.8 377.8 594 1 7.89
Sm2O3 monoclinic[27] C2/m 12 mS30 1418 362.4 885.5 6 7.76
Sm2O3 cubic[28] Ia3 206 cI80 1093 1093 1093 16 7.1
SmH2 cubic[29] Fm3m 225 cF12 537.73 537.73 537.73 4 6.51
SmH3 hexagonal[30] P3c1 165 hP24 377.1 377.1 667.2 6
Sm2B5 gray monoclinic[31] P21/c 14 mP28 717.9 718 720.5 4 6.49
SmB2 hexagonal[32] P6/mmm 191 hP3 331 331 401.9 1 7.49
SmB4 tetragonal[33] P4/mbm 127 tP20 717.9 717.9 406.7 4 6.14
SmB6 cubic[34] Pm3m 221 cP7 413.4 413.4 413.4 1 5.06
SmB66 cubic[35] Fm3c 226 cF1936 2348.7 2348.7 2348.7 24 2.66
Sm2C3 cubic[36] I43d 220 cI40 839.89 839.89 839.89 8 7.55
SmC2 tetragonal[36] I4/mmm 139 tI6 377 377 633.1 2 6.44
SmF2 purple[37] cubic[38] Fm3m 225 cF12 587.1 587.1 587.1 4 6.18
SmF3 white[37] orthorhombic[38] Pnma 62 oP16 667.22 705.85 440.43 4 6.64
SmCl2 brown[37] orthorhombic[39] Pnma 62 oP12 756.28 450.77 901.09 4 4.79
SmCl3 yellow[37] hexagonal[38] P63/m 176 hP8 737.33 737.33 416.84 2 4.35
SmBr2 brown[37] orthorhombic[40] Pnma 62 oP12 797.7 475.4 950.6 4 5.72
SmBr3 yellow[37] orthorhombic[41] Cmcm 63 oS16 404 1265 908 2 5.58
SmI2 green[37] monoclinic P21/c 14 mP12
SmI3 orange[37] trigonal[42] R3 63 hR24 749 749 2080 6 5.24
SmN cubic[43] Fm3m 225 cF8 357 357 357 4 8.48
SmP cubic[44] Fm3m 225 cF8 576 576 576 4 6.3
SmAs cubic[45] Fm3m 225 cF8 591.5 591.5 591.5 4 7.23

Oxides

[edit]

The most stable oxide of samarium is the sesquioxide Sm2O3. Like many samarium compounds, it exists in several crystalline phases. The trigonal form is obtained by slow cooling from the melt. The melting point of Sm2O3 is high (2345 °C), so it is usually melted not by direct heating, but with induction heating, through a radio-frequency coil. Sm2O3 crystals of monoclinic symmetry can be grown by the flame fusion method (Verneuil process) from Sm2O3 powder, that yields cylindrical boules up to several centimeters long and about one centimeter in diameter. The boules are transparent when pure and defect-free and are orange otherwise. Heating the metastable trigonal Sm2O3 to 1,900 °C (3,450 °F) converts it to the more stable monoclinic phase.[27] Cubic Sm2O3 has also been described.[28]

Samarium is one of the few lanthanides that form a monoxide, SmO. This lustrous golden-yellow compound was obtained by reducing Sm2O3 with samarium metal at high temperature (1000 °C) and a pressure above 50 kbar; lowering the pressure resulted in incomplete reaction. SmO has cubic rock-salt lattice structure.[26][46]

Chalcogenides

[edit]

Samarium forms a trivalent sulfide, selenide and telluride. Divalent chalcogenides SmS, SmSe and SmTe with a cubic rock-salt crystal structure are known. These chalcogenides convert from a semiconducting to metallic state at room temperature upon application of pressure.[47] Whereas the transition is continuous and occurs at about 20–30 kbar in SmSe and SmTe, it is abrupt in SmS and requires only 6.5 kbar. This effect results in a spectacular color change in SmS from black to golden yellow when its crystals of films are scratched or polished. The transition does not change the lattice symmetry, but there is a sharp decrease (~15%) in the crystal volume.[48] It exhibits hysteresis, i.e., when the pressure is released, SmS returns to the semiconducting state at a much lower pressure of about 0.4 kbar.[11][49]

Halides

[edit]
Samarium trichloride

Samarium metal reacts with all the halogens, forming trihalides:[50]

2 Sm (s) + 3 X2 (g) → 2 SmX3 (s) (X = F, Cl, Br or I)

Their further reduction with samarium, lithium or sodium metals at elevated temperatures (about 700–900 °C) yields the dihalides.[39] The diiodide can also be prepared by heating SmI3, or by reacting the metal with 1,2-diiodoethane in anhydrous tetrahydrofuran at room temperature:[51]

Sm (s) + ICH2-CH2I → SmI2 + CH2=CH2.

In addition to dihalides, the reduction also produces many non-stoichiometric samarium halides with a well-defined crystal structure, such as Sm3F7, Sm14F33, Sm27F64,[38] Sm11Br24, Sm5Br11 and Sm6Br13.[52]

Samarium halides change their crystal structures when one type of halide anion is substituted for another, which is an uncommon behavior for most elements (e.g. actinides). Many halides have two major crystal phases for one composition, one being significantly more stable and another being metastable. The latter is formed upon compression or heating, followed by quenching to ambient conditions. For example, compressing the usual monoclinic samarium diiodide and releasing the pressure results in a PbCl2-type orthorhombic structure (density 5.90 g/cm3),[53] and similar treatment results in a new phase of samarium triiodide (density 5.97 g/cm3).[54]

Borides

[edit]

Sintering powders of samarium oxide and boron, in a vacuum, yields a powder containing several samarium boride phases; the ratio between these phases can be controlled through the mixing proportion.[55] The powder can be converted into larger crystals of samarium borides using arc melting or zone melting techniques, relying on the different melting/crystallization temperature of SmB6 (2580 °C), SmB4 (about 2300 °C) and SmB66 (2150 °C). All these materials are hard, brittle, dark-gray solids with the hardness increasing with the boron content.[34] Samarium diboride is too volatile to be produced with these methods and requires high pressure (about 65 kbar) and low temperatures between 1140 and 1240 °C to stabilize its growth. Increasing the temperature results in the preferential formation of SmB6.[32]

Samarium hexaboride

[edit]

Samarium hexaboride is a typical intermediate-valence compound where samarium is present both as Sm2+ and Sm3+ ions in a 3:7 ratio.[55] It belongs to a class of Kondo insulators; at temperatures above 50 K, its properties are typical of a Kondo metal, with metallic electrical conductivity characterized by strong electron scattering, whereas at lower temperatures, it behaves as a non-magnetic insulator with a narrow band gap of about 4–14 meV.[56] The cooling-induced metal-insulator transition in SmB6 is accompanied by a sharp increase in the thermal conductivity, peaking at about 15 K. The reason for this increase is that electrons themselves do not contribute to the thermal conductivity at low temperatures, which is dominated by phonons, but the decrease in electron concentration reduces the rate of electron-phonon scattering.[57]

Other inorganic compounds

[edit]
A tube of samarium sulfate
Samarium sulfate, Sm2(SO4)3

Samarium carbides are prepared by melting a graphite-metal mixture in an inert atmosphere. After the synthesis, they are unstable in air and need to be studied under an inert atmosphere.[36] Samarium monophosphide SmP is a semiconductor with a bandgap of 1.10 eV, the same as in silicon, and electrical conductivity of n-type. It can be prepared by annealing at 1,100 °C (2,010 °F) an evacuated quartz ampoule containing mixed powders of phosphorus and samarium. Phosphorus is highly volatile at high temperatures and may explode, thus the heating rate has to be kept well below 1 °C/min.[44] A similar procedure is adopted for the monarsenide SmAs, but the synthesis temperature is higher at 1,800 °C (3,270 °F).[45]

Numerous crystalline binary compounds are known for samarium and one of the group 14, 15, or 16 elements X, where X is Si, Ge, Sn, Pb, Sb or Te, and metallic alloys of samarium form another large group. They are all prepared by annealing mixed powders of the corresponding elements. Many of the resulting compounds are non-stoichiometric and have nominal compositions SmaXb, where the b/a ratio varies between 0.5 and 3.[58][59]

Organometallic compounds

[edit]

Samarium forms a cyclopentadienide Sm(C5H5)3 and its chloroderivatives Sm(C5H5)2Cl and Sm(C5H5)Cl2. They are prepared by reacting samarium trichloride with NaC5H5 in tetrahydrofuran. Contrary to cyclopentadienides of most other lanthanides, in Sm(C5H5)3 some C5H5 rings bridge each other by forming ring vertexes η1 or edges η2 toward another neighboring samarium, thus creating polymeric chains.[24] The chloroderivative Sm(C5H5)2Cl has a dimer structure, which is more accurately expressed as (η(5)−C5H5)2Sm(−Cl)2(η(5)−C5H5)2. There, the chlorine bridges can be replaced, for instance, by iodine, hydrogen or nitrogen atoms or by CN groups.[60]

The (C5H5) ion in samarium cyclopentadienides can be replaced by the indenide (C9H7) or cyclooctatetraenide (C8H8)2− ring, resulting in Sm(C9H7)3 or KSm(η(8)−C8H8)2. The latter compound has a structure similar to uranocene. There is also a cyclopentadienide of divalent samarium, Sm(C5H5)2 a solid that sublimates at about 85 °C (185 °F). Contrary to ferrocene, the C5H5 rings in Sm(C5H5)2 are not parallel but are tilted by 40°.[60][61]

A metathesis reaction in tetrahydrofuran or ether gives alkyls and aryls of samarium:[60]

SmCl3 + 3LiR → SmR3 + 3LiCl
Sm(OR)3 + 3LiCH(SiMe3)2 → Sm{CH(SiMe3)2}3 + 3LiOR

Here R is a hydrocarbon group and Me = methyl.

Isotopes

[edit]

Naturally occurring samarium is composed of five stable isotopes: 144Sm, 149Sm, 150Sm, 152Sm and 154Sm, and two extremely long-lived radioisotopes, 147Sm (half-life t1/2 = 1.066×1011 years) and 148Sm (6.3×1015 years), with 152Sm being the most abundant (26.75%).[9] 149Sm is listed by various sources as being stable,[9][62] but some sources state that it is radioactive;[63] the lower bound on its half-life is 2×1015 years.[9] Some observationally stable samarium isotopes are predicted to decay to isotopes of neodymium.[64] The long-lived isotopes 146Sm, 147Sm, and 148Sm (and 149Sm if it decays) undergo alpha decay to neodymium isotopes. Lighter unstable isotopes of samarium mainly decay by electron capture to promethium, while heavier ones beta decay to europium.[9] The known isotopes range from 129Sm to 168Sm.[65] The half-lives of 151Sm and 145Sm are 94.6 years and 340 days, respectively. All remaining radioisotopes have half-lives that are less than 2 days, and most these have half-life less than 48 seconds.[9] Natural samarium has a radioactivity of 127 Bq/g, mostly due to 147Sm,[66] whose alpha decay to 143Nd is used in samarium–neodymium dating.[67][68] 146Sm is an extinct radionuclide, with the half-life of 9.20×107 years.[10] There have been searches of samarium-146 as a primordial nuclide, because its half-life is long enough such that minute quantities of the element should persist today.[69] It can be used in radiometric dating.[70]

Samarium-149 is an observationally stable isotope of samarium and a product of the decay chain from the fission product 149Nd (yield 1.0888%). 149Sm is a significant neutron absorber in nuclear reactors, with a neutron poison effect that is second in importance for reactor design and operation only to 135Xe.[71][72] Its neutron cross section is 41000 barns for thermal neutrons.[73] Because samarium-149 is not radioactive and is not removed by decay, it presents problems somewhat different from those encountered with xenon-135. The equilibrium concentration (and thus the poisoning effect) builds to an equilibrium value during reactor operations in about 500 hours (about three weeks) as the isotope does not measurably vanish except through neutron capture.[74]

Chemical structure of samarium (153Sm) lexidronam
Chemical structure of Sm-EDTMP

Samarium-153 is a beta emitter with a half-life of 46.285 hours. It is used to kill cancer cells in lung cancer, prostate cancer, breast cancer, and osteosarcoma. For this purpose, samarium-153 is chelated with ethylene diamine tetramethylene phosphonate (EDTMP) and injected intravenously. The chelation prevents accumulation of radioactive samarium in the body that would result in excessive irradiation and generation of new cancer cells.[11] The corresponding drug has several names including samarium (153Sm) lexidronam; its trade name is Quadramet.[75][76][77]

History

[edit]
Lecoq de Boisbaudran
Paul Émile Lecoq de Boisbaudran, the discoverer of samarium

Detection of samarium and related elements was announced by several scientists in the second half of the 19th century; however, most sources give priority to French chemist Paul-Émile Lecoq de Boisbaudran.[78][79] Boisbaudran isolated samarium oxide and/or hydroxide in Paris in 1879 from the mineral samarskite ((Y,Ce,U,Fe)3(Nb,Ta,Ti)5O16) and identified a new element in it via sharp optical absorption lines.[13] Swiss chemist Marc Delafontaine announced a new element decipium (from Latin: decipiens meaning "deceptive, misleading") in 1878,[80][81] but later in 1880–1881 demonstrated that it was a mix of several elements, one being identical to Boisbaudran's samarium.[82][83] Though samarskite was first found in the Ural Mountains in Russia, by the late 1870s it had been found in other places, making it available to many researchers. In particular, it was found that the samarium isolated by Boisbaudran was also impure and had a comparable amount of europium. The pure samarium(III) oxide was produced only in 1901 by Eugène-Anatole Demarçay,[84][85][86] and in 1903 Wilhelm Muthmann isolated the element.

Boisbaudran named his element samarium after the mineral samarskite, which in turn honored Vassili Samarsky-Bykhovets (1803–1870). Samarsky-Bykhovets, as the Chief of Staff of the Russian Corps of Mining Engineers, had granted access for two German mineralogists, the brothers Gustav and Heinrich Rose, to study the mineral samples from the Urals.[87][88][89] Samarium was thus the first chemical element to be named after a person.[84][90] The word samaria is sometimes used to mean samarium(III) oxide, by analogy with yttria, zirconia, alumina, ceria, holmia, etc. The symbol Sm was suggested for samarium, but an alternative Sa was often used instead until the 1920s.[84][91]

Before the advent of ion-exchange separation technology in the 1950s, pure samarium had no commercial uses. However, a by-product of fractional crystallization purification of neodymium was a mix of samarium and gadolinium that got the name "Lindsay Mix" after the company that made it, and was used for nuclear control rods in some early nuclear reactors.[92] Nowadays, a similar commodity product has the name "samarium-europium-gadolinium" (SEG) concentrate.[90] It is prepared by solvent extraction from the mixed lanthanides isolated from bastnäsite (or monazite). Since heavier lanthanides have more affinity for the solvent used, they are easily extracted from the bulk using relatively small proportions of solvent. Not all rare-earth producers who process bastnäsite do so on a large enough scale to continue by separating the components of SEG, which typically makes up only 1–2% of the original ore. Such producers therefore make SEG with a view to marketing it to the specialized processors. In this manner, the valuable europium in the ore is rescued for use in making phosphor. Samarium purification follows the removal of the europium. As of 2012, being in oversupply, samarium oxide is cheaper on a commercial scale than its relative abundance in the ore might suggest.[93]

Occurrence and production

[edit]
Samarskite
Samarskite

Samarium concentration in soils varies between 2 and 23 ppm, and oceans contain about 0.5–0.8 parts per trillion.[11] The median value for its abundance in the Earth's crust used by the CRC Handbook is 7 parts per million (ppm)[94] and is the 40th most abundant element.[95] Distribution of samarium in soils strongly depends on its chemical state and is very inhomogeneous: in sandy soils, samarium concentration is about 200 times higher at the surface of soil particles than in the water trapped between them, and this ratio can exceed 1,000 in clays.[96]

Samarium is not found free in nature, but, like other rare earth elements, is contained in many minerals, including monazite, bastnäsite, cerite, gadolinite and samarskite; monazite (in which samarium occurs at concentrations of up to 2.8%)[13] and bastnäsite are mostly used as commercial sources. World resources of samarium are estimated at two million tonnes; they are mostly located in China, US, Brazil, India, Sri Lanka and Australia, and the annual production is about 700 tonnes.[11] Country production reports are usually given for all rare-earth metals combined. By far, China has the largest production with 120,000 tonnes mined per year; it is followed by the US (about 5,000 tonnes)[96] and India (2,700 tonnes).[97] Samarium is usually sold as oxide, which at the price of about US$30/kg is one of the cheapest lanthanide oxides.[93] Whereas mischmetal – a mixture of rare earth metals containing about 1% of samarium – has long been used, relatively pure samarium has been isolated only recently, through ion exchange processes, solvent extraction techniques, and electrochemical deposition. The metal is often prepared by electrolysis of a molten mixture of samarium(III) chloride with sodium chloride or calcium chloride. Samarium can also be obtained by reducing its oxide with lanthanum. The product is then distilled to separate samarium (boiling point 1,794 °C) and lanthanum (b.p. 3,464 °C).[79]

Very few minerals have samarium being the most dominant element. Minerals with essential (dominant) samarium include monazite-(Sm) and florencite-(Sm). These minerals are very rare and are usually found containing other elements, usually cerium or neodymium.[98][99][100][101] It is also made by neutron capture by samarium-149, which is added to the control rods of nuclear reactors. Therefore, 151Sm is present in spent nuclear fuel and radioactive waste.[96]

Separating samarium from minerals involves nearly 100 individual processes and extremely strong acids.[102]

Geopolitics

[edit]

Western militaries across the world relied on a single samarium production plant in La Rochelle, France from the 1970s until the plant's closure in 1994.[102] The facility sourced its samarium from Australia.[102] A $1 billion United States government effort to re-open a closed rare earths mine in Mountain Pass, California resulted in the facility going bankrupt.[102]

As of 2025, China produces all of the world's usable samarium; refining is concentrated in Baotou.[102] The Biden administration signed two contracts for samarium production plants in the United States, but neither materialized.[102] During US president Donald Trump's second-term tariff war, China leveled strict limits on the export of samarium, among other rare earth metals, as part of the long-running rare earths trade dispute (and larger trade war) between the two nations.[102]

Applications

[edit]

Magnets

[edit]

An important use of samarium is samarium–cobalt magnets, which are nominally SmCo5 or Sm2Co17.[103] They have high permanent magnetization, about 10,000 times that of iron and second only to neodymium magnets. However, samarium magnets resist demagnetization better; they are stable to temperatures above 700 °C (1,292 °F) (cf. 300–400 °C for neodymium magnets). These magnets are found in small motors, headphones, and high-end magnetic pickups for guitars and related musical instruments.[11] For example, they are used in the motors of a solar-powered electric aircraft, the Solar Challenger, and in the Samarium Cobalt Noiseless electric guitar and bass pickups.

Due to their heat resistance, samarium magnets are also used for military applications and are needed to manufacture modern aircraft and missiles.[102] A single F-35 fighter jet contains about 50 pounds (23 kg) of samarium magnets.[102]

Chemical reagent

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Barbier reaction using samarium diiodide
Barbier reaction using SmI2

Samarium and its compounds are important as catalysts and chemical reagents. Samarium catalysts help the decomposition of plastics, dechlorination of pollutants such as polychlorinated biphenyls (PCB), as well as dehydration and dehydrogenation of ethanol.[13] Samarium(III) triflate Sm(OTf)3, that is Sm(CF3SO3)3, is one of the most efficient Lewis acid catalysts for a halogen-promoted Friedel–Crafts reaction with alkenes.[104] Samarium(II) iodide is a very common reducing and coupling agent in organic synthesis, for example in desulfonylation reactions; annulation; Danishefsky, Kuwajima, Mukaiyama and Holton Taxol total syntheses; strychnine total synthesis; Barbier reaction and other reductions with samarium(II) iodide.[105]

In its usual oxidized form, samarium is added to ceramics and glasses where it increases absorption of infrared light. As a (minor) part of mischmetal, samarium is found in the "flint" ignition devices of many lighters and torches.[11][13]

Neutron absorber

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Samarium-149 has a high cross section for neutron capture (41,000 barns) and so is used in control rods of nuclear reactors. Its advantage compared to competing materials, such as boron and cadmium, is stability of absorption – most of the fusion products of 149Sm are other isotopes of samarium that are also good neutron absorbers. For example, the cross section of samarium-151 is 15,000 barns, it is on the order of hundreds of barns for 150Sm, 152Sm, and 153Sm, and 6,800 barns for natural (mixed-isotope) samarium.[13][96][106]

Lasers

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Samarium-doped calcium fluoride crystals were used as an active medium in one of the first solid-state lasers designed and built by Peter Sorokin (co-inventor of the dye laser) and Mirek Stevenson at IBM research labs in early 1961. This samarium laser gave pulses of red light at 708.5 nm. It had to be cooled by liquid helium and so did not find practical applications.[107][108] Another samarium-based laser became the first saturated X-ray laser operating at wavelengths shorter than 10 nanometers. It gave 50-picosecond pulses at 7.3 and 6.8 nm suitable for uses in holography, high-resolution microscopy of biological specimens, deflectometry, interferometry, and radiography of dense plasmas related to confinement fusion and astrophysics. Saturated operation meant that the maximum possible power was extracted from the lasing medium, resulting in the high peak energy of 0.3 mJ. The active medium was samarium plasma produced by irradiating samarium-coated glass with a pulsed infrared Nd-glass laser (wavelength ~1.05 μm).[109]

Storage phosphor

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In 2007 it was shown that nanocrystalline BaFCl:Sm3+ as prepared by co-precipitation can serve as a very efficient X-ray storage phosphor.[110] The co-precipitation leads to nanocrystallites of the order of 100–200 nm in size and their sensitivity as X-ray storage phosphors is increased a remarkable ~500,000 times because of the specific arrangements and density of defect centers in comparison with microcrystalline samples prepared by sintering at high temperature.[111] The mechanism is based on reduction of Sm3+ to Sm2+ by trapping electrons that are created upon exposure to ionizing radiation in the BaFCl host. The 5DJ7FJ f–f luminescence lines can be very efficiently excited via the parity allowed 4f6→4f55d transition at ~417 nm. The latter wavelength is ideal for efficient excitation by blue-violet laser diodes as the transition is electric dipole allowed and thus relatively intense (400 L/(mol⋅cm)).[112] The phosphor has potential applications in personal dosimetry, dosimetry and imaging in radiotherapy, and medical imaging.[113]

Non-commercial and potential uses

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  • The change in electrical resistivity in samarium monochalcogenides can be used in a pressure sensor or in a memory device triggered between a low-resistance and high-resistance state by external pressure,[114] and such devices are being developed commercially.[115] Samarium monosulfide also generates electric voltage upon moderate heating to about 150 °C (302 °F) that can be applied in thermoelectric power converters.[116]
  • Analysis of relative concentrations of samarium and neodymium isotopes 147Sm, 144Nd, and 143Nd allows determination of the age and origin of rocks and meteorites in samarium–neodymium dating. Both elements are lanthanides and are very similar physically and chemically. Thus, Sm–Nd dating is either insensitive to partitioning of the marker elements during various geologic processes, or such partitioning can well be understood and modeled from the ionic radii of said elements.[117]
  • The Sm3+ ion is a potential activator for use in warm-white light emitting diodes. It offers high luminous efficacy due to narrow emission bands; but the generally low quantum efficiency and too little absorption in the UV-A to blue spectral region hinders commercial application.[118]
  • Samarium is used for ionosphere testing. A rocket spreads samarium monoxide as a red vapor at high altitude, and researchers test how the atmosphere disperses it and how it impacts radio transmissions.[119][120]
  • Samarium hexaboride, SmB6, has recently been shown to be a topological insulator with potential uses in quantum computing.[121][122][123][124]

Biological role and precautions

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Samarium
Hazards[125]
GHS labelling:
GHS02: Flammable
Warning
H261
P231+P232, P280, P370+P378, P501
NFPA 704 (fire diamond)

Samarium salts stimulate metabolism, but it is unclear whether this is from samarium or other lanthanides present with it. The total amount of samarium in adults is about 50 μg, mostly in liver and kidneys and with ~8 μg/L being dissolved in blood. Samarium is not absorbed by plants to a measurable concentration and so is normally not part of human diet. However, a few plants and vegetables may contain up to 1 part per million of samarium. Insoluble salts of samarium are non-toxic and the soluble ones are only slightly toxic.[11][127] When ingested, only 0.05% of samarium salts are absorbed into the bloodstream and the remainder are excreted. From the blood, 45% goes to the liver and 45% is deposited on the surface of the bones where it remains for 10 years; the remaining 10% is excreted.[96]

References

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Bibliography

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Revisions and contributorsEdit on WikipediaRead on Wikipedia
from Grokipedia
Samarium is a with the symbol Sm and 62, belonging to the series of rare-earth metals in the periodic table. It appears as a moderately hard, silvery lustrous metal that slowly tarnishes in air and has a density of 7.52 g/cm³ at . First isolated in by French chemist from the samarskite via spectroscopic detection of its unique absorption lines, samarium was named after the ore from which it was extracted, honoring Russian mine official Vasili Samarsky-Bykhovets. Although relatively abundant in at about 6 parts per million—more so than tin or —samarium occurs primarily in minerals like and and is obtained commercially through ion-exchange or solvent extraction from rare-earth ores. Key applications include samarium-cobalt alloys for high-performance permanent magnets resistant to demagnetization and elevated temperatures, exceeding neodymium-iron-boron magnets in thermal stability; as a absorber in control rods due to isotopes like ^{149}Sm with high thermal cross-sections; and radioactive ^{153}Sm chelates for palliative radiotherapy in painful bone metastases from cancer. Samarium diiodide serves as a versatile in , notably facilitating the for carbon-carbon bond formation.

Properties

Physical properties

Samarium is a silvery-white, moderately hard rare-earth metal that tarnishes slowly in air and ignites when heated. Its density is 7.52 g/cm³ at 25 °C. The element melts at 1072 °C and boils at 1794 °C. In its , samarium adopts a , characteristic of certain lanthanides. The is approximately 180 pm. Samarium exhibits electrical resistivity of 9.4 × 10⁻⁷ Ω·m and thermal conductivity of 13.3 W/(m·). Elemental samarium displays complex magnetic behavior, including antiferromagnetic ordering at low temperatures and paramagnetic properties at higher temperatures.
PropertyValueUnit
7.52g/cm³
Melting point1072°C
Boiling point1794°C
Thermal conductivity13.3W/(m·K)
Electrical resistivity9.4 × 10⁻⁷Ω·m

Chemical properties

Samarium, as a element, predominantly exhibits the +3 in its compounds, consistent with the loss of its 6s² s and one 4f , though it also forms stable +2 species analogous to due to the stability of its half-filled 4f⁵ configuration in Sm²⁺. The Pauling of samarium is 1.17, reflecting its electropositive nature and tendency to form ionic bonds with nonmetals. In air, bulk samarium metal tarnishes slowly at , oxidizing to samarium(III) (Sm₂O₃), a pale yellow to white powder; however, finely divided or powdered samarium reacts more rapidly and ignites spontaneously upon heating to 150 °C, producing intense flames and Sm₂O₃. Samarium reacts with to liberate gas and form samarium(III) (Sm(OH)₃), proceeding slowly with cold but vigorously with hot according to the equation: 2 Sm(s) + 6 H₂O(l) → 2 Sm(OH)₃(aq) + 3 H₂(g). Samarium dissolves readily in dilute acids, evolving and yielding samarium(III) salts; for instance, it reacts with dilute to produce samarium(III) sulfate (Sm₂(SO₄)₃). It also combines directly with at elevated temperatures to form trihalides such as samarium(III) chloride (SmCl₃) or bromide (SmBr₃), and with oxygen or to yield the corresponding oxides or sulfides. These reactions underscore samarium's reducing character, though less aggressive than that of lighter lanthanides like .

Compounds

Oxides


Samarium(III) oxide (Sm₂O₃) is the most stable and common of samarium, typically appearing as a light yellow or yellowish-white powder. It possesses a of 8.347 g/cm³, a of 2335 °C, and a boiling point of approximately 3780 °C. The compound is insoluble in water but dissolves readily in mineral acids, yielding a slurry pH of about 8.0.
Sm₂O₃ is prepared industrially via of samarium(III) precursors such as carbonates, hydroxides, nitrates, oxalates, or sulfates at high temperatures. Nanocrystalline forms can be synthesized through methods like hydrolysis or hydrothermal processes using samarium salts. The exhibits polymorphism, with the cubic C-type () structure ( Ia-3) being prominent, alongside hexagonal A-type and monoclinic B-type forms depending on synthesis conditions and temperature. Its wide of about 4.3 eV supports applications in and dielectrics. Samarium(II) oxide (SmO), a less stable monoxide, forms as a shiny, golden-yellow compound with a cubic rock-salt structure. It is synthesized by reducing Sm₂O₃ with metallic samarium under controlled conditions, distinguishing samarium among lanthanides for stable divalent oxide formation. SmO displays metallic conduction and has been studied in thin films for potential heavy-fermion properties.

Chalcogenides

Samarium chalcogenides encompass binary compounds with , , and , primarily in +2 (SmX) and +3 (Sm₂X₃) oxidation states, where X denotes the . The divalent SmX series (X = S, Se, Te) typically crystallizes in the cubic rock salt (NaCl-type) structure with space group Fm3m, exhibiting semiconducting properties that can transition to metallic under or other stimuli. These materials are synthesized via methods such as direct combination of elements at high temperatures or reactive evaporation, and they display varying electronic behaviors influenced by samarium's intermediate valence tendencies. Samarium(II) sulfide (SmS) is notable for its pressure-induced phase transition from a black semiconducting phase (high resistivity, ~10¹⁰ Ω·cm at room temperature) with a band gap of approximately 0.2 eV to a golden metallic phase at ~0.65–1.0 GPa, accompanied by a volume collapse of ~10%. In the semiconducting state, SmS adopts the NaCl structure with lattice parameter a ≈ 0.586–0.597 nm; the metallic phase shows a contracted lattice (a ≈ 0.580 nm) and enhanced conductivity up to 10³ Ω⁻¹·cm⁻¹. This switchable behavior arises from valence instability in Sm²⁺, enabling applications in piezochromic devices and sensors, though SmS oxidizes readily in air to form Sm₂O₂S or Sm₂O₃. Samarium(III) sulfide (Sm₂S₃) exists in multiple polymorphs, with the α-phase being orthorhombic ( Pnma) and semiconducting with a band gap of ~1.7 eV. It decomposes above 200°C and is prepared by reacting samarium with or at elevated temperatures, yielding red-brown powders stable under inert conditions. For selenides, SmSe (rock salt structure) and Sm₂Se₃ exhibit similar divalent and trivalent behaviors, with Sm₂Se₃ forming nanorods via chemical synthesis that demonstrate pseudocapacitive properties in electrochemical applications, achieving specific capacitances up to 400 F·g⁻¹. Samarium telluride (SmTe) also adopts the rock salt structure (a ≈ 0.6595 nm) and displays intermediate valence fluctuations, evidenced by showing mixed Sm²⁺/Sm³⁺ character, leading to metallic conductivity and potential thermoelectric uses. Higher tellurides like Sm₃Te₄ (Th₃P₄-type) and Sm₂Te₃ (Sb₂S₃-type) form in the Sm-Te system, with congruent melting points above 2000 K. These chalcogenides generally hydrolyze in moist air and require inert handling due to sensitivity to oxidation.

Halides

Samarium halides primarily exist in the +3 as SmX₃ (X = F, Cl, Br, I), forming ionic compounds with varying and structures depending on the . These compounds are synthesized by methods such as direct reaction of samarium metal with the halogen or by treating samarium with the corresponding hydrohalic . Samarium(III) (SmF₃) adopts an orthorhombic (space group Pnma, β-YF₃ type) at , transitioning to a rhombohedral LaF₃-type above 495 °C; it is a slightly hygroscopic used in optical coatings and as a precursor for other materials. Samarium(III) chloride (SmCl₃) is a white to yellow powder with a density of 4.465 g/cm³ and a of 686 °C; the form is hygroscopic and forms a hexahydrate (SmCl₃·6H₂O) that is highly soluble in . It acts as a moderately strong Lewis acid, classified as "hard" per the , and finds applications in and as a samarium source in synthesis. Samarium(III) bromide (SmBr₃) and (SmI₃) exhibit similar properties to the chloride but are less stable and more prone to reduction, with SmI₃ decomposing to SmI₂ under certain conditions. A notable exception is samarium(II) iodide (SmI₂), a green solution in THF known as Kagan's reagent, prepared by reducing SmI₃ or directly from samarium metal and iodine in . This one-electron reducing agent is widely used in for reactions including Barbier-type couplings, pinacol couplings, and carbonyl reductions, offering high tolerance and mild conditions compared to reductants. Its reactivity can be modulated with additives like HMPA or Ni(II) salts to enable specific transformations such as carbon-carbon bond formations.

Borides

Samarium forms several binary borides, including SmB₂, SmB₄, SmB₆, and higher-order phases such as SmB₆₆, within the Sm-B . These compounds are typically synthesized via high-temperature methods, such as arc melting, boro/carbothermal reduction of Sm₂O₃ with B₄C, or reactions of samarium halides with NaBH₄ in molten LiCl-KCl salts, allowing control over and morphology. The borides exhibit high melting points, , and , making them materials suitable for extreme environments. Samarium diboride (SmB₂) adopts a hexagonal crystal structure in the P6/mmm space group, featuring three-dimensional boron networks coordinated with samarium atoms. It is less studied compared to higher borides but shares general traits of rare-earth diborides, including metallic conductivity and potential for use in coatings or composites. Samarium tetraboride (SmB₄) and hexaboride (SmB₆) are more prominent, with SmB₆ crystallizing in a cubic structure analogous to other rare-earth hexaborides. SmB₆ displays intermediate valence between Sm²⁺ and Sm³⁺ (ratio approximately 3:7), leading to Kondo insulator behavior below ~40 K, where bulk resistivity increases while surface conduction persists due to predicted topological surface states. This has sparked debate on whether SmB₆ qualifies as a true topological insulator or exhibits trivial surface conductivity from impurities or defects, with experimental evidence showing robust metallic surface states down to millikelvin temperatures but inconsistent bulk gap confirmation. SmB₆ also demonstrates negative thermal expansion, attributed to transverse vibrational modes in its boron octahedra framework, and enhanced thermoelectric properties in doped variants. Mechanically, densified SmB₆ ceramics achieve Vickers hardness up to 28 GPa and fracture toughness around 3.5 MPa·m¹/² via spark plasma sintering at 1800°C. Higher borides like SmB₆₆ form complex icosahedral structures and are synthesized under conditions around 2150°C, contributing to the material's stability but limiting practical applications due to synthetic challenges. Overall, samarium borides' electronic, thermal, and mechanical properties position them for potential uses in thermoelectrics, , and high-temperature ceramics, though scalability and purity remain hurdles.

Other inorganic compounds

Samarium nitride (SmN) adopts a rock-salt and exhibits ferromagnetic semiconducting behavior, with a around 40 K in bulk form and potential for higher values in thin films due to strain effects. Thin films of SmN are synthesized via on MgO(001) substrates under conditions, achieving epitaxial growth with tunable electronic properties influenced by flux and substrate temperature, typically between 600–800 °C. The material displays p-type conduction and half-metallic in calculations, making it a for spintronic applications, though synthesis challenges include deficiency leading to metallic phases. Samarium dicarbide (SmC₂) possesses a calcium carbide-type tetragonal , appearing as a brittle solid with metallic luster, and is prepared by arc-melting samarium metal with or reacting samarium oxide with carbon at high temperatures above 2000 °C. Its is approximately -96.2 ± 8.4 kJ/mol at 298 K, determined from measurements of CO over the Sm-C-O system, indicating thermodynamic stability relative to elemental samarium and up to 1650 K. Vaporization studies via Knudsen reveal congruent evaporation primarily as Sm(g) and C(g) species above 2200 K, with non-stoichiometric phases like SmC_y (y ≈ 1.5) forming in carbon-rich regions. Samarium exists primarily as SmH₂ in cubic ( Fm-3m), formed by direct reaction of samarium metal with gas at temperatures between 300 and 500 °C, yielding a non-stoichiometric phase SmH_{2+x} (0 ≤ x ≤ 0.63) that is exothermic and reversible upon heating. A higher SmH₃ adopts a hexagonal structure and is accessible under elevated pressures, with phase transitions from cubic to hexagonal SmH₂ observed around 450–500 , accompanied by changes of about 2–3 kJ/mol H₂ derived from pressure-composition isotherms. These hydrides demonstrate significant absorption capacity, up to 2.1 wt% H, and are explored for due to their reversible dehydrogenation, though oxidation sensitivity limits practical use. Samarium phosphide (SmP) crystallizes in a rock-salt structure similar to SmN, but detailed synthesis and property data remain sparse, with reports limited to stoichiometric preparation via metal-phosphorus reactions at high temperatures. Other pnictides, such as arsenides, follow analogous structural motifs but lack extensive characterization beyond basic existence in rare-earth compound surveys.

Organometallic compounds

Organosamarium compounds feature direct carbon-samarium σ-bonds and exhibit high reactivity as strong one-electron reductants, particularly in the +2 . These species are often unstable and generated for applications in , where they facilitate carbon-carbon bond formation through radical or anionic mechanisms. A key reagent for preparing organosamarium intermediates is samarium(II) iodide (SmI₂), which undergoes single-electron transfer to organic halides, forming alkyl- or arylsamarium species that add to electrophiles like carbonyls in Barbier-type reactions. For instance, the reaction of SmI₂ with alkyl iodides or bromides in the presence of ketones yields tertiary alcohols via intermediate organosamarium addition. These processes mimic Grignard additions but proceed under milder conditions and tolerate functional groups sensitive to traditional organometallics. Stable organosamarium complexes, often stabilized by bulky cyclopentadienyl ligands, include compounds like [(MeC₅H₄)₂SmC≡CCMe₃], featuring samarium-alkyne bonds confirmed by . Such complexes demonstrate bent metallocene geometries and linear Sm-C≡C linkages, with Sm-C distances around 2.3–2.5 typical for lanthanide-carbon bonds. Additionally, the first structurally characterized σ-bonded organosamarium(II) compound, reported in 1997, reacts with ketones to form samarium(III) ketal complexes. Organosamarium(III) intermediates, such as (α-iminoalkyl)samarium species, enable selective C-C couplings, including additions to imines and enones. reactions with organochromium or other metals further expand their synthetic utility for low-temperature variants of classical couplings like Nozaki-Hiyama. These compounds' reactivity stems from samarium's large and low , promoting facile and bond formation.

Isotopes

Samarium (^{62}Sm) occurs naturally as a of seven isotopes with mass numbers 144, 147, 148, 149, 150, 152, and 154; five of these (^{144}Sm, ^{149}Sm, ^{150}Sm, ^{152}Sm, and ^{154}Sm) are stable, while ^{147}Sm and ^{148}Sm are radioactive but possess half-lives exceeding 10^{11} years, rendering their decay negligible on human timescales. The isotopic abundances reflect primordial processes, with ^{150}Sm dominating at 75.78%. The following table summarizes the natural isotopic composition of samarium, including relative atomic masses and abundances ( derived as 150.36(2)):
IsotopeRelative Atomic MassNatural Abundance (%)
^{144}Sm143.91199567(13)3.07(9)
^{147}Sm146.9148939(25)14.99(6)
^{148}Sm147.9148183(20)11.24(3)
^{149}Sm148.9171804(20)13.82(6)
^{150}Sm149.9172715(20)75.78(8)
^{152}Sm151.9197309(20)26.16(9)
^{154}Sm153.9222169(20)22.75(29)
The of ^{147}Sm to ^{143}Nd, with a of (1.06 ± 0.01) × 10^{11} years, enables the Sm-Nd system for of ancient terrestrial and meteoritic materials, providing insights into early Solar System differentiation. Similarly, ^{148}Sm decays via alpha emission with a of approximately 7 × 10^{15} years, though its rarity limits practical applications. Over 30 radioactive isotopes of samarium have been characterized, spanning mass numbers from 128 to 163, most with half-lives under 10 days and decaying primarily via beta minus emission, , or . Among artificially produced isotopes, ^{153}Sm is notable, with a of 46.28 hours and beta emission energies up to 0.81 MeV; it is generated via on ^{152}Sm and chelated as samarium-153 lexidronam (^{153}Sm-EDTMP) for targeted radiotherapy. This localizes in osteoblastic metastases, delivering localized radiation to alleviate pain from cancers such as or , with clinical trials demonstrating efficacy in reducing requirements and transient myelosuppression as the primary side effect.

History

In 1853, Swiss chemist Jean Charles Galissard de Marignac identified sharp absorption lines in a sample of didymia, a rare earth fraction from minerals, which were later recognized as belonging to samarium. These spectroscopic observations preceded the element's isolation, as didymia contained a mixture of lanthanides including samarium, , and . French chemist isolated samarium in 1879 by fractionally precipitating nitrate derived from the mineral samarskite. He dissolved samarskite in , separated the rare earths, and observed distinct absorption lines in the samarium fraction that differed from those of other lanthanides. This process confirmed the presence of a new element, which Lecoq named samarium after the source mineral. Samarskite, a complex niobate-tantalate containing , , , iron, and other rare earths, was identified in 1847 from samples collected in the Ilmen Mountains of . Initially named for its deceptive similarity to other minerals, it was renamed samarskite to honor Vasili Yevgrafovich Samarsky-Bykhovets (1803–1870), a Russian mining and official who supplied the specimens to German chemist Moritz Hermann von Gerhardt. Thus, samarium became the first indirectly named after a person through its mineral source. The pure metallic form of samarium was first obtained in 1937 through of samarium halides by French chemist Hippolyte Georges Fischer and German chemist Wilhelm Prandtl. Early research focused on its spectroscopic properties and separation from other rare earths, establishing samarium's position in the series amid challenges in distinguishing closely related elements.

Occurrence

Cosmic and terrestrial abundance

Samarium possesses a low cosmic abundance, consistent with other rare earth elements formed primarily through the in stars and r-process in mergers and supernovae. In the solar photosphere, its abundance is determined spectroscopically as log ε(Sm) = 1.01 ± 0.06 (normalized to at 12.00), corresponding to approximately 1.02 × 10^{-11} atoms of samarium per . This value derives from analysis of 26 neutral samarium lines, reflecting equilibrium conditions in the solar atmosphere. In carbonaceous chondritic meteorites, which serve as proxies for solar system bulk composition, samarium abundance reaches about 170 ppb by atoms or 20 ppb by mass, higher than in the Sun due to volatility fractionation but still trace-level relative to major elements like (normalized often to 10^6 Si atoms, where Sm is ~0.17). Terrestrially, samarium is enriched in the through lithophilic behavior and differentiation processes, concentrating in rocks and accessory minerals. The average crustal abundance is 7.05 ppm by mass (or 0.000705% by weight), ranking it as the 40th most abundant element and slightly more prevalent than tin (2.2 ppm). This figure stems from compilations of igneous, sedimentary, and analyses, with higher concentrations in granites (up to 10-15 ppm) versus basalts (~4 ppm). In , samarium levels are negligible at approximately 4.5 × 10^{-11}% by mass, limited by scavenging onto particulates and low of REE phosphates and carbonates. Oceanic inputs derive mainly from riverine fluxes and hydrothermal vents, but residence times are short (~300-1000 years) due to rapid removal.

Mineral sources

Samarium occurs primarily in rare earth-bearing minerals such as bastnäsite and monazite, which serve as the principal commercial sources for its extraction. Bastnäsite, with the formula (Ce,La)CO₃F, is a fluorocarbonate mineral rich in light rare earth elements, including cerium, lanthanum, and samarium as minor components. Monazite, typically (Ce,La,Nd,Th)PO₄, is a phosphate mineral that contains thorium and a mix of light rare earths, with samarium comprising a small but recoverable fraction. These minerals are processed to separate individual rare earth elements, as samarium is not found in native or highly concentrated deposits. Samarium is also present in other minerals like samarskite, a complex niobate-tantalate of uranium, iron, and rare earths from which the element was first isolated, though it is not a major commercial source due to lower yields and processing challenges. Xenotime, a yttrium phosphate (YPO₄), can contain trace amounts of samarium among heavier rare earth impurities. Concentrations of samarium in these ores vary, typically ranging from 0.5% to 2% of the rare earth oxide content, necessitating advanced separation techniques for recovery.

Production

Extraction and separation methods

Samarium is extracted from (REE)-bearing minerals, primarily , , and samarskite, through hydrometallurgical processes following initial mining and beneficiation. Ores are crushed, ground, and subjected to physical separation techniques such as , gravity concentration, or to yield a REE concentrate containing 30-70% total rare earth oxides (TREO). The concentrate is then leached with concentrated at elevated temperatures (typically 200-250°C) or to dissolve the REEs into solution as sulfates or chlorides, while materials like silica and are separated as insoluble residues. For , alkaline digestion with is sometimes used to produce rare earth phosphates, which are subsequently converted to oxides or chlorides via acid treatment. and impurities are removed early via solvent extraction or to comply with environmental regulations. Individual separation of samarium from the mixed REE relies on liquid-liquid solvent extraction, the dominant industrial method due to its scalability and selectivity. This involves partitioning REE ions between an aqueous nitrate or chloride feed and an organic phase containing acidic organophosphorus extractants, such as di(2-ethylhexyl) (D2EHPA) or PC88A (2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester), diluted in . Differences in extraction efficiency—governed by and stability constants—allow sequential separation; samarium, with a smaller than lighter lanthanides like , extracts preferentially in later stages. Counter-current multistage operations in mixer-settler cascades achieve purities exceeding 99.9% for samarium oxide (Sm₂O₃) after stripping, precipitation with , calcination, and reduction. Alternative methods, such as chromatography or selective precipitation, are less common industrially due to lower throughput but may be used for high-purity or small-scale production; for instance, europium-samarium separation can involve reduction of Eu³⁺ to Eu²⁺ with in media followed by selective extraction. Electrochemical extraction from molten salts has been explored experimentally for fission-derived samarium but remains non-commercial. Global samarium production, estimated at around 700 tonnes annually as of recent reports, is almost entirely controlled by , leveraging its dominance in REE mining and processing capacity.

Industrial processes

Samarium metal is primarily produced on an industrial scale by metallothermic reduction of high-purity samarium (Sm₂O₃), which is first obtained through solvent extraction and from rare earth concentrates. In this process, Sm₂O₃ is reduced using metal in a vacuum-sealed furnace at temperatures around 1000–1200°C, following the reaction Sm₂O₃ + 2 La → 2 Sm + La₂O₃. The resulting samarium vapor is then condensed and distilled under vacuum to achieve purity levels exceeding 99%, mitigating contamination from byproducts and exploiting samarium's relatively high (approximately 10⁻³ Pa at 1000°C). This method predominates due to its scalability and effectiveness in handling samarium's volatility, which complicates aqueous or standard approaches. An alternative electrolytic method involves the of molten samarium(III) chloride (SmCl₃) mixed with (NaCl) or (CaCl₂) as flux in a or crucible at 800–900°C. Samarium ions are reduced at the to deposit metallic samarium, while gas evolves at the ; the process requires inert atmospheres to prevent oxidation. This technique yields dendritic samarium deposits that are subsequently melted and cast under , but it is less common industrially for samarium owing to energy demands and the metal's tendency to reoxidize or volatilize during . Both processes demand stringent control over impurities, as even trace levels of oxygen or other rare earths degrade samarium's performance in applications like permanent magnets. Post-reduction, the metal is often vacuum-distilled or zone-refined to attain ultra-high purity (>99.9%), with global output concentrated in facilities in , where integrated rare earth processing chains enable efficient scaling. Safety protocols emphasize handling under inert gases, given samarium's pyrophoric upon exposure to air.

Geopolitical and supply risks

China refines 100% of the world's samarium supply, creating a critical dependency for global users despite the element's reserves being distributed more widely, with holding approximately 35% of known global reserves estimated at 9.6 million metric tons. This processing monopoly stems from 's broader control over 92% of rare earth refining capacity and 98% of production, where samarium is primarily used in high-temperature samarium-cobalt magnets. Geopolitical tensions have materialized in supply disruptions, notably China's imposition of export restrictions on samarium and six other rare earth elements in April 2025, enacted in retaliation to U.S. tariffs on Chinese goods. These controls halted samarium shipments, exacerbating vulnerabilities for U.S. defense applications, including heat-resistant magnets in F-35 fighter jets and missile systems, where domestic stockpiles are limited and alternatives are scarce. Analysts, including , have highlighted samarium as particularly susceptible to further export curbs amid escalating U.S.- trade frictions, potentially disrupting global supply chains for and electronics. Efforts to mitigate risks through diversification face significant hurdles, as non-Chinese refining capacity remains negligible, and development of alternative sources—such as Australia's Lynas Rare Earths or U.S. projects—lags due to environmental regulations, high costs, and technical complexities in separating samarium from mixed rare earth ores. This concentration amplifies supply volatility, with historical precedents like China's 2010 rare earth embargo on Japan underscoring the potential for weaponization of export controls in territorial or trade disputes.

Applications

Permanent magnets

Samarium-cobalt (SmCo) magnets represent a class of high-performance rare-earth permanent magnets where samarium constitutes approximately 25-35% by weight of the alloy, primarily alloyed with and minor additions of elements such as , , and to enhance magnetic properties. These magnets were first developed in the late through research initiated by Karl Strnat, marking the advent of commercial rare-earth magnets capable of superior compared to earlier ferrite or types. Commercial introduction occurred around 1970, driven by military and demands for compact, stable magnetic fields. SmCo magnets exist in two primary phases: the 1:5 type (SmCo₅), which offers higher but lower product, and the 2:17 type (Sm₂Co₁₇), which provides higher maximum products (typically 16-32 MGOe) at the expense of slightly reduced intrinsic . The 2:17 variants, often stabilized with Zr and Cu, achieve (B_r) values of 0.8-1.1 T and intrinsic (H_ci) exceeding 1,000 kA/m, enabling operation at temperatures up to 350°C without significant demagnetization—far surpassing neodymium-iron-boron (NdFeB) magnets, which lose strength above 150-200°C. Their ranges from 700-800°C, attributed to strong exchange interactions in the hexagonal . These properties stem from samarium's 4f electron configuration, which contributes to high , combined with cobalt's ferromagnetic alignment, yielding resistance to demagnetization fields and degradation. SmCo magnets exhibit excellent resistance due to their oxide-forming surface, obviating the need for coatings in many environments, though they are brittle and more costly to produce than NdFeB alternatives owing to samarium's scarcity and complex sintering processes involving and . Applications leverage these attributes in scenarios requiring reliability under extreme conditions, including high-temperature electric motors, actuators, and generators in turbo-machinery; sensors and magnetic bearings in industrial and automotive systems; and specialized medical devices like MRI components or traveling wave tubes. In contexts, they power guidance systems and inertial due to dimensional stability and low of (typically -0.03%/°C). Despite comprising a smaller than NdFeB—estimated at under 10% of production—SmCo's niche persists where cost premiums are justified by performance in corrosive or high-heat settings, such as oilfield downhole tools.

Nuclear applications

Samarium-149 (^149Sm), comprising 13.82% of naturally occurring samarium, exhibits a cross-section of approximately 42,000 barns, rendering it one of the most effective absorbers among isotopes. This characteristic enables its use in control rods, where samarium metal or compounds are incorporated to dampen chain reactions by capturing s without significant transmutation into other isotopes. In operating reactors, ^149Sm also accumulates as a direct fission product from , with a cumulative yield of about 1.08% per fission event, gradually increasing its concentration and exerting a poisoning effect that reduces reactivity over time. Unlike shorter-lived poisons such as , ^149Sm remains stable post-shutdown, necessitating strategic power reduction protocols in certain designs to allow partial and avoid prolonged "samarium poisoning" that could delay restarts. Efforts to mitigate initial reactivity excess in fresh fuel assemblies have included engineered burnable poisons designed to mimic the gradual ^149Sm buildup, as outlined in patents for samarium-compensating systems that deploy alternative absorbers like or to achieve equilibrium without relying solely on in-situ production. Such applications underscore samarium's role in enhancing fuel cycle efficiency and margins in pressurized water reactors and other light-water designs.

Medical uses

Samarium-153 lexidronam, also known as Quadramet, is a employed for the palliative relief of in patients with osteoblastic metastatic bone lesions from various cancers, including , , and malignancies. The agent consists of the beta- and gamma-emitting radioisotope samarium-153 chelated to ethylenediaminetetramethylene (EDTMP), which selectively binds to crystals in areas of active , such as metastatic sites. Administered as a single intravenous dose of 1 mCi/kg over one minute, samarium-153 lexidronam delivers targeted beta to tumor-laden , inducing local while the accompanying gamma emissions allow for scintigraphic imaging to confirm biodistribution. Pain relief typically manifests within 7-14 days post-administration, with response rates reported in 60-80% of patients and duration of effect averaging 2-3 months, often reducing the need for analgesics. Common adverse effects are hematologic, including transient myelosuppression such as (up to 30% incidence) and , which generally resolve within 8 weeks; contraindications include severe compromise or to EDTMP. While primarily palliative, preclinical and early clinical data suggest potential antitumor effects beyond pain control in certain malignancies, though not yet established as standard therapy. Samarium-153 has also been explored in radiation for inflammatory joint diseases using particulate forms like samarium-153 , but this remains investigational with limited routine clinical adoption.

Chemical and catalytic roles

Samarium primarily exhibits the +3 in its compounds, though the +2 state is accessible in samarium(II) (SmI₂), a deep blue reagent widely used as a single-electron in . First prepared by Kagan and co-workers in 1980, SmI₂ enables diverse transformations including the reduction of alkyl, allyl, and vinyl halides to hydrocarbons, as well as carbonyl compounds to alcohols or pinacols via coupling. Its reactivity stems from the low of Sm³⁺/Sm²⁺ (-1.55 V vs. SCE in THF), allowing selective under mild conditions, often with additives like HMPA or proton donors to tune selectivity. In carbon-carbon bond formation, SmI₂ mediates Barbier and Reformatsky-type reactions, where organosamarium intermediates generated couple with electrophiles such as aldehydes or ketones. For example, allyl halides react with carbonyls in the presence of SmI₂ to yield homoallylic alcohols with high efficiency, bypassing the need for preformed organometallics. Cross-coupling applications extend to aryl halides and ketones, forming diarylmethanes, with yields often exceeding 80% under anaerobic conditions in THF. Catalytic applications leverage samarium's properties for turnover. -active SmI₂ systems, regenerated via Sm(III)-to-Sm(II) reduction using , , or chemical oxidants, catalyze of carbonyls and with turnover numbers up to hundreds. For instance, SmI₂ combined with alcohols or mediates electrochemical reduction to with 82% Faradaic efficiency, the highest reported for non-aqueous systems as of 2025. Similarly, Sm(III)- complexes enable electrocatalytic of ketones to alcohols, addressing limitations of stoichiometric SmI₂. Samarium(III) triflate (Sm(OTf)₃) functions as a robust Lewis acid catalyst, tolerant to water and air, promoting reactions like aldol additions, Diels-Alder cycloadditions, and glycosylations with catalyst loadings as low as 1-5 mol%. In heterogeneous catalysis, samarium promoters enhance metal catalysts; for example, Sm-modified Cu/Al₂O₃ improves methanol steam reforming selectivity to CO₂ by stabilizing Cu particles and optimizing H₂ adsorption sites, achieving up to 20% higher CO₂ yield at 250°C. These roles underscore samarium's utility in fine chemical synthesis and process catalysis, driven by its unique electron-transfer capabilities.

Emerging and research applications

Samarium compounds, particularly samarium diiodide (SmI₂), have garnered attention in recent organic synthesis research for enabling reductive cross-couplings and electrocatalytic processes previously challenging with traditional reductants. In 2024, researchers developed a mild protonolysis method using Sm(III)-alkoxide intermediates to facilitate intermolecular reductive coupling of ketones and acrylates, expanding SmI₂'s utility beyond stoichiometric use to catalytic regimes with turnover numbers exceeding 10 in select cases. This approach leverages samarium's variable oxidation states (+2 and +3) for selective electron transfer, addressing limitations in scalability observed in earlier SmI₂ applications that required harsh conditions for bond cleavage. In electrocatalysis, samarium-mediated systems show promise for and CO₂ reduction. A 2025 study demonstrated SmI₂ combined with alcohols or water as an electron-transfer mediator for molybdenum-catalyzed dinitrogen reduction to , achieving yields up to 20% under ambient conditions by shuttling electrons without direct metal-nitrogen bonding on samarium. Similarly, bismuth-samarium bimetallic catalysts (e.g., Bi₄Sm₁) prepared via tuning exhibited formate production rates of 150 mA/cm² at -0.9 V vs. RHE for CO₂ electroreduction, attributed to samarium's role in modulating bismuth's electronic structure for enhanced CO₂ adsorption. Samarium hexaboride (SmB₆) emerges as a prototypical in research, hosting protected surface conduction states resistant to backscattering, which could underpin fault-tolerant architectures. Observations of magneto-quantum oscillations in SmB₆ single crystals in 2024 confirmed the presence of Dirac-like surface electrons, suggesting potential for creating Majorana quasiparticles via atomic defects for stabilization. This builds on prior findings of bulk hybridization gaps in SmB₆, positioning it as a candidate for low-dissipation interconnects in quantum processors, though bulk conductivity debates persist due to impurity effects in samples. Superconducting applications involving samarium include doped variants in high-temperature oxide systems, such as samarium-barium-substituted (RE)BCO grains, where samarium enhances for levitation-based technologies under development. Research in quantified optimal Sm/Ba ratios (up to 0.3) for stable growth of single-grain superconductors with critical currents over 100 A at 77 , informing next-generation and fault-current limiters. Ferromagnetic superconductivity has also been reported in samarium hexaiodide semiconductors, combining semiconducting gaps with Tc ≈ 1.5 , offering a platform for studying unconventional mechanisms.

Biological role and safety

Biological interactions

Samarium has no established essential biological role in humans, animals, or , consistent with the general lack of vital functions among rare earth elements in higher organisms. Some early observations suggest it may stimulate metabolic processes, though the mechanism remains unclear and unsupported by comprehensive mechanistic studies. Gastrointestinal absorption of samarium in mammals is low, with provisional toxicity assessments indicating minimal uptake from oral exposure, akin to other rare earth elements. Net absorption in models has been measured near zero for dietary samarium, limiting systemic exposure under typical environmental conditions. When absorbed, samarium distributes primarily to the , binding to due to its similarity to calcium (approximately 0.958 Å for Sm³⁺ versus 1.00 Å for Ca²⁺), facilitating bone-seeking behavior observed in biodistribution studies. At the cellular level, samarium ions can interact with calcium-binding sites in enzymes and proteins, partially restoring activity in calcium-deprived systems such as α-amylase (up to 56% recovery). Rare earth elements like samarium exhibit low in soils due to strong to phosphates and clays, resulting in limited uptake by (e.g., ), though influences root absorption. In microorganisms, occurs via non-specific metal transporters, but no specific samarium-dependent pathways have been identified beyond general interactions in bacterial enzymes.

Health precautions and toxicity

Samarium metal is pyrophoric and poses and risks upon exposure to air or moisture, necessitating storage under inert atmospheres such as or to prevent spontaneous ignition. Inhalation of samarium dust or fumes can irritate the , potentially leading to symptoms like coughing or with chronic exposure, similar to other rare earth metals that accumulate in lungs. contact may cause mild irritation or allergic reactions, particularly with prolonged exposure, while eye contact can result in lacrimation, , or chemical burns. Acute oral toxicity of samarium compounds, such as samarium oxide, is low, with an LD50 exceeding 5 g/kg in , indicating it is not highly poisonous via ingestion. However, soluble samarium salts can be absorbed through the and may deposit in bones, liver, and kidneys, potentially causing organ damage upon repeated exposure, as observed in rat studies where samarium induced hepatic and renal effects. Rare earth elements like samarium are associated with , production, and DNA damage in cellular models, though human epidemiological data remain limited. Handling precautions include using such as gloves, safety goggles, and respirators in well-ventilated areas or under fume hoods to minimize generation and inhalation risks. like local exhaust ventilation are recommended, and spills should be cleaned with non-sparking tools to avoid ignition. For radioactive isotopes like samarium-153 used in medical applications, additional shielding, , and are required due to risks of radiation-induced burns, tissue destruction, , and . Samarium is not classified as a by OSHA, but chronic exposure to rare earth warrants monitoring for cumulative effects.

Environmental considerations

The mining of samarium-bearing rare earth ores, such as and bastnasite, generates radioactive containing and , which exceed 1 Bq/g in activity and pose long-term risks of contamination and exposure. Processing steps, including roasting and solvent extraction, produce acidic , fluoride emissions (e.g., HF), and , with beneficiation alone generating up to 40 tons of per ton of rare earth oxide equivalent. In , the dominant producer, rare earth extraction has resulted in widespread , river , and incidents, including elevated samarium concentrations in contaminated soils ranging from 25 to 492 mg/kg against natural backgrounds of 1–5 mg/kg. Samarium released from industrial and agricultural wastes interacts strongly with soils at low concentrations, achieving over 99% and less than 2% desorption, primarily via , carbonates, and clay minerals, which limits short-term mobility but heightens risks at higher loadings where retention declines. This can facilitate leaching into aquifers during or rainfall, potentially incorporating samarium into the and causing water concentrations up to 130 μg/L in affected regions like . Ion-adsorption clay deposits, a source for heavier rare earths including samarium, exacerbate through ammonium sulfate byproducts, contributing disproportionately to marine and freshwater impacts in life-cycle assessments. End-of-life samarium-cobalt magnets from applications in and defense generate , with rates below 1% globally for rare earths, leading to accumulation and potential leaching of metals; however, hydrometallurgical methods, such as and , enable recovery of over 90% of samarium and , reducing the need for primary and associated . Radioactive samarium isotopes, like samarium-151 (half-life 90 years), from or medical uses introduce mid-term persistence risks in waste repositories, though stable samarium exhibits low aquatic toxicity and is not deemed persistent, bioaccumulative, or toxic under standard regulatory criteria. strategies, including and cleaner processing at sites like , can lower particulate matter and energy-related emissions by up to 90% compared to conventional methods.

References

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