Scandium

Scandium,  21Sc
General properties
Pronunciation /ˈskændiəm/
SKAN-dee-əm
Appearance silvery white
Scandium in the periodic table
–
↑
Sc
↓
Y
calcium ← scandium → titanium ‍
Atomic number (Z) 21
Group, period group 3, period 4
Block d-block
Element category   transition metal
Standard atomic weight (Ar) 44.955908(5)[1]
Electron configuration [Ar] 3d1 4s2
Electrons per shell
 2, 8, 9, 2
Physical properties
Phase (at STP) solid
Melting point 1814 K ​(1541 °C, ​2806 °F)
Boiling point 3109 K ​(2836 °C, ​5136 °F)
Density near r.t. 2.985 g/cm3
when liquid, at m.p. 2.80 g/cm3
Heat of fusion 14.1 kJ/mol
Heat of vaporization 332.7 kJ/mol
Molar heat capacity 25.52 J/(mol·K)

Vapor pressure

P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 1645 1804 (2006) (2266) (2613) (3101)
Atomic properties
Oxidation states 3, 2,[2] 1[3] ​(an amphoteric oxide)
Electronegativity Pauling scale: 1.36
Ionization energies
  • 1st: 633.1 kJ/mol
  • 2nd: 1235.0 kJ/mol
  • 3rd: 2388.6 kJ/mol
  • (more)
Atomic radius empirical: 162 pm
Covalent radius 170±7 pm
Van der Waals radius 211 pm
Miscellanea
Crystal structure

​hexagonal close-packed (hcp)

Hexagonal close packed crystal structure for scandium
Thermal expansion α, poly: 10.2 µm/(m·K) (at r.t.)
Thermal conductivity 15.8 W/(m·K)
Electrical resistivity α, poly: 562 nΩ·m (at r.t., calculated)
Magnetic ordering paramagnetic
Magnetic susceptibility (χmol) +315.0·10−6 cm3/mol (292 K)[4]
Young's modulus 74.4 GPa
Shear modulus 29.1 GPa
Bulk modulus 56.6 GPa
Poisson ratio 0.279
Brinell hardness 736–1200 MPa
CAS Number 7440-20-2
History
Naming after Scandinavia
Prediction Dmitri Mendeleev (1871)
Discovery and first isolation Lars Fredrik Nilson (1879)
Main isotopes of scandium
Iso­tope Abun­dance Half-life (t1/2) Decay mode Pro­duct
44m2Sc syn 58.61 h IT 44Sc
γ 44Sc
ε 44Ca
45Sc 100% stable
46Sc syn 83.79 d β− 46Ti
γ –
47Sc syn 80.38 d β− 47Ti
γ –
48Sc syn 43.67 h β− 48Ti
γ –

Scandium is a chemical element with symbol Sc and atomic number 21. A silvery-white metallic d-block element, it has historically been sometimes classified as a rare earth element, together with yttrium and the lanthanides. It was discovered in 1879 by spectral analysis of the minerals euxenite and gadolinite from Scandinavia.

Scandium is present in most of the deposits of rare earth and uranium compounds, but it is extracted from these ores in only a few mines worldwide. Because of the low availability and the difficulties in the preparation of metallic scandium, which was first done in 1937, applications for scandium were not developed until the 1970s. The positive effects of scandium on aluminium alloys were discovered in the 1970s, and its use in such alloys remains its only major application. The global trade of scandium oxide is about 10 tonnes per year.

The properties of scandium compounds are intermediate between those of aluminium and yttrium. A diagonal relationship exists between the behavior of magnesium and scandium, just as there is between beryllium and aluminium. In the chemical compounds of the elements in group 3, the predominant oxidation state is +3.

Properties

Chemical characteristics

Scandium is a soft metal with a silvery appearance. It develops a slightly yellowish or pinkish cast when oxidized by air. It is susceptible to weathering and dissolves slowly in most dilute acids. It does not react with a 1:1 mixture of nitric acid (HNO3) and 48% hydrofluoric acid (HF), possibly due to the formation of an impermeable passive layer. Scandium turnings ignite in air with a brilliant yellow flame to form scandium(III) oxide.[5]

Isotopes

In nature, scandium is found exclusively as the isotope 45Sc, which has a nuclear spin of 7/2; this is its only stable isotope. Thirteen radioisotopes have been characterized with the most stable being 46Sc, which has a half-life of 83.8 days; 47Sc, 3.35 days; the positron emitter 44Sc, 4 h; and 48Sc, 43.7 hours. All of the remaining radioactive isotopes have half-lives less than 4 hours, and the majority of these have half-lives less than 2 minutes. This element also has five meta states, with the most stable being 44mSc (t1/2 = 58.6 h).[6]

The isotopes of scandium range from 36Sc to 60Sc. The primary decay mode at masses lower than the only stable isotope, 45Sc, is electron capture, and the primary mode at masses above it is beta emission. The primary decay products at atomic weights below 45Sc are calcium isotopes and the primary products from higher atomic weights are titanium isotopes.[6]

Occurrence

In Earth's crust, scandium is not rare. Estimates vary from 18 to 25 ppm, which is comparable to the abundance of cobalt (20–30 ppm). Scandium is only the 50th most common element on Earth (35th most abundant in the crust), but it is the 23rd most common element in the Sun.[7] However, scandium is distributed sparsely and occurs in trace amounts in many minerals.[8] Rare minerals from Scandinavia[9] and Madagascar[10] such as thortveitite, euxenite, and gadolinite are the only known concentrated sources of this element. Thortveitite can contain up to 45% of scandium in the form of scandium(III) oxide.[9]

The stable form of scandium is created in supernovas via the r-process.[11]

Production

The world production of scandium is in the order of 10 tonnes per year, in the form of scandium oxide. The demand is about 50% higher, and both the production and demand keep increasing. In 2003, only three mines produced scandium: the uranium and iron mines in Zhovti Vody in Ukraine, the rare earth mines in Bayan Obo, China, and the apatite mines in the Kola peninsula, Russia; since then many other countries have built scandium-producing facilities. In each case scandium is a byproduct from the extraction of other elements and is sold as scandium oxide.[12][13][14]

To produce metallic scandium, the oxide is converted to scandium fluoride and reduced with metallic calcium.

Madagascar and Iveland-Evje region in Norway have the only deposits of minerals with high scandium content, thortveitite (Sc,Y)2(Si2O7) and kolbeckite ScPO4·2H2O, but these are not being exploited.[13]

The absence of reliable, secure, stable, and long term production has limited commercial applications of scandium. Despite this low level of use, scandium offers significant benefits. Particularly promising is the strengthening of aluminium alloys with as little as 0.5% scandium. Scandium-stabilized zirconia enjoys a growing market demand for use as a high efficiency electrolyte in solid oxide fuel cells.

Compounds

Scandium chemistry is almost completely dominated by the trivalent ion, Sc3+. The radii of M3+ ions in the table below indicate that the chemical properties of scandium ions have more in common with yttrium ions than with aluminium ions. In part because of this similarity, scandium is often classified as a lanthanide-like element.

Ionic radii (pm)
AlScYLaLu
53.574.590.0103.286.1

Oxides and hydroxides

The oxide Sc2O3 and the hydroxide Sc(OH)3 are amphoteric:[15]

Sc(OH)3 + 3 OH− → [Sc(OH)
6]3−
Sc(OH)3 + 3 H+ + 3 H2O → [Sc(H2O)6]3+

The α- and γ- forms of scandium oxide hydroxide (ScO(OH)), are isostructural with their aluminium oxide hydroxide counterparts.[16] Solutions of Sc3+ in water are acidic because of hydrolysis.

Halides and pseudohalides

The halides, ScX3, are very soluble in water where X = Cl, Br, or I, but ScF3 is insoluble. In all four halides, the scandium is 6-coordinated. The halides are Lewis acids; for example, ScF3 dissolves in a solution containing excess fluoride ion to form [ScF6]3−. The coordination number 6 is typical of Sc(III). In the larger Y3+ and La3+ ions, coordination numbers of 8 and 9 are common. Scandium(III) triflate is sometimes used as a Lewis acid catalyst in organic chemistry.

Organic derivatives

Scandium forms a series of organometallic compounds with cyclopentadienyl ligands (Cp), similar to the behavior of the lanthanides. One example is the chlorine-bridged dimer, [ScCp2Cl]2 and related derivatives of pentamethylcyclopentadienyl ligands.[17]

Uncommon oxidation states

Compounds that feature scandium in the oxidation state other than +3 are rare but well characterized. The blue-black compound CsScCl3 is one of the simplest. This material adopts a sheet-like structure that exhibits extensive bonding between the scandium(II) centers.[18] Scandium hydride is not well understood, although it appears not to be a saline hydride of Sc(II).[2] As is observed for most elements, a diatomic scandium hydride has been observed spectroscopically at high temperatures in the gas phase.[3] Scandium borides and carbides are non-stoichiometric, as is typical for neighboring elements.[19]

Lower oxidation states (+2, +1, 0) have also been observed in organoscandium compounds.[20][21][22][23]

History

Dmitri Mendeleev, who is referred to as the father of the periodic table, predicted the existence of an element ekaboron, with an atomic mass between 40 and 48 in 1869. Lars Fredrik Nilson and his team detected this element in the minerals euxenite and gadolinite. Nilson prepared 2 grams of scandium oxide of high purity.[24][25] He named the element scandium, from the Latin Scandia meaning "Scandinavia". Nilson was apparently unaware of Mendeleev's prediction, but Per Teodor Cleve recognized the correspondence and notified Mendeleev.[26]

Metallic scandium was produced for the first time in 1937 by electrolysis of a eutectic mixture of potassium, lithium, and scandium chlorides, at 700–800 °C.[27] The first pound of 99% pure scandium metal was produced in 1960. Production of aluminium alloys began in 1971, following a US patent.[28] Aluminium-scandium alloys were also developed in the USSR.[29]

Laser crystals of gadolinium-scandium-gallium garnet (GSGG) were used in strategic defense applications developed for the Strategic Defense Initiative (SDI) in the 1980s and 1990s.[30][31]

Applications

Parts of the MiG-29 are made from Al-Sc alloy.[32]

The addition of scandium to aluminium limits the grain growth in the heat zone of welded aluminium components. This has two beneficial effects: the precipitated Al3Sc forms smaller crystals than in other aluminium alloys,[32] and the volume of precipitate-free zones at the grain boundaries of age-hardening aluminium alloys is reduced.[32] Both of these effects increase the usefulness of the alloy. However, titanium alloys, which are similar in lightness and strength, are cheaper and much more widely used.[33]

The alloy Al20Li20Mg10Sc20Ti30 is as strong as titanium, light as aluminium, and hard as ceramic.[34]

The main application of scandium by weight is in aluminium-scandium alloys for minor aerospace industry components. These alloys contain between 0.1% and 0.5% of scandium. They were used in the Russian military aircraft, specifically the MiG-21 and MiG-29.[32]

Some items of sports equipment, which rely on high performance materials, have been made with scandium-aluminium alloys, including baseball bats[35] and bicycle frames and components.[36] Lacrosse sticks are also made with scandium. The American firearm manufacturing company, Smith & Wesson, produces semi-automatic pistols and revolvers with frames of scandium alloy and cylinders of titanium or carbon steel.[37][38]

Dentists use erbium, chromium: yttrium-scandium-gallium garnet (Er,Cr:YSGG) lasers for cavity preparation and in endodontics.[39]

The first scandium-based metal halide lamps were patented by General Electric and initially made in North America, although they are now produced in all major industrialized countries. Approximately 20 kg (as Sc2O3) of scandium is used annually in the United States for high-intensity discharge lamps.[40] One type of metal halide lamp, similar to the mercury-vapor lamp, is made from Scandium iodide and sodium iodide. This lamp is a white light source with high color rendering index that sufficiently resembles sunlight to allow good color-reproduction with TV cameras.[41] About 80 kg of scandium is used in metal halide lamps/light bulbs globally per year.

The radioactive isotope 46Sc is used in oil refineries as a tracing agent.[40] Scandium triflate is a catalytic Lewis acid used in organic chemistry.[42]

Health and safety

Elemental scandium is considered non-toxic, though extensive animal testing of scandium compounds has not been done.[43] The median lethal dose (LD50) levels for scandium(III) chloride for rats have been determined as 4 mg/kg for intraperitoneal and 755 mg/kg for oral administration.[44] In the light of these results compounds of scandium should be handled as compounds of moderate toxicity.

See also

References

  1. ↑ Meija, J.; et al. (2016). "Atomic weights of the elements 2013 (IUPAC Technical Report)". Pure Appl. Chem. 88 (3): 265–91. doi:10.1515/pac-2015-0305.
  2. 1 2 McGuire, Joseph C.; Kempter, Charles P. (1960). "Preparation and Properties of Scandium Dihydride". Journal of Chemical Physics. 33: 1584–1585. Bibcode:1960JChPh..33.1584M. doi:10.1063/1.1731452.
  3. 1 2 Smith, R. E. (1973). "Diatomic Hydride and Deuteride Spectra of the Second Row Transition Metals". Proceedings of the Royal Society of London. Series A, Mathematical and Physical Sciences. 332 (1588): 113–127. Bibcode:1973RSPSA.332..113S. doi:10.1098/rspa.1973.0015.
  4. ↑ Weast, Robert (1984). CRC, Handbook of Chemistry and Physics. Boca Raton, Florida: Chemical Rubber Company Publishing. pp. E110. ISBN 0-8493-0464-4.
  5. ↑ "Scandium." Los Alamos National Laboratory. Retrieved 2013-07-17.
  6. 1 2 Audi, Georges; Bersillon, O.; Blachot, J.; Wapstra, A. H. (2003). "The NUBASE Evaluation of Nuclear and Decay Properties". Nuclear Physics A. Atomic Mass Data Center. 729: 3–128. Bibcode:2003NuPhA.729....3A. doi:10.1016/j.nuclphysa.2003.11.001.
  7. ↑ Lide, David R. (2004). CRC Handbook of Chemistry and Physics. Boca Raton: CRC Press. pp. 4–28. ISBN 978-0-8493-0485-9.
  8. ↑ Bernhard, F. (2001). "Scandium mineralization associated with hydrothermal lazurite-quartz veins in the Lower Austroalpie Grobgneis complex, East Alps, Austria". Mineral Deposits in the Beginning of the 21st Century. Lisse: Balkema. ISBN 90-265-1846-3.
  9. 1 2 Kristiansen, Roy (2003). "Scandium – Mineraler I Norge" (PDF). Stein (in Norwegian): 14–23.
  10. ↑ von Knorring, O.; Condliffe, E. (1987). "Mineralized pegmatites in Africa". Geological Journal. 22: 253. doi:10.1002/gj.3350220619.
  11. ↑ Cameron, A.G.W. (June 1957). "Stellar Evolution, Nuclear Astrophysics, and Nucleogenesis" (PDF). CRL-41.
  12. ↑ Deschamps, Y. "Scandium" (PDF). mineralinfo.com. Retrieved 2008-10-21.
  13. 1 2 "Mineral Commodity Summaries 2015: Scandium" (PDF). United States Geological Survey.
  14. ↑ Scandium. USGS
  15. ↑ Cotton, Simon (2006). Lanthanide and actinide chemistry. John Wiley and Sons. pp. 108–. ISBN 978-0-470-01006-8. Retrieved 2011-06-23.
  16. ↑ Christensen, A. Nørlund; Stig Jorgo Jensen (1967). "Hydrothermal Preparation of alpha-ScOOH and of gamma-ScOOH. Crystal Structure of alpha-ScOOH". Acta Chemica Scandinavica. 21: 1121–126. doi:10.3891/acta.chem.scand.21-0121.
  17. ↑ Shapiro, Pamela J.; et al. (1994). "Model Ziegler-Natta a-Olefin Polymerization Catalysts Derived from [{(η5-C5Me4)SiMe2(η1-NCMe3)}(PMe3)Sc(μ2-H)]2 and [{(η5-C5Me4)SiMe2(η1-NCMe3)}Sc(μ2-CH2CH2CH3)]2. Synthesis, Structures and Kinetic and Equilibrium Investigations of the Catalytically active Species in Solution". J. Am. Chem. Soc. 116 (11): 4623. doi:10.1021/ja00090a011.
  18. ↑ Corbett, J. D. (1981). "Extended metal-metal bonding in halides of the early transition metals". Acc. Chem. Res. 14 (8): 239–246. doi:10.1021/ar00068a003.
  19. ↑ Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN 0-12-352651-5.
  20. ↑ Polly L. Arnold; F. Geoffrey; N. Cloke; Peter B. Hitchcock & John F. Nixon (1996). "The First Example of a Formal Scandium(I) Complex:  Synthesis and Molecular Structure of a 22-Electron Scandium Triple Decker Incorporating the Novel 1,3,5-Triphosphabenzene Ring". J. Am. Chem. Soc. 118 (32): 7630–7631. doi:10.1021/ja961253o.
  21. ↑ F. Geoffrey N. Cloke; Karl Khan & Robin N. Perutz (1991). "η-Arene complexes of scandium(0) and scandium(II)". J. Chem. Soc., Chem. Commun. (19): 1372–1373. doi:10.1039/C39910001372.
  22. ↑ Ana Mirela Neculai; Dante Neculai; Herbert W. Roesky; Jörg Magull; Marc Baldus; et al. (2002). "Stabilization of a Diamagnetic ScIBr Molecule in a Sandwich-Like Structure". Organometallics. 21 (13): 2590–2592. doi:10.1021/om020090b.
  23. ↑ Polly L. Arnold; F. Geoffrey; N. Cloke & John F. Nixon (1998). "The first stable scandocene: synthesis and characterisation of bis(η-2,4,5-tri-tert-butyl-1,3-diphosphacyclopentadienyl)scandium(II)". Chem. Commun. (7): 797–798. doi:10.1039/A800089A.
  24. ↑ Nilson, Lars Fredrik (1879). "Sur l'ytterbine, terre nouvelle de M. Marignac". Comptes Rendus (in French). 88: 642–647.
  25. ↑ Nilson, Lars Fredrik (1879). "Ueber Scandium, ein neues Erdmetall". Berichte der deutschen chemischen Gesellschaft (in German). 12 (1): 554–557. doi:10.1002/cber.187901201157.
  26. ↑ Cleve, Per Teodor (1879). "Sur le scandium". Comptes Rendus (in French). 89: 419–422.
  27. ↑ Fischer, Werner; Brünger, Karl; Grieneisen, Hans (1937). "Über das metallische Scandium". Zeitschrift für anorganische und allgemeine Chemie (in German). 231 (1–2): 54–62. doi:10.1002/zaac.19372310107.
  28. ↑ Burrell, A. Willey Lower "Aluminum scandium alloy" U.S. Patent 3,619,181 issued on November 9, 1971.
  29. ↑ Zakharov, V. V. (2003). "Effect of Scandium on the Structure and Properties of Aluminum Alloys". Metal Science and Heat Treatment. 45 (7/8): 246. doi:10.1023/A:1027368032062.
  30. ↑ Hedrick, James B. "Scandium". REEhandbook. Pro-Edge.com. Retrieved 2012-05-09.
  31. ↑ Samstag, Tony (1987). "Star-wars intrigue greets scandium find". New Scientist: 26.
  32. 1 2 3 4 Ahmad, Zaki (2003). "The properties and application of scandium-reinforced aluminum". JOM. 55 (2): 35. Bibcode:2003JOM....55b..35A. doi:10.1007/s11837-003-0224-6.
  33. ↑ Schwarz, James A.; Contescu, Cristian I.; Putyera, Karol (2004). Dekker encyclopédia of nanoscience and nanotechnology. 3. CRC Press. p. 2274. ISBN 0-8247-5049-7.
  34. ↑ Khaled M. Youssefa, Alexander J. Zaddachb, Changning Niub, Douglas L. Irvingb & Carl C. Koch "A Novel Low-Density, High-Hardness, High-entropy Alloy with Close-packed Single-phase Nanocrystalline Structures" DOI: 10.1080/21663831.2014.985855 Materials Research Letters, 9 December 2014. Accessed: 11 December 2014.
  35. ↑ Bjerklie, Steve (2006). "A batty business: Anodized metal bats have revolutionized baseball. But are finishers losing the sweet spot?". Metal Finishing. 104 (4): 61. doi:10.1016/S0026-0576(06)80099-1.
  36. ↑ "Easton Technology Report : Materials / Scandium" (PDF). EastonBike.com. Retrieved 2009-04-03.
  37. ↑ James, Frank (15 December 2004). Effective handgun defense. Krause Publications. pp. 207–. ISBN 978-0-87349-899-9. Retrieved 2011-06-08.
  38. ↑ Sweeney, Patrick (13 December 2004). The Gun Digest Book of Smith & Wesson. Gun Digest Books. pp. 34–. ISBN 978-0-87349-792-3. Retrieved 2011-06-08.
  39. ↑ Nouri, Keyvan (2011-11-09). "History of Laser Dentistry". Lasers in Dermatology and Medicine. pp. 464–465. ISBN 978-0-85729-280-3.
  40. 1 2 Hammond, C.R. in CRC Handbook of Chemistry and Physics 85th ed., Section 4; The Elements
  41. ↑ Simpson, Robert S. (2003). Lighting Control: Technology and Applications. Focal Press. p. 108. ISBN 978-0-240-51566-3.
  42. ↑ Kobayashi, Shu; Manabe, Kei (2000). "Green Lewis acid catalysis in organic synthesis" (PDF). Pure Appl. Chem. 72 (7): 1373–1380. doi:10.1351/pac200072071373.
  43. ↑ Horovitz, Chaim T.; Birmingham, Scott D. (1999). Biochemistry of Scandium and Yttrium. Springer. ISBN 978-0-306-45657-2.
  44. ↑ Haley, Thomas J.; Komesu, L.; Mavis, N.; Cawthorne, J.; Upham, H. C. (1962). "Pharmacology and toxicology of scandium chloride". Journal of Pharmaceutical Sciences. 51 (11): 1043–5. PMID 13952089. doi:10.1002/jps.2600511107.

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