Scandium

Scandium,  ₂₁Sc

General properties
Name, symbol	scandium, Sc
Appearance	silvery white
Pronunciation	/ˈskændiəm/ SKAN-dee-əm
Scandium in the periodic table
– ↑ Sc ↓ Y calcium ← scandium → titanium
Atomic number (Z)	21
Group, block	group 3, d-block
Period	period 4
Element category	transition metal
Standard atomic weight (±) (Ar)	44.955908(5)[1]
Electron configuration	[Ar] 3d^1 4s^2
per shell	2, 8, 9, 2
Physical properties
Phase	solid
Melting point	1814 K ​(1541 °C, ​2806 °F)
Boiling point	3109 K ​(2836 °C, ​5136 °F)
Density near r.t.	2.985 g/cm^3
when liquid, at m.p.	2.80 g/cm^3
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)
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
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)
Most stable isotopes of scandium
iso NA half-life DM DE (MeV) DP ^44m2Sc syn 58.61 h IT 0.2709 ^44Sc γ 1.0, 1.1, 1.1 ^44Sc ε – ^44Ca ^45Sc 100% ^45Sc is stable with 24 neutrons ^46Sc syn 83.79 d β^− 0.3569 ^46Ti γ 0.889, 1.120 – ^47Sc syn 3.3492 d β^− 0.44, 0.60 ^47Ti γ 0.159 – ^48Sc syn 43.67 h β^− 0.661 ^48Ti γ 0.9, 1.3, 1.0 –

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 lanthanoids. 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, it took until the 1970s before applications for scandium were developed. 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 of the element

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.^[4]

Isotopes

Scandium exists naturally exclusively as the isotope ⁴⁵Sc, which has a nuclear spin of 7/2. Thirteen radioisotopes have been characterized with the most stable being ⁴⁶Sc with a half-life of 83.8 days, ⁴⁷Sc with a half-life of 3.35 days,the positron emitter ⁴⁴Sc with a half-live of 4 h, and ⁴⁸Sc with a half-life of 43.7 hours. All of the remaining radioactive isotopes have half-lives that are less than 4 hours, and the majority of these have half-lives that are less than 2 minutes. This element also has five meta states with the most stable being ^44mSc (t_1/2 = 58.6 h).^[5]

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.^[5]

Occurrence

In terms of Earth's crust, scandium is not particularly 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.^[6] However, scandium is distributed sparsely and occurs in trace amounts in many minerals.^[7] Rare minerals from Scandinavia^[8] and Madagascar^[9] 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.^[8]

The stable form of scandium is created in supernovas via the r-process.^[10]

Production

The world production of scandium is in the order of 10 tonnes per year, in the form of scandium oxide. The demand is ca. 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.^[11][12][13]

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.^[12]

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

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

Ionic radii (pm)

Al	Sc	Y	La	Lu
53.5	74.5	90.0	103.2	86.1

Oxides and hydroxides

The oxide Sc₂O₃ and the hydroxide Sc(OH)₃ are amphoteric:^[14]

Sc(OH)₃ + 3 OH⁻ → Sc(OH)3−
6

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.^[15] Solutions of Sc³⁺ in water are acidic because of hydrolysis.

Halides and pseudohalides

The halides ScX₃ (X = Cl, Br, I) are very soluble in water, 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.^[16]

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.^[17] 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.^[18]

Lower oxidation states (+2, +1, 0) have also been observed in organoscandium compounds.^{[19][20][21][22]}

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.^[23][24] 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.^[25]

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.^[26] The first pound of 99% pure scandium metal was produced in 1960. The use for aluminium alloys began in 1971, following a US patent.^[27] Aluminium-scandium alloys were also developed in the USSR.^[28]

Laser crystals of gadolinium-scandium-gallium garnet (GSGG) were used in strategic defense applications developed in the Strategic Defense Initiative (SDI) in the 1980s and the 1990s.^[29][30]

Applications

Parts of the MiG-29 are made from Al-Sc alloy.^[31]

The addition of scandium to aluminium limits the excessive grain growth that occurs in the heat-affected zone of welded aluminium components. This has two beneficial effects: the precipitated Al₃Sc forms smaller crystals than are found in other aluminium alloys,^[31] and the volume of precipitate-free zones that normally exist at the grain boundaries of age-hardening aluminium alloys is reduced.^[31] 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.^[32]

An alloy called Al₂₀Li₂₀Mg₁₀Sc₂₀Ti₃₀ has been shown to be as strong as titanium, light as aluminium, and hard as ceramic.^[33]

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.^[31]

Some items of sports equipment, which rely on high performance materials, have been made with scandium-aluminium alloys, including baseball bats,^[34] and bicycle^[35] frames and components. Lacrosse sticks are also made with scandium. The American firearm manufacturing company Smith & Wesson produces revolvers with frames composed of scandium alloy and cylinders of titanium or carbon steel.^[36][37]

Dentists use erbium, chromium: yttrium-scandium-gallium garnet (Er,Cr:YSGG) lasers for cavity preparation and in endodontics.^[38]

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 to make high-intensity discharge lamps.^[39] Scandium iodide, along with sodium iodide, when added to a modified form of mercury-vapor lamp, produces a form of metal halide lamp. This lamp is a white light source with high color rendering index that sufficiently resembles sunlight to allow good color-reproduction with TV cameras.^[40] 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.^[39] Scandium triflate is a catalytic Lewis acid used in organic chemistry.^[41]

Health and safety

Elemental scandium is considered non-toxic and little animal testing of scandium compounds has been done.^[42] 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.^[43] In the light of these results compounds of scandium should be handled as compounds of moderate toxicity.

See also

• Rare earth element

References

1. Standard Atomic Weights 2013. Commission on Isotopic Abundances and Atomic Weights
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. 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.
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5. 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.
6. Lide, David R. (2004). CRC Handbook of Chemistry and Physics. Boca Raton: CRC Press. pp. 4–28. ISBN 978-0-8493-0485-9.
7. 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.
8. Kristiansen, Roy (2003). "Scandium – Mineraler I Norge" (PDF). Stein (in Norwegian): 14–23.
9. von Knorring, O.; Condliffe, E. (1987). "Mineralized pegmatites in Africa". Geological Journal 22: 253. doi:10.1002/gj.3350220619.
10. Cameron, A.G.W. (June 1957). "Stellar Evolution, Nuclear Astrophysics, and Nucleogenesis" (PDF). CRL-41.
11. Deschamps, Y. "Scandium" (PDF). mineralinfo.com. Retrieved 2008-10-21.
12. "Mineral Commodity Summaries 2015: Scandium" (PDF). United States Geological Survey.
13. Scandium. USGS
14. Cotton, Simon (2006). Lanthanide and actinide chemistry. John Wiley and Sons. pp. 108–. ISBN 978-0-470-01006-8. Retrieved 2011-06-23.
15. 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.
16. 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: 4623. doi:10.1021/ja00090a011.
17. 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.
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19. 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.
20. 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.
21. Ana Mirela Neculai; Dante Neculai; Herbert W. Roesky; Jörg Magull; Marc Baldus; et al. (2002). "Stabilization of a Diamagnetic Sc^IBr Molecule in a Sandwich-Like Structure". Organometallics 21 (13): 2590–2592. doi:10.1021/om020090b.
22. 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.
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24. 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.
25. Cleve, Per Teodor (1879). "Sur le scandium". Comptes Rendus (in French) 89: 419–422.
26. 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.
27. Burrell, A. Willey Lower "Aluminum scandium alloy" U.S. Patent 3,619,181 issued on November 9, 1971.
28. 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.
29. Hedrick, James B. "Scandium". REEhandbook. Pro-Edge.com. Retrieved 2012-05-09.
30. Samstag, Tony (1987). "Star-wars intrigue greets scandium find". New Scientist: 26.
31. 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.
32. 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.
33. 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.
34. 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.
35. "Easton Technology Report : Materials / Scandium" (PDF). EastonBike.com. Retrieved 2009-04-03.
36. James, Frank (15 December 2004). Effective handgun defense. Krause Publications. pp. 207–. ISBN 978-0-87349-899-9. Retrieved 2011-06-08.
37. 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.
38. Nouri, Keyvan (2011-11-09). "History of Laser Dentistry". Lasers in Dermatology and Medicine. pp. 464–465. ISBN 978-0-85729-280-3.
39. Hammond, C.R. in CRC Handbook of Chemistry and Physics 85th ed., Section 4; The Elements
40. Simpson, Robert S. (2003). Lighting Control: Technology and Applications. Focal Press. p. 108. ISBN 978-0-240-51566-3.
41. Kobayashi, Shu; Manabe, Kei (2000). "Green Lewis acid catalysis in organic synthesis" (PDF). Pure Appl. Chem. 72 (7): 1373–1380. doi:10.1351/pac200072071373.
42. Horovitz, Chaim T.; Birmingham, Scott D. (1999). Biochemistry of Scandium and Yttrium. Springer. ISBN 978-0-306-45657-2.
43. 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. doi:10.1002/jps.2600511107. PMID 13952089.

Further reading

• Scerri, Eric R. (2007). The Periodic System: Its Story and Its Significance. Oxford, UK: Oxford University Press. ISBN 9780195305739. OCLC 62766695.

External links

• Scandium at The Periodic Table of Videos (University of Nottingham)
• WebElements.com – Scandium
•  "Scandium". Encyclopædia Britannica (11th ed.). 1911.