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Europium

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Europium (Template:IPAc-en Template:Respell) is a chemical element with the symbol Eu and atomic number 63. It is named after the continent of Europe. It is a moderately hard silvery metal which readily oxidizes in air and water. Being a typical member of the lanthanide series, europium usually assumes the oxidation state +3, but the oxidation state +2 is also common: all europium compounds with oxidation state +2 are slightly reducing. Europium has no significant biological role and is relatively non-toxic compared to other heavy metals. Most applications of europium exploit the phosphorescence of europium compounds.

Characteristics[]

Physical properties[]

Eu-Block

About 300 g of dendritic sublimated 99.998% pure europium handled in a glove box

File:Europium on air oxidized.jpg

Oxidized europium, coated with yellow europium(II) carbonate

Europium is a ductile metal with a hardness similar to that of lead. It crystallizes in a body-centered cubic lattice.[1] Some properties of europium are strongly influenced by its half-filled electron shell. Europium has the second lowest melting point and the lowest density of all lanthanides.[1]

Europium becomes a superconductor when it is cooled below 5.6 K and compressed to above 80 GPa. This is because europium is divalent in the metallic state,[2] and is converted into the trivalent state by the applied pressure. In the divalent state, the strong local magnetic moment (J = 7/2) suppresses the superconductivity, which is induced by eliminating this local moment (J = 0 in Eu3+).[3]

Chemical properties[]

Europium is the most reactive rare earth element. It rapidly oxidizes in air, so that bulk oxidation of a centimeter-sized sample occurs within several days.[4] Its reactivity with water is comparable to that of calcium, and the reaction is

2 Eu + 6 H2O → 2 Eu(OH)3 + 3 H2

Because of the high reactivity, samples of solid europium rarely have the shiny appearance of the fresh metal, even when coated with a protective layer of mineral oil. Europium ignites in air at 150 to 180 °C to form europium(III) oxide:

4 Eu + 3 O2 → 2 Eu2

Europium dissolves readily in dilute sulfuric acid to form pale pink solutions of the hydrated Eu(III), which exist as a nonahydrate:[5]

2 Eu + 3 H2SO4 + 18 H2O → 2 [Eu(OH2)9]3+ + 3 SO2−
4 + 3 H2

Eu(II) vs. Eu(III)[]

Although usually trivalent, europium readily forms divalent compounds. This behavior is unusual to most lanthanides, which almost exclusively form compounds with an oxidation state of +3. The +2 state has an electron configuration 4f7 because the half-filled f-shell gives more stability. In terms of size and coordination number, europium(II) and barium(II) are similar. For example, the sulfates of both barium and europium(II) are also highly insoluble in water.[6] Divalent europium is a mild reducing agent, oxidizing in air to form Eu(III) compounds. In anaerobic, and particularly geothermal conditions, the divalent form is sufficiently stable that it tends to be incorporated into minerals of calcium and the other alkaline earths. This ion-exchange process is the basis of the "negative europium anomaly", the low europium content in many lanthanide minerals such as monazite, relative to the chondritic abundance. Bastnäsite tends to show less of a negative europium anomaly than does monazite, and hence is the major source of europium today. The development of easy methods to separate europium from the other trivalent lanthanides made europium accessible even when present in low concentration, as it usually is.

Isotopes[]

Main article: Isotopes of europium

Naturally occurring europium is composed of 2 isotopes, 151Eu and 153Eu, with 153Eu being the most abundant (52.2% natural abundance). While 153Eu is stable, 151Eu was recently found to be unstable to alpha decay with half-life of Template:Val,[7] giving about 1 alpha decay per two minutes in every kilogram of natural europium. This value is in reasonable agreement with theoretical predictions. Besides the natural radioisotope 151Eu, 35 artificial radioisotopes have been characterized, the most stable being 150Eu with a half-life of 36.9 years, 152Eu with a half-life of 13.516 years, and 154Eu with a half-life of 8.593 years. All the remaining radioactive isotopes have half-lives shorter than 4.7612 years, and the majority of these have half-lives shorter than 12.2 seconds. This element also has 8 meta states, with the most stable being 150mEu (T½=12.8 hours), 152m1Eu (T½=9.3116 hours) and 152m2Eu (T½=96 minutes).[8]

The primary decay mode for isotopes lighter than 153Eu is electron capture, and the primary mode for heavier isotopes is beta minus decay. The primary decay products before 153Eu are isotopes of samarium (Sm) and the primary products after are isotopes of gadolinium (Gd).[8]

Europium as a nuclear fission product[]

Thermal neutron capture cross sections
Isotope 151Eu 152Eu 153Eu 154Eu 155Eu
Yield ~10 low 1580 >2.5 330
Barns 5900 12800 312 1340 3950

Template:Medium-lived fission products Europium is produced by nuclear fission, but the fission product yields of europium isotopes are low near the top of the mass range for fission products.

Like other lanthanides, many isotopes, especially isotopes with odd mass numbers and neutron-poor isotopes like 152Eu, have high cross sections for neutron capture, often high enough to be neutron poisons.

151Eu is the beta decay product of samarium-151, but since this has a long decay half-life and short mean time to neutron absorption, most 151Sm instead ends up as 152Sm.

152Eu (half-life 13.516 years) and 154Eu (half-life 8.593 years) cannot be beta decay products because 152Sm and 154Sm are non-radioactive, but 154Eu is the only long-lived "shielded" nuclide, other than 134Cs, to have a fission yield of more than 2.5 parts per million fissions.[9] A larger amount of 154Eu is produced by neutron activation of a significant portion of the non-radioactive153Eu; however, much of this is further converted to 155Eu.

155Eu (half-life 4.7612 years) has a fission yield of 330 parts per million (ppm) for uranium-235 and thermal neutrons; most of it is transmuted to non-radioactive and nonabsorptive gadolinium-156 by the end of fuel burnup.

Overall, europium is overshadowed by caesium-137 and strontium-90 as a radiation hazard, and by samarium and others as a neutron poison.[10][11][12][13][14][15][16]

Occurrence[]

File:Monazit - Mosambik, O-Afrika.jpg

Monazite

Europium is not found in nature as a free element. Many minerals contain europium, with the most important sources being bastnäsite, monazite, xenotime and loparite.[17]

Depletion or enrichment of europium in minerals relative to other rare earth elements is known as the europium anomaly.[18] Europium is commonly included in trace element studies in geochemistry and petrology to understand the processes that form igneous rocks (rocks that cooled from magma or lava). The nature of the europium anomaly found helps reconstruct the relationships within a suite of igneous rocks.

Divalent europium (Eu2+) in small amounts is the activator of the bright blue fluorescence of some samples of the mineral fluorite (CaF2). The reduction from Eu3+ to Eu2+ is induced by irradiation with energetic particles.[19] The most outstanding examples of this originated around Weardale and adjacent parts of northern England; it was the fluorite found here that fluorescence was named after, although it was not until much later that europium was determined to be the cause.[20][21][22][23]

Production[]

Europium is associated with the other rare earth elements and is therefore mined together with them. Separation of the rare earth elements is a step in the later processing. Rare earth elements are found in the minerals bastnäsite, loparite, xenotime, and monazite in mineable quantities. The first two are orthophosphate minerals LnPO4 (Ln denotes a mixture of all the lanthanides except promethium), and the third is a fluorocarbonate LnCO3F. Monazite also contains thorium and yttrium, which complicates handling because thorium and its decay products are radioactive. For the extraction from the ore and the isolation of individual lanthanides, several methods have been developed. The choice of method is based on the concentration and composition of the ore and on the distribution of the individual lanthanides in the resulting concentrate. Roasting the ore and subsequent acidic and basic leaching is used mostly to produce a concentrate of lanthanides. If cerium is the dominant lanthanide, then it is converted from cerium(III) to cerium(IV) and then precipitated. Further separation by solvent extractions or ion exchange chromatography yields a fraction which is enriched in europium. This fraction is reduced with zinc, zinc/amalgam, electrolysis or other methods converting the europium(III) to europium(II). Europium(II) reacts in a way similar to that of alkaline earth metals and therefore it can be precipitated as carbonate or is co-precipitated with barium sulfate.[24] Europium metal is available through the electrolysis of a mixture of molten EuCl3 and NaCl (or CaCl2) in a graphite cell, which serves as cathode, using graphite as anode. The other product is chlorine gas.[17][24][25][26][27]

A few large deposits produce or produced a significant amount of the world production. The Bayan Obo iron ore deposit contains significant amounts of bastnäsite and monazite and is, with an estimated 36 million tonnes of rare earth element oxides, the largest known deposit.[28][29][30] The mining operations at the Bayan Obo deposit made China the largest supplier of rare earth elements in the 1990s. Only 0.2% of the rare earth element content is europium. The second large source for rare earth elements between 1965 and its closure in the late 1990s was the Mountain Pass rare earth mine. The bastnäsite mined there is especially rich in the light rare earth elements (La-Gd, Sc, and Y) and contains only 0.1% of europium. Another large source for rare earth elements is the loparite found on the Kola peninsula. It contains besides niobium, tantalum and titanium up to 30% rare earth elements and is the largest source for these elements in Russia.[17][31]

Compounds[]

Template:See also

File:Eu-sulfate.jpg

Europium sulfate, Eu2(SO4)3

File:Eu-sulfate-luminescence.jpg

Europium sulfate fluorescing red under ultraviolet light

Halides[]

Europium metal reacts with all the halogens:

2 Eu + 3 X2 → 2 EuX3 (X = F, Cl, Br, I)

This route gives white europium(III) fluoride (EuF3), yellow europium(III) chloride (EuCl3), gray europium(III) bromide (EuBr3), and colorless europium(III) iodide (EuI3). Europium also forms the corresponding dihalides: yellow-green europium(II) fluoride (EuF2), colorless europium(II) chloride (EuCl2), colorless europium(II) bromide (EuBr2), and green europium(II) iodide (EuI2).[1]

Chalcogenides and pnictides[]

Europium forms stable compounds with all of the chalcogenides, but the heavier chalcogenides stabilize the lower oxidation state. Three oxides are known: europium(II) oxide (EuO), europium(III) oxide (Eu2O3), and the mixed oxide (Eu3O4). Otherwise, the main chalcogenides are europium(II) sulfide (EuS), europium(II) selenide (EuSe) and europium(II) telluride (EuTe): all three of these are black solids. EuS is prepared by sulfiding the oxide at temperatures sufficiently high to decompose the Eu2O3:[32]

Eu2O3 + 3 H2S → 2 EuS + 3 H2O + S

The main nitride is europium(III) nitride (EuN).

History[]

Although europium is present in most of the minerals containing the other rare elements, due to the difficulties in separating the elements it was not until the late 1800s that the element was isolated. William Crookes observed the phosphorescent spectra of the rare elements and observed spectral lines later associated to europium.[33]

Europium was first found by Paul Émile Lecoq de Boisbaudran in 1890, who obtained basic fractions from samarium-gadolinium concentrates which had spectral lines not accounted for by samarium or gadolinium. However, the discovery of europium is generally credited to French chemist Eugène-Anatole Demarçay, who suspected samples of the recently discovered element samarium were contaminated with an unknown element in 1896 and who was able to isolate it in 1901; he then named it europium.[34][35]

When the europium-doped yttrium orthovanadate red phosphor was discovered in the early 1960s, and understood to be about to cause a revolution in the color television industry, there was a scramble for the limited supply of europium on hand among the monazite processors,[36] as the typical europium content in monazite is about 0.05%. However, the Molycorp bastnäsite deposit at the Mountain Pass rare earth mine, California, whose lanthanides had an unusually high europium content of 0.1%, was about to come on-line and provide sufficient europium to sustain the industry. Prior to europium, the color-TV red phosphor was very weak, and the other phosphor colors had to be muted, to maintain color balance. With the brilliant red europium phosphor, it was no longer necessary to mute the other colors, and a much brighter color TV picture was the result.[36] Europium has continued in use in the TV industry ever since, and, of course, also in computer monitors. Californian bastnäsite now faces stiff competition from Bayan Obo, China, with an even "richer" europium content of 0.2%.

Frank Spedding, celebrated for his development of the ion-exchange technology that revolutionized the rare earth industry in the mid-1950s once related the story of how[37] he was lecturing on the rare earths in the 1930s when an elderly gentleman approached him with an offer of a gift of several pounds of europium oxide. This was an unheard-of quantity at the time, and Spedding did not take the man seriously. However, a package duly arrived in the mail, containing several pounds of genuine europium oxide. The elderly gentleman had turned out to be Herbert Newby McCoy who had developed a famous method of europium purification involving redox chemistry.[26][38]

Following the lighter neptunium, plutonium, and heavier curium, americium was the fourth transuranium element to be discovered. At the time of the discovery of americium in 1944, the periodic table had been restructured by Glenn T. Seaborg to its present layout, containing the actinide row below the lanthanide one. This led to americium being located right below its twin lanthanide element europium; it was thus by analogy named after another continent, America: "The name americium (after the Americas) and the symbol Am are suggested for the element on the basis of its position as the sixth member of the actinide rare-earth series, analogous to europium, Eu, of the lanthanide series."[39][40][41]

Applications[]

File:Aperture Grille.jpg

Europium is one of the elements used to make the red color in CRT televisions.

Relative to most other elements, commercial applications for europium are few and rather specialized. Almost invariably, they exploit its phosphorescence, either in the +2 or +3 oxidation state.

It is a dopant in some types of glass in lasers and other optoelectronic devices. Europium oxide (Eu2O3) is widely used as a red phosphor in television sets and fluorescent lamps, and as an activator for yttrium-based phosphors.[42][43] Color TV screens contain between 0.5 and 1 g of europium.[44] Whereas trivalent europium gives red phosphors, the luminescence of divalent europium depends on the host lattice, but tends to be on the blue side. The two classes of europium-based phosphor (red and blue), combined with the yellow/green terbium phosphors give "white" light, the color temperature of which can be varied by altering the proportion or specific composition of the individual phosphors. This phosphor system is typically encountered in helical fluorescent light bulbs. Combining the same three classes is one way to make trichromatic systems in TV and computer screens.[42] Europium is also used in the manufacture of fluorescent glass. One of the more common persistent after-glow phosphors besides copper doped zinc sulfide is europium doped strontium aluminate.[45] Europium fluorescence is used to interrogate biomolecular interactions in drug-discovery screens. It is also used in the anti-counterfeiting phosphors in Euro banknotes.[46][47]

An application that has almost fallen out of use with the introduction of affordable superconducting magnets is the use of europium complexes, such as Eu(fod)3, as shift reagents in NMR spectroscopy. Chiral shift reagents, such as Eu(hfc)3 are still used to determine enantiomeric purity.[48][49][50][51][52]

Precautions[]

There are no clear indications that europium is particularly toxic compared to other heavy metals. Europium chloride nitrate and oxide have been tested for toxicity: europium chloride shows an acute intraperitoneal LD50 toxicity of 550 mg/kg and the acute oral LD50 toxicity is 5000 mg/kg. Europium nitrate shows a slightly higher intraperitoneal LD50 toxicity of 320 mg/kg, while the oral toxicity is above 5000 mg/kg.[53][54] The metal dust presents a fire and explosion hazard.[55]

See also[]

  • Europium anomaly

References[]

  1. ↑ 1.0 1.1 1.2 Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN 0-12-352651-5.
  2. ↑ (1975) "Generalized phase diagram for the rare-earth elements: Calculations and correlations of bulk properties". Physical Review B 11 (8): 2836–2857. DOI:10.1103/PhysRevB.11.2836.
  3. ↑ (2009) "Pressure-Induced Superconducting State of Europium Metal at Low Temperatures". Phys. Rev. Lett. 102 (19). DOI:10.1103/PhysRevLett.102.197002.
  4. ↑ Rare-Earth Metal Long Term Air Exposure Test. Retrieved on 2009-08-08.
  5. ↑ Chemical reactions of Europium. Webelements. Retrieved on 2009-06-06.
  6. ↑ (1946) "Inorganic Syntheses" 2: 69–73. DOI:10.1002/9780470132333.ch19.
  7. ↑ Belli, P. (2007). "Search for α decay of natural europium". Nuclear Physics A 789: 15–29. DOI:10.1016/j.nuclphysa.2007.03.001.
  8. ↑ 8.0 8.1 Nucleonica (2007-2011). Nucleonica: Universal Nuclide Chart. Nucleonica: Universal Nuclide Chart. Nucleonica. Retrieved on July 22, 2011.
  9. ↑ Tables of Nuclear Data, Japan Atomic Energy Agency
  10. ↑ (2000) "Neutron cross section evaluations of fission products below the fast energy region". DOI:10.2172/759039.
  11. ↑ (1947) "Activities Induced by Pile Neutron Bombardment of Samarium". Physical Review 71 (9): 643–643. DOI:10.1103/PhysRev.71.643.
  12. ↑ (1949) "Reactions Induced by Slow Neutron Irradiation of Europium". Physical Review 75 (10): 1500–1507. DOI:10.1103/PhysRev.75.1500.
  13. ↑ (1954) "Activation Analysis of Several Rare Earth Elements". Analytical Chemistry 26 (5): 907–909. DOI:10.1021/ac60089a030.
  14. ↑ (1962) "Cumulative yields of the heavy fragments in U235 thermal neutron fission". Nuclear Physics 34 (2): 367–381. DOI:10.1016/0029-5582(62)90227-4.
  15. ↑ (1950) "U235 Fission Yields in the Rare Earth Region". Physical Review 79 (2): 271–274. DOI:10.1103/PhysRev.79.271.
  16. ↑ (1941) "A Note on the Radiochemistry of Europium". Physical Review 60 (7): 533–534. DOI:10.1103/PhysRev.60.533.2.
  17. ↑ 17.0 17.1 17.2 "Kirk-Othmer Encyclopedia of Chemical Technology" 14: 1096–1120. DOI:10.1002/0471238961.120114201901021.
  18. ↑ Sinha, Shyama P. (1983). "Systematics and the properties of the lanthanides": 550–553.
  19. ↑ (1978) "Color centers, associated rare-earth ions and the origin of coloration in natural fluorites". Physics and Chemistry of Minerals 3 (2): 117–131. DOI:10.1007/BF00308116.
  20. ↑ (2011) "A Brief History of Fluorescence and Phosphorescence before the Emergence of Quantum Theory". Journal of Chemical Education 88 (6): 731–738. DOI:10.1021/ed100182h.
  21. ↑ (1975) "Europium-activated cathodoluminescence in minerals". Geochimica et Cosmochimica Acta 39 (5): 649–660. DOI:10.1016/0016-7037(75)90008-3.
  22. ↑ (2003) "Natural fluorite emitting yellow fluorescence under UV light". Physics and Chemistry of Minerals 30 (8): 478–485. DOI:10.1007/s00269-003-0341-3.
  23. ↑ (1935) "Fluorescence of Fluorite and the Bivalent Europium Ion". Nature 135 (3403): 100–100. DOI:10.1038/135100a0.
  24. ↑ 24.0 24.1 (1992) "Extractive metallurgy of rare earths". International Materials Reviews 37: 197–248.
  25. ↑ (2001) "Recovery of europium by chemical reduction of a commercial solution of europium and gadolinium chlorides". Hydrometallurgy 60 (3): 247–253. DOI:10.1016/S0304-386X(01)00156-6.
  26. ↑ 26.0 26.1 (1936) "{{{title}}}". Journal of the American Chemical Society 58 (9): 1577–1580. DOI:10.1021/ja01300a020.
  27. ↑ (2009-01-15)"Handbook of Non-Ferrous Metal Powders: Technologies and Applications".
  28. ↑ Lawrence J. Drewa, Meng Qingrunb and Sun Weijun (1990). "The Bayan Obo iron-rare-earth-niobium deposits, Inner Mongolia, China". Lithos 26 (1-2): 43–65. DOI:10.1016/0024-4937(90)90040-8.
  29. ↑ Xue-Ming Yang, Michael J. Le Bas (2004). "Chemical compositions of carbonate minerals from Bayan Obo, Inner Mongolia, China: implications for petrogenesis". Lithos 72 (1-2): 97–116. DOI:10.1016/j.lithos.2003.09.002.
  30. ↑ Chengyu Wu (2007). "Bayan Obo Controversy: Carbonatites versus Iron Oxide-Cu-Au-(REE-U)". Resource Geology 58 (4): 348. DOI:10.1111/j.1751-3928.2008.00069.x.
  31. ↑ (1997) "Loparite, a rare-earth ore (Ce, Na, Sr, Ca)(Ti, Nb, Ta, Fe+3)O3". Journal of Alloys and Compounds 250: 467–470. DOI:10.1016/S0925-8388(96)02824-1.
  32. ↑ (1967) "Inorganic Syntheses" 10: 77–79. DOI:10.1002/9780470132418.ch15.
  33. ↑ (1905) "On the Phosphorescent Spectra of S δ and Europium". Proceedings of the Royal Society of London 76 (511): 411–414.
  34. ↑ Demarçay, Eugène-Anatole (1901). "Sur un nouvel élément l'europium". Comptes rendus 132: 1484–1486.
  35. ↑ (1932) "The discovery of the elements. XVI. The rare earth elements". Journal of Chemical Education 9 (10): 1751. DOI:10.1021/ed009p1751.
  36. ↑ 36.0 36.1 (2003) "Phosphors". The Electrochemical Society Interface: 48–51.
  37. ↑ (1949) "Large-scale separation of rare-earth salts and the preparation of the pure metals". Discussions of the Faraday Society 7: 214. DOI:10.1039/DF9490700214.
  38. ↑ Corbett, John D.. "Frank Harold Spedding". Biographical Memoirs National Academy of Sciences 80.
  39. ↑ Seaborg, G. T.; James, R.A. and Morgan, L. O.: "The New Element Americium (Atomic Number 95)", THIN PPR(National Nuclear Energy Series, Plutonium Project Record), Vol 14 B The Transuranium Elements: Research Papers, Paper No. 22.1, McGraw-Hill Book Co., Inc., New York, 1949. Abstract; Full text (January 1948), Retrieved 28 November 2010
  40. ↑ (1950) "The Isotopes of Americium". Physical Review 79 (3). DOI:10.1103/PhysRev.79.530.
  41. ↑ Greenwood, p. 1252
  42. ↑ 42.0 42.1 (1998-06-01)"Rare earths": 323–325.
  43. ↑ (2001). "Chromic phenomena: technological applications of colour chemistry": 159–171.
  44. ↑ (1992) "Extractive metallurgy of rare earths". International Materials Reviews 37: 197–248.
  45. ↑ (2008). "Luminescence and Display Phosphors: Phenomena and Applications".
  46. ↑ Europium and the Euro. Retrieved on 2009-06-06.
  47. ↑ (2006). "Lanthanide and actinide chemistry".
  48. ↑ (2011-02-15)"Essential Practical NMR for Organic Chemistry".
  49. ↑ (2009). "Introduction to spectroscopy".
  50. ↑ (2007). "Discrimination of chiral compounds using NMR spectroscopy".
  51. ↑ (2006). "Lanthanide and actinide chemistry".
  52. ↑ (2005-09-26)"Handbook on the Physics and Chemistry of Rare Earths".
  53. ↑ (1965) "Pharmacology and toxicology of europium chloride". Journal of Pharmaceutical Sciences 54 (4): 643–5. DOI:10.1002/jps.2600540435.
  54. ↑ (1963) "The acute mammalian toxicity of rare earth nitrates and oxides*1". Toxicology and Applied Pharmacology 5 (6): 750. DOI:10.1016/0041-008X(63)90067-X.
  55. ↑ Lenntech BV. Europium (Eu) - Chemical properties, Health and Environmental effects. Lenntech Periodic Table. Lenntech BV. Retrieved on July 20, 2011.



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