Europium - Wikipedia, the free encyclopedia

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Europium
From Wikipedia, the free encyclopedia

Europium ( /jropim/ ew-ROH-pee-m) 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 signicant biological role and is relatively non-toxic compared to other heavy metals. Most applications of europium exploit the phosphorescence of europium compounds.

samarium europium gadolinium 63Eu Eu Periodic table Am

Appearance silvery white, but rarely seen without oxide discoloration

Contents
1 Characteristics 1.1 Physical properties 1.2 Chemical properties 1.2.1 Eu(II) vs. Eu(III) 1.3 Isotopes 1.3.1 Europium as a nuclear ssion product 1.4 Occurrence 2 Production 3 Compounds 3.1 Halides 3.2 Chalcogenides and pnictides 4 5 6 7 8 9 History Applications Precautions See also References External links
General properties Name, symbol, number Pronunciation Element category Group, period, block Standard atomic weight Electron conguration Electrons per shell 2, 8, 18, 25, 8, 2 (Image) Physical properties Phase solid 5.264 gcm3 [Xe] 4f7 6s2 151.964 /jropim/ yoo-ROH-pee-m lanthanide n/a, 6, f europium, Eu, 63

Characteristics
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Density (near r.t.)

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Physical properties
Europium is a ductile metal with a hardness similar to that of lead. It crystallizes in a body-centered [2] cubic lattice. Some properties of europium are strongly inuenced by its half-lled electron shell. Europium has the second lowest melting point and the lowest density of all [2] lanthanides.

Liquid density at m.p. Melting point Boiling point Heat of fusion Heat of vaporization

5.13 gcm3 1099 K,826 C, 1519 F 1802 K,1529 C, 2784 F 9.21 kJmol1 176 kJmol1

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

Molar heat capacity 27.66 Jmol1K1 Vapor pressure P (Pa) 1 10 100 1k 10 k 100 k

at T (K) 863 957 1072 1234 1452 1796 Atomic properties Oxidation states Electronegativity 3, 2 (mildly basic oxide) ? 1.2 (Pauling scale) 2nd: 1085 kJmol1 3rd: 2404 kJmol1 Atomic radius Covalent radius 180 pm 1986 pm Ionization energies 1st: 547.1 kJmol1

Europium becomes a Oxidized europium, coated superconductor with yellow europium(II) when it is cooled carbonate below 1.8 K and compressed to above 80 GPa. This is because europium is [3] divalent in the metallic state, and is converted into the trivalent state by the applied pressure. In the divalent state, the strong local 7 magnetic moment (J = /2) suppresses the superconductivity, which is induced by 3+ [4] eliminating this local moment (J = 0 in Eu ).

Miscellanea Crystal structure Magnetic ordering body-centered cubic paramagnetic[1] m Thermal est. 13.9 Wm1K1 conductivity Thermal expansion (r.t.) (poly) 35.0 m/(mK) Young's modulus Shear modulus Bulk modulus Poisson ratio Vickers hardness 18.2 GPa 7.9 GPa 8.3 GPa 0.152 167 MPa

Electrical resistivity (r.t.) (poly) 0.900

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 [5] within several days. Its reactivity with water is comparable to that of calcium, and the reaction is 2 Eu + 6 H2O 2 Eu(OH)3 + 3 H2

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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 Eu2O3 Europium dissolves readily in dilute sulfuric acid to form pale pink solutions of the hydrated [6] Eu(III), which exist as a nonahydrate: 2 Eu + 3 H2SO4 + 18 H2O 2 [Eu(OH2)9]
2 + 3 SO4 + 3 H2
3+

CAS registry number

7440-53-1

Most stable isotopes Main article: Isotopes of europium iso

150 151

NA syn

half-life DM 36.9 y y

DE
(MeV)

DP
150

Eu

2.261

Sm Pm

Eu 47.8% 51018 Eu syn 13.516 y

147

152

1.874 1.819

152

Sm Gd

152

Eu(II) vs. Eu(III)

153

Eu 52.2%

153

Eu is stable with 90 neutrons

Although usually trivalent, europium readily forms divalent compounds. This behavior is unusual to most lanthanides, which almost exclusively form compounds with an 7 oxidation state of +3. The +2 state has an electron conguration 4f because the half-lled 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 [7] europium(II) are also highly insoluble in water. 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 suciently 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. Bastnsite 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
151 Eu and 153Eu, with 153Eu Naturally occurring europium is composed of 2 isotopes, 153 Eu is stable, 151Eu was being the most abundant (52.2% natural abundance). While 18 [8] recently found to be unstable to alpha decay with half-life of 5 3 10 years, 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 151 Eu, 35 articial radioisotopes have been characterized, the most stable radioisotope 150 152 Eu with a half-life of 36.9 years, Eu with a half-life of 13.516 years, and being 154 Eu with a half-life of 8.593 years. All the remaining radioactive isotopes have

+11

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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 150m Eu (T=12.8 hours), 152m1Eu (T=9.3116 hours) and 152m2Eu (T=96 minutes).[9] The primary decay mode for isotopes lighter than Eu is electron capture, and the primary mode for heavier isotopes is beta minus decay. The primary decay products 153 Eu are isotopes of samarium (Sm) and the primary products after are isotopes before [9] of gadolinium (Gd). Europium as a nuclear ssion product Medium-lived Europium is ssion products produced Prop: t Yield Q * by nuclear % Unit: a keV * ssion, but 155 Eu 4.76 .0803 252 the ssion 85 product Kr 10.76 .2180 687 yields of 113m .0008 316 Cd 14.1 europium 90 isotopes are 4.505 2826 Sr 28.9 low near 137 Cs 30.23 6.337 1176 the top of 121m the mass Sn 43.9 .00005 390 range for 151 .5314 77 Sm 90 ssion products. Thermal neutron capture cross sections Isotope 151Eu 152Eu 153Eu 154Eu 155Eu Yield ~10 low 1580 >2.5 330 1340 3950 Barns 5900 12800 312
153

Like other lanthanides, many isotopes, especially isotopes with odd mass numbers and 152 Eu, have high cross sections for neutron capture, often neutron-poor isotopes like high enough to be neutron poisons. Eu is the beta decay product of samarium-151, but since this has a long decay 151 Sm instead winds up as half-life and short mean time to neutron absorption, most 152 Sm. Eu (half-life 13.516 years) and 154Eu (half-life 8.593 years) cannot be beta decay 152 Sm and 154Sm are non-radioactive, but 154Eu is the only long-lived products because 134 Cs, to have a ssion yield of more than 2.5 parts per "shielded" nuclide, other than [10] A larger amount of 154Eu is produced by neutron activation of a million ssions. 153 Eu; however, much of this is further signicant portion of the non-radioactive 155 Eu. converted to Eu (half-life 4.7612 years) has a ssion 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
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[11][12][13][14][15][16][17]

hazard, and by samarium and others as a neutron poison.

Occurrence
Europium is not found in nature as a free element. Many minerals contain europium, with the most important sources being bastnsite, monazite, xenotime and [18] loparite. Depletion or enrichment of europium in minerals relative to other rare earth elements is known as the europium [19] Europium is commonly included in trace anomaly. 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.
2+

Monazite

Divalent europium (Eu ) in small amounts is the activator of the bright blue 3+ to uorescence of some samples of the mineral uorite (CaF2). The reduction from Eu 2+ [20] is induced by irradiation with energetic particles. The most outstanding Eu examples of this originated around Weardale and adjacent parts of northern England; it was the uorite found here that uorescence was named after, although it was not until much later that europium was determined to be the cause.

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 bastnsite, loparite, xenotime, and monazite in mineable quantities. The rst two are orthophosphate minerals LnPO4 (Ln denotes a mixture of all the lanthanides except promethium), and the third is a uorocarbonate 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 [21] Europium metal precipitated as carbonate or is co-precipitated with barium sulfate. is available through the electrolysis of a mixture of molten EuCl 3 and NaCl (or CaCl2) in a graphite cell, which serves as cathode, using graphite as anode. The other product is [18][21][22][23][24] chlorine gas.
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A few large deposits produce or produced a signicant amount of the world production. The Bayan Obo iron ore deposit contains signicant amounts of bastnsite and monazite and is, with an estimated 36 million tonnes of rare earth element oxides, the largest [25][26][27] The mining operations at the Bayan Obo deposit made China known deposit. 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 bastnsite 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 [18][28] Russia.

Compounds
See also: Category:Europium compounds

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) uoride (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) uoride (EuF2), colorless europium(II) chloride (EuCl2), colorless europium(II) [2] bromide (EuBr2), and green europium(II) iodide (EuI2).

Europium sulfate, Eu2(SO4)3

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) sulde (EuS), europium(II) selenide (EuSe) and europium(II) telluride (EuTe): all three of these are black solids. EuS is prepared by sulding the oxide at [29] temperatures suciently high to decompose the Eu2O3: Eu2O3 + 3 H2S 2 EuS + 3 H2O + S The main nitride is europium(III) nitride (EuN).

Europium sulfate uorescing red under ultraviolet light

History
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Although europium is present in most of the minerals containing the other rare elements, due to the diculties 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 [30] Europium was rst found by Paul mile Lecoq de Boisbaudran in 1890, europium. 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 Eugne-Anatole Demaray, 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 [31][32] it europium. 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 [33] as the typical europium content in monazite is about 0.05%. monazite processors, However, the Molycorp bastnsite 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 sucient 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 [33] Europium has continued in use in the TV industry ever since, and, of the result. course, also in computer monitors. Californian bastnsite now faces sti 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 [34] revolutionized the rare earth industry in the mid-1950s once related the story of how he was lecturing on the rare earths in the 1930s when an elderly gentleman approached him with an oer 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 [23][35] famous method of europium purication involving redox chemistry. 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 [36][37][38] series."

Applications
Relative to most other elements, commercial applications for europium are few and

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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 uorescent lamps, and as an activator for yttrium-based phosphors. [39][40] Color TV screens contain between 0.5 and 1 g of [41] Whereas trivalent europium gives red europium. 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 Europium is one of the phosphors give "white" light, the color temperature of elements used to make the which can be varied by altering the proportion or specic red color in CRT televisions. composition of the individual phosphors. This phosphor system is typically encountered in the helical uorescent light bulbs. Combining the same three classes is one way to make trichromatic systems [39] Europium is also used in the manufacture of uorescent in TV and computer screens. glass. One of the more common persistent after-glow phosphors besides copper doped [42] Europium uorescence is used zinc sulde is europium doped strontium aluminate. to interrogate biomolecular interactions in drug-discovery screens. It is also used in the [43][44] anti-counterfeiting phosphors in Euro banknotes. An application that has almost fallen out of use with the introduction of aordable 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 [45][46][47][48][49] determine enantiomeric purity.

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. [50][51] [52] The metal dust presents a re and explosion hazard.

See also
Europium anomaly

References
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External links
It's Elemental Europium (http://education.jlab.org/itselemental/ele063.html) Retrieved from "http://en.wikipedia.org/w/index.php?title=Europium& oldid=461199955" Categories: Chemical elements Lanthanides Europium Neutron poisons Reducing agents This page was last modied on 18 November 2011 at 00:21. Text is available under the Creative Commons Attribution-ShareAlike License; additional terms may apply. See Terms of use for details. Wikipedia is a registered trademark of the Wikimedia Foundation, Inc., a non-prot organization.

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