Europium

Europium, ₆₃Eu

Europium
Pronunciation	/jʊˈroʊpiəm/ ​(yuu-ROH-pee-əm)
Appearance	silvery white, with a pale yellow tint; but rarely seen without oxide discoloration
Standard atomic weight Ar°(Eu)
	151.964±0.001 151.96±0.01 (abridged)
Europium 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 – ↑ Eu ↓ Am samarium ← europium → gadolinium
Atomic number (Z)	63
Group	f-block groups (no number)
Period	period 6
Block	f-block
Electron configuration	[Xe] 4f7 6s2
Electrons per shell	2, 8, 18, 25, 8, 2
Physical properties
Phase at STP	solid
Melting point	1099 K ​(826 °C, ​1519 °F)
Boiling point	1802 K ​(1529 °C, ​2784 °F)
Density (at 20° C)	5.246 g/cm3
when liquid (at m.p.)	5.13 g/cm3
Heat of fusion	9.21 kJ/mol
Heat of vaporization	176 kJ/mol
Molar heat capacity	27.66 J/(mol·K)
Vapor pressure P (Pa) 1 10 100 1 k 10 k 100 k at T (K) 863 957 1072 1234 1452 1796
Atomic properties
Oxidation states	common: +2, +3 0
Electronegativity	Pauling scale: 1.2
Ionization energies	1st: 547.1 kJ/mol 2nd: 1085 kJ/mol 3rd: 2404 kJ/mol
Atomic radius	empirical: 180 pm
Covalent radius	198±6 pm
Spectral lines of europium
Other properties
Natural occurrence	primordial
Crystal structure	​body-centered cubic (bcc) (cI2)
Lattice constant	a = 458.22 pm (at 20 °C)
Thermal expansion	26.3×10−6/K (at 20 °C)
Thermal conductivity	est. 13.9 W/(m⋅K)
Electrical resistivity	poly: 0.900 µΩ⋅m (at r.t.)
Magnetic ordering	paramagnetic
Molar magnetic susceptibility	+34000.0×10−6 cm3/mol
Young's modulus	18.2 GPa
Shear modulus	7.9 GPa
Bulk modulus	8.3 GPa
Poisson ratio	0.152
Vickers hardness	165–200 MPa
CAS Number	7440-53-1
History
Naming	after Europe
Discovery and first isolation	Eugène-Anatole Demarçay (1896, 1901)
Isotopes of europium
Main isotopes Decay abun­dance half-life (t1/2) mode pro­duct 150Eu synth 36.9 y β+ 150Sm 151Eu 47.8% 4.62×1018 y α 147Pm 152Eu synth 13.54 y ε 152Sm β− 152Gd 153Eu 52.2% stable 154Eu synth 8.59 y β− 154Gd 155Eu synth 4.76 y β− 155Gd

Europium (Template:Pron-en, yoo-ROH-pee-əm) is a chemical element with the symbol Eu and atomic number 63. It was named after the continent of Europe.

Characteristics

Physical

dendritic sublimated Eu handled in a glovebox (~300 g; purity 99.998%)

Europium is a metal about as hard as lead and is quite ductile. It becomes a superconductor when it is simultaneously at both high pressure (80 GPa) and at low temperature (1.8 K). The occurrence of superconductivity is due to the applied pressure driving europium from a divalent (J = 7/2) state into a trivalent (J = 0) state. In the divalent state, the strong local magnetic moment is thought to play a role in suppressing the superconductivity and so through eliminating this local moment the opportunity for superconductivity arises.

Chemical

Europium is the most reactive of the rare earth elements; it rapidly oxidizes in air (bulk oxidation of a centimeter-sized sample within several days) and resembles calcium in its reaction with water. Samples of the metal element in solid form, even when coated with a protective layer of mineral oil, are rarely shiny. Europium ignites in air at 150 °C to 180 °C to form europium(III) oxide:

4 Eu + 3 O₂ → 2 Eu₂O₃

Europium is quite electropositive and reacts slowly with cold water and quite quickly with hot water to form europium hydroxide:

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

Europium metal reacts with all the halogens:

2 Eu (s) + 3 F₂ (g) → 2 EuF₃ (s) [white]

2 Eu (s) + 3 Cl₂ (g) → 2 EuCl₃ (s) [yellow]

2 Eu (s) + 3 Br₂ (g) → 2 EuBr₃ (s) [gray]

2 Eu (s) + 3 I₂ (g) → 2 EuI₃ (s)

Europium dissolves readily in dilute sulfuric acid to form solutions containing very pale pink Eu(III) ions, which exist as a [Eu(OH₂)₉]³⁺ complexes:

2 Eu (s) + 3 H₂SO₄ (aq) → 2 Eu³⁺ (aq) + 3 SO²⁻
₄ (aq) + 3 H₂ (g)

Compounds

See also: Category:Europium compounds

Europium compounds include:

• Fluorides: EuF₂, EuF₃
• Chlorides: EuCl₂, EuCl₃
• Bromides: EuBr₂, EuBr₃
• Iodides: EuI₂, EuI₃
• Oxides: EuO, Eu₂O₃, Eu₃O₄
• Sulfides: EuS
• Selenides: EuSe
• Tellurides: EuTe
• Nitrides: EuN.

Europium(II) compounds tend to predominate, in contrast to most lanthanides which generally form compounds with an oxidation state of +3. Europium(II) chemistry is very similar to barium(II) chemistry, as they have similar ionic radii. Divalent europium is a mild reducing agent, such that under atmospheric conditions, it is the trivalent form that predominates. Under anaerobic, and particularly under geothermal conditions, the divalent form is sufficiently stable such that it tends to be incorporated into minerals of calcium and the other alkaline earths. This is the cause of the "negative europium anomaly", that depletes europium from being incorporated into the most usual light lanthanide minerals such as monazite, relative to the chondritic abundance. Bastnäsite tends to show less of a negative europium anomaly than monazite does, and hence is the major source of europium today. The accessible divalency of europium has always made it one of the easiest lanthanides to extract and purify, 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 $5_{-3}^{+11}\times 10^{18}$ yr (in reasonable agreement with theoretical predictions), giving about 1 alpha decay per two minutes in every kilogram of natural europium. Besides natural radioisotope ¹⁵¹Eu, 35 artificial radioisotopes have been characterized, with 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 of the remaining radioactive isotopes have half-lives that are less than 4.7612 years, and the majority of these have half-lives that are less than 12.2 seconds. This element also has 8 meta states, with the most stable being ^150mEu (T_½=12.8 hours), ^152m1Eu (T_½=9.3116 hours) and ^152m2Eu (T_½=96 minutes).

The primary decay mode before the most abundant stable isotope, ¹⁵³Eu, is electron capture, and the primary mode after 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).

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

Medium-lived
fission products

	t½ (year)	Yield (%)	Q (keV)	βγ
155Eu	4.76	0.0803	252	βγ
85Kr	10.76	0.2180	687	βγ
113mCd	14.1	0.0008	316	β
90Sr	28.9	4.505	2826	β
137Cs	30.23	6.337	1176	βγ
121mSn	43.9	0.00005	390	βγ
151Sm	88.8	0.5314	77	β

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 Sm-151, but since this has a long decay half-life and short mean time to neutron absorption, most ¹⁵¹Sm instead winds up as ¹⁵²Sm.

¹⁵²Eu (half-life 13.516 years) and ¹⁵⁴Eu (halflife 8.593 years) cannot be beta decay products because ¹⁵²Sm and ¹⁵⁴Sm are nonradioactive, 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. A larger amount of ¹⁵⁴Eu will be produced by neutron activation of a significant portion of the nonradioactive¹⁵³Eu; however, much of this will be further converted to ¹⁵⁵Eu.

¹⁵⁵Eu (halflife 4.7612 years) has a fission yield of 330 ppm for U-235 and thermal neutrons. Most will be transmuted to nonradioactive and nonabsorptive Gadolinium-156 by the end of fuel burnup.

Overall, europium is overshadowed by Cs-137 and Sr-90 as a radiation hazard, and by samarium and others as a neutron poison.

History

Europium was first found by Paul Émile Lecoq de Boisbaudran in 1890, who obtained basic fraction 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 europium in 1901. 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 mad scramble for the limited supply of europium on hand among the monazite processors. (Typical europium content in monazite was about 0.05%.) Luckily, Molycorp, with its bastnäsite deposit at Mountain Pass, California, whose lanthanides had an unusually "rich" 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. 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, in the 1930s, he was lecturing on the rare earths 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 Dr. McCoy who had developed a famous method of europium purification involving redox chemistry.

Occurrence

Monazite

Europium is never found in nature as a free element; however, there are many minerals containing europium, with the most important sources being bastnäsite and monazite. Europium has also been identified in the spectra of the sun and certain stars. Depletion or enrichment of europium in minerals relative to other rare earth elements is known as the europium anomaly.

Divalent europium in small amounts happens to be the activator of the bright blue fluorescence of some samples of the mineral fluorite (calcium difluoride). The most outstanding examples of this originated around Weardale, and adjacent parts of northern England, and indeed it was this fluorite that gave its name to the phenomenon of fluorescence, although it was not until much later that europium was discovered or determined to be the cause.

Production

Main article: Monazite

Europium is found in minerals xenotime, monazite, and bastnäsite. The first two are orthophosphate minerals LnPO₄ (Ln denotes a mixture of all the lanthanides except promethium which is vanishingly rare due to being radioactive) and the third is a fluoride carbonate LnCO₃F. Lanthanoids with even atomic numbers are more common. The most common lanthanides in these minerals are, in order, cerium, lanthanum, neodymium, and praseodymium. Monazite also contains thorium and yttrium, which makes handling difficult since thorium and its decomposition products are radioactive.

For many purposes it is not particularly necessary to separate the metals, but if separation into individual metals is required, the process is complex. Initially, the metals are extracted as salts from the ores by extraction with sulfuric acid (H₂SO₄), hydrochloric acid (HCl), and sodium hydroxide (NaOH). Modern purification techniques for these lanthanide salt mixtures involve selective complexation techniques, solvent extractions, and ion exchange chromatography.

Pure europium is available through the electrolysis of a mixture of molten EuCl₃ and NaCl (or CaCl₂) in a graphite cell which acts as cathode, using graphite as anode. The other product is chlorine gas.

Applications

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

There are many commercial applications for europium metal: it has been used to dope some types of glass to make lasers, as well as for screening for Down syndrome and some other genetic diseases. Due to its ability to absorb neutrons, it is also being studied for use in nuclear reactors. Europium oxide (Eu₂O₃) is widely used as a red phosphor in television sets and fluorescent lamps, and as an activator for yttrium-based phosphors. 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 europium phosphor classes (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 is the phosphor system typically encountered in the helical fluorescent lightbulbs. Combining the same three classes is one way to make trichromatic systems in TV and computer screens. It is also being used as an agent for the manufacture of fluorescent glass. Europium fluorescence is used to interrogate biomolecular interactions in drug-discovery screens. It is also used in the anti-counterfeiting phosphors in Euro banknotes.

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 is used to help reconstruct the relationships within a suite of igneous rocks.

Precautions

The toxicity of europium compounds has not been fully investigated, but there are no clear indications that europium is highly toxic compared to other heavy metals. The metal dust presents a fire and explosion hazard. Europium has no known biological role.

See also

• Europium anomaly

External links

• WebElements.com – Europium
• It's Elemental – Europium