Europium(III) Oxide
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Europium is a
chemical element A chemical element is a chemical substance whose atoms all have the same number of protons. The number of protons is called the atomic number of that element. For example, oxygen has an atomic number of 8: each oxygen atom has 8 protons in its ...
; it has
symbol A symbol is a mark, Sign (semiotics), sign, or word that indicates, signifies, or is understood as representing an idea, physical object, object, or wikt:relationship, relationship. Symbols allow people to go beyond what is known or seen by cr ...
Eu and atomic number 63. It is a silvery-white metal of the lanthanide series that reacts readily with air to form a dark oxide coating. Europium is the most chemically reactive, least dense, and softest of the lanthanides. It is soft enough to be cut with a knife. Europium was discovered in 1896, provisionally designated as Σ; in 1901, it was named after the continent of
Europe Europe is a continent located entirely in the Northern Hemisphere and mostly in the Eastern Hemisphere. It is bordered by the Arctic Ocean to the north, the Atlantic Ocean to the west, the Mediterranean Sea to the south, and Asia to the east ...
. Europium usually assumes the oxidation state +3, like other members of the lanthanide series, but compounds having oxidation state +2 are 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. Europium is one of the rarest of the rare-earth elements on Earth.Stwertka, Albert. ''A Guide to the Elements'', Oxford University Press, 1996, p. 156.


Etymology

Its discoverer, Eugène-Anatole Demarçay, named the element after the continent of
Europe Europe is a continent located entirely in the Northern Hemisphere and mostly in the Eastern Hemisphere. It is bordered by the Arctic Ocean to the north, the Atlantic Ocean to the west, the Mediterranean Sea to the south, and Asia to the east ...
.


Characteristics


Physical properties

Europium is a ductile metal with a hardness similar to that of
lead Lead () is a chemical element; it has Chemical symbol, symbol Pb (from Latin ) and atomic number 82. It is a Heavy metal (elements), heavy metal that is density, denser than most common materials. Lead is Mohs scale, soft and Ductility, malleabl ...
. It crystallizes in a body-centered cubic lattice. 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.


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. Its reactivity with water is comparable to that of calcium, and the reaction is : 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: : Europium dissolves readily in dilute sulfuric acid to form pale pink solutions of : :


Eu(II) vs. Eu(III)

Although usually trivalent, europium readily forms divalent compounds. This behavior is unusual for most lanthanides, which almost exclusively form compounds with an oxidation state of +3. The +2 state has an electron configuration 4''f''7 because the half-filled ''f''-shell provides more stability. In terms of size and coordination number, europium(II) and barium(II) are similar. The sulfates of both barium and 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 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 divalent europium from the other (trivalent) lanthanides made europium accessible even when present in low concentration, as it usually is.


Isotopes

Naturally occurring europium is composed of two
isotope Isotopes are distinct nuclear species (or ''nuclides'') of the same chemical element. They have the same atomic number (number of protons in their Atomic nucleus, nuclei) and position in the periodic table (and hence belong to the same chemica ...
s, 151Eu and 153Eu, which occur in almost equal proportions; 153Eu is slightly more abundant (52.2% natural abundance). While 153Eu is stable, 151Eu was found to be unstable to alpha decay with a
half-life Half-life is a mathematical and scientific description of exponential or gradual decay. Half-life, half life or halflife may also refer to: Film * Half-Life (film), ''Half-Life'' (film), a 2008 independent film by Jennifer Phang * ''Half Life: ...
of in 2007, giving about one 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; the known isotopes of europium range from 130Eu to 170Eu. This element also has 17 meta states, with the most stable being 150mEu (''t''1/2=12.8 hours), 152m1Eu (''t''1/2=9.3116 hours) and 152m2Eu (''t''1/2=96 minutes). 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).


Europium as a nuclear fission product

Europium is produced by nuclear fission; 155Eu (half-life 4.7612 years) has a fission yield of 330 parts per million (ppm) for uranium-235 and thermal neutrons. The fission product yields of europium isotopes are low near the top of the mass range for fission products. As with other lanthanides, many isotopes of europium, especially those that have odd mass numbers or are neutron-poor 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. A larger amount of 154Eu is produced by neutron activation of a significant portion of the non-radioactive 153Eu; however, much of this is further converted to 155Eu.


Occurrence

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-(Ce). No europium-dominant minerals are known yet, despite a single find of a tiny possible Eu–O or Eu–O–C system phase in the Moon's regolith. Depletion or enrichment of europium in minerals relative to other rare-earth elements is known as the europium anomaly. 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 Magma () is the molten or semi-molten natural material from which all igneous rocks are formed. Magma (sometimes colloquially but incorrectly referred to as ''lava'') is found beneath the surface of the Earth, and evidence of magmatism has also ...
or
lava Lava is molten or partially molten rock (magma) that has been expelled from the interior of a terrestrial planet (such as Earth) or a Natural satellite, moon onto its surface. Lava may be erupted at a volcano or through a Fissure vent, fractu ...
). The nature of the europium anomaly found helps reconstruct the relationships within a suite of igneous rocks. The median crustal abundance of europium is 2 ppm; values of the less abundant elements may vary with location by several orders of magnitude.ABUNDANCE OF ELEMENTS IN THE EARTH’S CRUST AND IN THE SEA, ''CRC Handbook of Chemistry and Physics,'' 97th edition (2016–2017), p. 14-17 Divalent europium (Eu2+) in small amounts is the activator of the bright blue
fluorescence Fluorescence is one of two kinds of photoluminescence, the emission of light by a substance that has absorbed light or other electromagnetic radiation. When exposed to ultraviolet radiation, many substances will glow (fluoresce) with colore ...
of some samples of the mineral fluorite (CaF2). The reduction from Eu3+ to Eu2+ is induced by irradiation with energetic particles. 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 in 1852, although it was not until much later that europium was determined to be the cause. In astrophysics, the signature of europium in stellar spectra can be used to classify stars and inform theories of how or where a particular star was born. For instance, astronomers used the relative levels of europium to iron within the star LAMOST J112456.61+453531.3 to propose that the accretion process for star occurred late.


Production

Europium is associated with the other rare-earth elements and is, therefore, mined together with them. Separation of the rare-earth elements occurs during later processing. Rare-earth elements are found in the minerals bastnäsite, loparite-(Ce), xenotime, and monazite in mineable quantities. Bastnäsite is a group of related fluorocarbonates, Ln(CO3)(F,OH). Monazite is a group of related of orthophosphate minerals (Ln denotes a mixture of all the lanthanides except promethium), loparite-(Ce) is an oxide, and xenotime is an orthophosphate (Y,Yb,Er,...)PO4. Monazite also contains thorium and
yttrium Yttrium is a chemical element; it has Symbol (chemistry), symbol Y and atomic number 39. It is a silvery-metallic transition metal chemically similar to the lanthanides and has often been classified as a "rare-earth element". Yttrium is almost a ...
, 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, followed by 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 a carbonate or co-precipitated with barium sulfate. 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 Chlorine is a chemical element; it has Symbol (chemistry), symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between ...
gas. A few large deposits produce or produced a significant amount of the world production. The Bayan Obo iron ore deposit in
Inner Mongolia Inner Mongolia, officially the Inner Mongolia Autonomous Region, is an Autonomous regions of China, autonomous region of China. Its border includes two-thirds of the length of China's China–Mongolia border, border with the country of Mongolia. ...
contains significant amounts of bastnäsite and monazite and is, with an estimated 36 million tonnes of rare-earth element oxides, the largest known deposit. 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 in California. 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.


Compounds

Europium compounds tend to exist in a trivalent oxidation state under most conditions. Commonly these compounds feature Eu(III) bound by 6–9 oxygenic ligands. The Eu(III) sulfates, nitrates and chlorides are soluble in water or polar organic solvents. Lipophilic europium complexes often feature acetylacetonate-like ligands, such as EuFOD.


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) (although it has a bright blue fluorescence under UV light), colorless europium(II) bromide (EuBr2), and green europium(II) iodide (EuI2).Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. .


Chalcogenides and pnictides

Europium forms stable compounds with all of the chalcogens, but the heavier chalcogens (S, Se, and Te) stabilize the lower oxidation state. Three oxides are known: europium(II) oxide (EuO), europium(III) oxide (Eu2O3), and the mixed-valence oxide Eu3O4, consisting of both Eu(II) and Eu(III). 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. Europium(II) sulfide is prepared by sulfiding the oxide at temperatures sufficiently high to decompose the Eu2O3: :Eu2O3 + 3 H2S → 2 EuS + 3 H2O + S The main nitride of europium 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 including those eventually assigned to europium. Europium was first found in 1892 by Paul Émile Lecoq de Boisbaudran, 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 A chemist (from Greek ''chēm(ía)'' alchemy; replacing ''chymist'' from Medieval Latin ''alchemist'') is a graduated scientist trained in the study of chemistry, or an officially enrolled student in the field. Chemists study the composition of ...
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''. 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, as the typical europium content in monazite is about 0.05%. However, the Molycorp bastnäsite deposit at the Mountain Pass rare earth mine,
California California () is a U.S. state, state in the Western United States that lies on the West Coast of the United States, Pacific Coast. It borders Oregon to the north, Nevada and Arizona to the east, and shares Mexico–United States border, an ...
, 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. Europium has continued to be in use in the TV industry ever since as well as 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 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.


Applications

Relative to most other elements, commercial applications for europium are few and rather specialized. Almost invariably, its phosphorescence is exploited, either in the +2 or +3 oxidation state. It is a dopant in some types of
glass Glass is an amorphous (non-crystalline solid, non-crystalline) solid. Because it is often transparency and translucency, transparent and chemically inert, glass has found widespread practical, technological, and decorative use in window pane ...
in
laser A laser is a device that emits light through a process of optical amplification based on the stimulated emission of electromagnetic radiation. The word ''laser'' originated as an acronym for light amplification by stimulated emission of radi ...
s 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 Yttrium is a chemical element; it has Symbol (chemistry), symbol Y and atomic number 39. It is a silvery-metallic transition metal chemically similar to the lanthanides and has often been classified as a "rare-earth element". Yttrium is almost a ...
-based phosphors. Color TV screens contain between 0.5 and 1 g of europium oxide. Whereas trivalent europium gives red phosphors, the luminescence of divalent europium depends strongly on the composition of the host structure. UV to deep red luminescence can be achieved. 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, but as an additive, it can be particularly effective in improving the intensity of red phosphor. Europium is also used in the manufacture of fluorescent glass, increasing the general efficiency of fluorescent lamps. One of the more common persistent after-glow phosphors besides copper-doped zinc sulfide is europium-doped strontium aluminate. Europium fluorescence is used to interrogate biomolecular interactions in drug-discovery screens. It is also used in the anti-counterfeiting phosphors in euro banknotes. 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
enantiomer In chemistry, an enantiomer (Help:IPA/English, /ɪˈnænti.əmər, ɛ-, -oʊ-/ Help:Pronunciation respelling key, ''ih-NAN-tee-ə-mər''), also known as an optical isomer, antipode, or optical antipode, is one of a pair of molecular entities whi ...
ic purity. Europium compounds are used to label antibodies for sensitive detection of antigens in body fluids, a form of immunoassay. When these europium-labeled antibodies bind to specific antigens, the resulting complex can be detected with laser excited fluorescence.


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. The metal dust presents a fire and explosion hazard.


References


External links


It's Elemental – Europium
{{Authority control Chemical elements Chemical elements with body-centered cubic structure Lanthanides Neutron poisons Reducing agents