Europium

Europium is a chemical element with the symbol Eu

and atomic number 63. Europium is the most reactive Europium, 63Eu
lanthanide by far, having to be stored under an inert
fluid to protect it from atmospheric oxygen or
moisture. Europium is also the softest lanthanide, as
it can be dented with a fingernail and easily cut with
a knife. When oxidation is removed a shiny-white
metal is visible. Europium was isolated in 1901 and is
named after the continent of Europe.[5] 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 Europium
metals. Most applications of europium exploit the Pronunciation /jʊəˈroʊpiəm/
phosphorescence of europium compounds. Europium (yoor-OH-pee-əm)
is one of the rarest of the rare earth elements on
Earth.[6] Appearance silvery white, with a pale
yellow tint;[1] but rarely seen
without oxide discoloration
151.964(1)[2]
Contents Standard atomic
weight Ar, std(Eu)
Characteristics Europium in the periodic table
Physical properties
Chemical properties –
↑
Eu(II) vs. Eu(III) Eu
↓
Isotopes Am
Europium as a nuclear fission product samarium ← europium → gadolinium
Occurrence Atomic number (Z) 63
Production Group group n/a
Compounds Period period 6
Halides
Block f-block
Chalcogenides and pnictides
Element category Lanthanide
History
Electron [Xe] 4f7 6s2
Applications configuration
Precautions
Electrons per 2, 8, 18, 25, 8, 2
References shell
External links Physical properties
Phase at STP solid

Characteristics Melting point 1099 K (826 °C, 1519 °F)

 Boiling point 1802 K (1529 °C, 2784 °F)
Density (near r.t.) 5.264 g/cm3
Physical properties
when liquid 5.13 g/cm3
(at m.p.)
Heat of fusion 9.21 kJ/mol
Heat of 176 kJ/mol
vaporization
Molar heat 27.66 J/(mol·K)
capacity
About 300 g of dendritic sublimated Vapor pressure
99.998% pure europium handled in a
P (Pa) 1 10 100 1k 10 k 100 k
glove box
at T (K) 863 957 1072 1234 1452 1796

Atomic properties
Oxidation states +1, +2, +3 (a mildly basic
oxide)
Electronegativity Pauling scale: 1.2
Ionization 1st: 547.1 kJ/mol
energies 2nd: 1085 kJ/mol
3rd: 2404 kJ/mol

Oxidized europium, coated with Atomic radius empirical: 180 pm

yellow europium(II) carbonate
Covalent radius 198±6 pm

Europium is a ductile metal with a hardness similar to

that of lead. It crystallizes in a body-centered cubic
Spectral lines of europium
lattice.[7] Some properties of europium are strongly
influenced by its half-filled electron shell. Europium Other properties
has the second lowest melting point and the lowest Natural primordial
density of all lanthanides.[7] occurrence

Europium becomes a superconductor when it is Crystal structure body-centered cubic (bcc)

cooled below 1.8 K and compressed to above 80
GPa. This occurs because europium is divalent in the
metallic state,[8] and is converted into the trivalent
state by the applied pressure. In the divalent state, the Thermal poly: 35.0 µm/(m·K) (at r.t.)
strong local magnetic moment (J = 7/2) suppresses the expansion
superconductivity, which is induced by eliminating
Thermal est. 13.9 W/(m·K)
this local moment (J = 0 in Eu3+).[9]
conductivity
Electrical poly: 0.900 µΩ·m (at r.t.)
Chemical properties resistivity
Magnetic ordering paramagnetic[3]
Europium is the most reactive rare-earth element. It
rapidly oxidizes in air, so that bulk oxidation of a Magnetic +34,000.0·10−6 cm3/mol[4]
centimeter-sized sample occurs within several susceptibility
days.[10] Its reactivity with water is comparable to
that of calcium, and the reaction is Young's modulus 18.2 GPa
Shear modulus 7.9 GPa
2 Eu + 6 H2O → 2 Eu(OH)3 + 3 H2
Bulk modulus 8.3 GPa
Because of the high reactivity, samples of solid Poisson ratio 0.152
europium rarely have the shiny appearance of the
fresh metal, even when coated with a protective layer Vickers hardness 165–200 MPa
of mineral oil. Europium ignites in air at 150 to CAS Number 7440-53-1
180 °C to form europium(III) oxide:
History
4 Eu + 3 O2 → 2 Eu2O3 Naming after Europe
Discovery and Eugène-Anatole Demarçay
Europium dissolves readily in dilute sulfuric acid to
first isolation (1896, 1901)
form pale pink solutions of the hydrated Eu(III),
which exist as a nonahydrate:[11] Main isotopes of europium

2 Eu + 3 H2SO4 + 18 H2O → 2 Iso‐ Abun‐ Half-life Decay Pro‐

[Eu(H2O)9]3+ + 3 SO2−
4 + 3 H2
tope dance (t1/2) mode duct

150Eu syn 36.9 y ε 150Sm

Eu(II) vs. Eu(III) 151Eu 47.8% 5×1018 y α 147Pm

Although usually trivalent, europium readily forms ε 152Sm

152Eu
divalent compounds. This behavior is unusual for syn 13.54 y
most lanthanides, which almost exclusively form β− 152Gd

compounds with an oxidation state of +3. The +2 153Eu 52.2% stable

state has an electron configuration 4f7 because the
half-filled f-shell provides more stability. In terms of 154Eu syn 8.59 y β− 154Gd

size and coordination number, europium(II) and

155Eu syn 4.76 y β− 155Gd
barium(II) are similar. The sulfates of both barium
and europium(II) are also highly insoluble in
water.[12] 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.[13]

Isotopes

Naturally occurring europium is composed of 2 isotopes, 151Eu and 153Eu, which occur in almost equal
proportions; 153Eu is slightly more abundant (52.2% natural abundance). While 153Eu is stable, 151Eu was
+11
found to be unstable to alpha decay with a half-life of 5 −3 × 1018 years in 2007,[14] 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 (t1/2=12.8 hours), 152m1Eu (t1/2=9.3116 hours) and
152m2Eu (t =96 minutes).[15]
1/2

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).[15]

Europium as a nuclear fission product

Medium-lived Thermal neutron capture cross sections
fission products
Isotope 151Eu 152Eu 153Eu 154Eu 155Eu
Prop: t½ Yield Q * βγ *
Unit: (a) (%) (keV) Yield ~10 low 1580 >2.5 330
155Eu 4.76 0.0803 252 βγ
Barns 5900 12800 312 1340 3950
85Kr 10.76 0.2180 687 βγ
113mCd 14.1 0.0008 316 β
90Sr28.9 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.

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.[16] 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.
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.[17][18][19][20][21][22][23]

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).[24] 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.[25]

Depletion or enrichment of europium in minerals relative to other

rare-earth elements is known as the europium anomaly.[26]
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. The average crustal abundance of
europium is 2–2.2 ppm.

Monazite 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.[27] 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.[28][29][30][31][32]

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 recently identified higher-than-
expected levels of europium within the star J1124+4535, hypothesizing that this star originated in a dwarf
galaxy that collided with the Milky Way billions of years ago.[33][34]

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 LnPO4
(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, 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.[35] 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.[24][35][36][37][38]

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.[39][40][41] 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.[24][42]

Compounds
Europium compounds tend to exist trivalent oxidation state under most
conditions. Commonly these compounds feature Eu(III) bound by 6–9
oxygenic ligands, typically water. These compounds, the chlorides,
sulfates, nitrates, are soluble in water or polar organic solvent.
Lipophilic europium complexes often feature acetylacetonate-like
ligands, e.g., Eufod.

Halides

Europium metal reacts with all the halogens:

2 Eu + 3 X2 → 2 EuX3 (X = F, Cl, Br, I) Europium sulfate, Eu2(SO4)3

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).[7]

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. Europium sulfate fluorescing red
Three oxides are known: europium(II) oxide (EuO), europium(III) under ultraviolet light
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. EuS is prepared by sulfiding the oxide at temperatures sufficiently high to decompose the Eu2O3:[43]

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 including those eventually assigned to
europium.[44]
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 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.[45][46][47][48][49]

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,[50] 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.[50] 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[51] 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.[37][52]

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 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.[53][54] Color TV screens
contain between 0.5 and 1 g of europium oxide.[55] Whereas
trivalent europium gives red phosphors,[56] the luminescence of
divalent europium depends strongly on the composition of the host
structure. UV to deep red luminescence can be achieved.[57][58] The
Europium is one of the elements
two classes of europium-based phosphor (red and blue), combined
involved in emitting red light in CRT
with the yellow/green terbium phosphors give "white" light, the
televisions.
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,[53]
but as an additive, it can be particularly effective in improving the intensity of red phosphor.[6] Europium is
also used in the manufacture of fluorescent glass, increasing the general efficiency of fluorescent lamps.[6]
One of the more common persistent after-glow phosphors besides copper-doped zinc sulfide is europium-
doped strontium aluminate.[59] Europium fluorescence is used to interrogate biomolecular interactions in
drug-discovery screens. It is also used in the anti-counterfeiting phosphors in euro banknotes.[60][61]
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.[62][63][64][65][66]

A recent (2015) application of europium is in quantum memory chips which can reliably store information
for days at a time; these could allow sensitive quantum data to be stored to a hard disk-like device and
shipped around.[67]

Precautions
There are no clear indications that europium is particularly toxic Europium
compared to other heavy metals. Europium chloride, nitrate and
Hazards
oxide have been tested for toxicity: europium chloride shows an
acute intraperitoneal LD50 toxicity of 550 mg/kg and the acute oral GHS pictograms
LD50 toxicity is 5000 mg/kg. Europium nitrate shows a slightly
higher intraperitoneal LD50 toxicity of 320 mg/kg, while the oral
GHS Signal word Danger
toxicity is above 5000 mg/kg.[69][70] The metal dust presents a fire
and explosion hazard.[71] GHS hazard H250
statements
GHS precautionary P222, P231,
References statements P422[68]
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External links
It's Elemental – Europium (http://education.jlab.org/itselemental/ele063.html)

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