Gadolinium

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Gadolinium, 64Gd
Gadolinium-4.jpg
General properties
Name, symbol gadolinium, Gd
Pronunciation /?gd?'l?ni?m/
gad-?-lin-ee-?m
Appearance silvery white
Gadolinium in the periodic table
Hydrogen (diatomic nonmetal)
Helium (noble gas)
Lithium (alkali metal)
Beryllium (alkaline earth metal)
Boron (metalloid)
Carbon (polyatomic nonmetal)
Nitrogen (diatomic nonmetal)
Oxygen (diatomic nonmetal)
Fluorine (diatomic nonmetal)
Neon (noble gas)
Sodium (alkali metal)
Magnesium (alkaline earth metal)
Aluminium (post-transition metal)
Silicon (metalloid)
Phosphorus (polyatomic nonmetal)
Sulfur (polyatomic nonmetal)
Chlorine (diatomic nonmetal)
Argon (noble gas)
Potassium (alkali metal)
Calcium (alkaline earth metal)
Scandium (transition metal)
Titanium (transition metal)
Vanadium (transition metal)
Chromium (transition metal)
Manganese (transition metal)
Iron (transition metal)
Cobalt (transition metal)
Nickel (transition metal)
Copper (transition metal)
Zinc (transition metal)
Gallium (post-transition metal)
Germanium (metalloid)
Arsenic (metalloid)
Selenium (polyatomic nonmetal)
Bromine (diatomic nonmetal)
Krypton (noble gas)
Rubidium (alkali metal)
Strontium (alkaline earth metal)
Yttrium (transition metal)
Zirconium (transition metal)
Niobium (transition metal)
Molybdenum (transition metal)
Technetium (transition metal)
Ruthenium (transition metal)
Rhodium (transition metal)
Palladium (transition metal)
Silver (transition metal)
Cadmium (transition metal)
Indium (post-transition metal)
Tin (post-transition metal)
Antimony (metalloid)
Tellurium (metalloid)
Iodine (diatomic nonmetal)
Xenon (noble gas)
Caesium (alkali metal)
Barium (alkaline earth metal)
Lanthanum (lanthanide)
Cerium (lanthanide)
Praseodymium (lanthanide)
Neodymium (lanthanide)
Promethium (lanthanide)
Samarium (lanthanide)
Europium (lanthanide)
Gadolinium (lanthanide)
Terbium (lanthanide)
Dysprosium (lanthanide)
Holmium (lanthanide)
Erbium (lanthanide)
Thulium (lanthanide)
Ytterbium (lanthanide)
Lutetium (lanthanide)
Hafnium (transition metal)
Tantalum (transition metal)
Tungsten (transition metal)
Rhenium (transition metal)
Osmium (transition metal)
Iridium (transition metal)
Platinum (transition metal)
Gold (transition metal)
Mercury (transition metal)
Thallium (post-transition metal)
Lead (post-transition metal)
Bismuth (post-transition metal)
Polonium (post-transition metal)
Astatine (metalloid)
Radon (noble gas)
Francium (alkali metal)
Radium (alkaline earth metal)
Actinium (actinide)
Thorium (actinide)
Protactinium (actinide)
Uranium (actinide)
Neptunium (actinide)
Plutonium (actinide)
Americium (actinide)
Curium (actinide)
Berkelium (actinide)
Californium (actinide)
Einsteinium (actinide)
Fermium (actinide)
Mendelevium (actinide)
Nobelium (actinide)
Lawrencium (actinide)
Rutherfordium (transition metal)
Dubnium (transition metal)
Seaborgium (transition metal)
Bohrium (transition metal)
Hassium (transition metal)
Meitnerium (unknown chemical properties)
Darmstadtium (unknown chemical properties)
Roentgenium (unknown chemical properties)
Copernicium (transition metal)
Nihonium (unknown chemical properties)
Flerovium (post-transition metal)
Moscovium (unknown chemical properties)
Livermorium (unknown chemical properties)
Tennessine (unknown chemical properties)
Oganesson (unknown chemical properties)
?
Gd
?
Cm
europium ? gadolinium ? terbium
Atomic number (Z) 64
Group, block group n/a, f-block
Period period 6
Element category lanthanide
Standard atomic weight () (Ar) 157.25(3)[1]
Electron configuration [Xe] 4f7 5d1 6s2
Electrons per shell
2, 8, 18, 25, 9, 2
Physical properties
Phase solid
Melting point 1585 K ?(1312 C, ?2394 F)
Boiling point 3273 K ?(3000 C, ?5432 F)
Density near r.t. 7.90 g/cm3
when liquid, at m.p. 7.4 g/cm3
Heat of fusion 10.05 kJ/mol
Heat of vaporization 301.3 kJ/mol
Molar heat capacity 37.03 J/(molK)
Vapor pressure (calculated)
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 1836 2028 2267 2573 2976 3535
Atomic properties
Oxidation states 1, 2, 3 ?(a mildly basic oxide)
Electronegativity Pauling scale: 1.20
Ionization energies 1st: 593.4 kJ/mol
2nd: 1170 kJ/mol
3rd: 1990 kJ/mol
Atomic radius empirical: 180 pm
Covalent radius 1966 pm
Miscellanea
Crystal structure ?hexagonal close-packed (hcp) Hexagonal close packed cry
stal structure for gadolinium
Speed of sound thin rod 2680 m/s (at 20 C)
Thermal expansion a poly: 9.4 m/(mK) (at 100 C)
Thermal conductivity 10.6 W/(mK)
Electrical resistivity a, poly: 1.310 Om
Magnetic ordering ferromagnetic-paramagnetic transition at 293.4 K
Magnetic susceptibility (?mol) +755,000.010-6 cm3/mol (300.6 K)[2]
Young's modulus a form: 54.8 GPa
Shear modulus a form: 21.8 GPa
Bulk modulus a form: 37.9 GPa
Poisson ratio a form: 0.259
Vickers hardness 510 950 MPa
CAS Number 7440-54-2
History
Naming after the mineral Gadolinite (itself named after Johan Gadolin)
Discovery Jean Charles Galissard de Marignac (1880)
First isolation Lecoq de Boisbaudran (1886)
Most stable isotopes of gadolinium
iso NA half-life DM DE (MeV) DP
148Gd syn 75 y a 3.271 144Sm
150Gd syn 1.8106 y a 2.808 146Sm
152Gd 0.20% 1.081014 y a 2.205 148Sm
154Gd 2.18% is stable with 90 neutrons
155Gd 14.80% is stable with 91 neutrons
156Gd 20.47% is stable with 92 neutrons
157Gd 15.65% is stable with 93 neutrons
158Gd 24.84% is stable with 94 neutrons
160Gd 21.86% is stable with 96 neutrons
view talk edit | references | in Wikidata
Gadolinium is a chemical element with symbol Gd and atomic number 64. Gadolinium
is a silvery-white, malleable, and ductile rare earth metals It is found in nat
ure only in oxidized form, and even when separated, it usually has impurities of
the other rare earths. Gadolinium was discovered in 1880 by Jean Charles de Mar
ignac, who detected its oxide by using spectroscopy. It named for the mineral ga
dolinite, which is one of the minerals in which it is found, itself named for th
e chemist Johan Gadolin. Pure gadolinium was first isolated by the chemist Paul
Emile Lecoq de Boisbaudran in about 1886.
Gadolinium possesses unusual metallurgical properties, to the extent that as lit
tle as 1.0 percent of gadolinium can significantly improve the workability and r
esistance to oxidation at high temperatures of iron, chromium, and related metal
s. Gadolinium as a metal or a salt absorbs neutrons, and it is, therefore, used
sometimes for shielding in neutron radiography, and also in nuclear reactors.
Like most of the rare earths, gadolinium forms trivalent ions with fluorescent p
roperties, and salts of gadolinium(III) are used as phosphors in various applica
tions.
The kinds of gadolinium(III) ions occurring in water-soluble salts are toxic to
mammals. However, chelated gadolinium(III) compounds are far less toxic because
they carry gadolinium(III) through the kidneys, and out of the body, before the
free ion can be released into the tissues. Because of its paramagnetic propertie
s, solutions of chelated organic gadolinium complexes are used as intravenously
administered gadolinium-based MRI contrast agents in medical magnetic resonance
imaging.
Contents [hide]
1 Characteristics
1.1 Physical properties
1.2 Chemical properties
1.2.1 Chemical compounds
1.3 Isotopes
2 History
3 Occurrence
4 Production
5 Applications
6 Biological role
7 Safety
8 References
9 External links
Characteristics[edit]
A sample of gadolinium metal
Physical properties[edit]
Gadolinium is a silvery-white malleable and ductile rare earth metal. It crystal
lizes in hexagonal, in the close-packed a-form at room temperature, but, when he
ated to temperatures above 1235 C, it transforms into its -form, which has a body-
centered cubic structure.[3]
The isotope gadolinium-157 has the highest thermal neutron capture cross-section
among any stable nuclide: about 259,000 barns. Only xenon-135 has a higher capt
ure cross section, about 2.0 million barns, but this isotope is radioactive.[4]
Gadolinium is believed to be ferromagnetic at temperatures below 20 C (68 F)[5] an
d it is strongly paramagnetic above this temperature. There is evidence that gad
olinium is a helical antiferromagnetic, rather than a ferromagnetic, below 20 C (
68 F).[6] Gadolinium demonstrates a magnetocaloric effect whereby its temperature
increases when it enters a magnetic field, and decreases when it leaves the mag
netic field. The temperature is lowered to 5 C (41 F) for the gadolinium alloy Gd8
5Er15, and this effect is considerably stronger for the alloy Gd5(Si2Ge2), but a
t a much lower temperature (<85 K (-188.2 C; -306.7 F)).[7] A significant magnetoc
aloric effect is observed at higher temperatures, up to about 300 kelvin, in the
compounds Gd5(SixGe1-x)4.[8]
Individual gadolinium atoms can be isolated by encapsulating them into fullerene
molecules, where they can be visualized with transmission electron microscope.[
9] Individual Gd atoms and small Gd clusters can be incorporated into carbon nan
otubes.[10]
Chemical properties[edit]
See also: Category:Gadolinium compounds
Gadolinium combines with most elements to form Gd(III) derivatives. It also comb
ines with nitrogen, carbon, sulfur, phosphorus, boron, selenium, silicon, and ar
senic at elevated temperatures, forming binary compounds.[11]
Unlike the other rare earth elements, metallic gadolinium is relatively stable i
n dry air. However, it tarnishes quickly in moist air, forming a loosely-adherin
g gadolinium(III) oxide (Gd2O3), which spalls off, exposing more surface to oxid
ation.
4 Gd + 3 O2 ? 2 Gd2O3
Gadolinium is a strong reducing agent, which reduces oxides of several metals in
to their elements. Gadolinium is quite electropositive and reacts slowly with co
ld water and quite quickly with hot water to form gadolinium hydroxide:
2 Gd + 6 H2O ? 2 Gd(OH)3 + 3 H2
Gadolinium metal is attacked readily by dilute sulfuric acid to form solutions c
ontaining the colorless Gd(III) ions, which exist as [Gd(H2O)9]3+ complexes:[12]
2 Gd + 3 H2SO4 + 18 H2O ? 2 [Gd(H2O)9]3+ + 3 SO2-
4 + 3 H2
Gadolinium metal reacts with the halogens (X2) at temperature about 200 C:
2 Gd + 3 X2 ? 2 GdX3
Chemical compounds[edit]
In the great majority of its compounds, gadolinium adopts the oxidation state +3
. All four trihalides are known. All are white except for the iodide, which is y
ellow. Most commonly encountered of the halides is gadolinium(III) chloride (GdC
l3). The oxide dissolves in acids to give the salts, such as gadolinium(III) nit
rate.
Gadolinium(III), like most lanthanide ions, forms complexes with high coordinati
on numbers. This tendency is illustrated by the use of the chelating agent DOTA,
an octadentate ligand. Salts of [Gd(DOTA)]- are useful in magnetic resonance im
aging. A variety of related chelate complexes have been developed, including gad
odiamide.
Reduced gadolinium compounds are known, especially in the solid state. Gadoliniu
m(II) halides are obtained by heating Gd(III) halides in presence of metallic Gd
in tantalum containers. Gadolinium also form sesquichloride Gd2Cl3, which can b
e further reduced to GdCl by annealing at 800 C. This gadolinium(I) chloride form
s platelets with layered graphite-like structure.[13]
Isotopes[edit]
Main article: Isotopes of gadolinium
Naturally occurring gadolinium is composed of six stable isotopes, 154Gd, 155Gd,
156Gd, 157Gd, 158Gd and 160Gd, and one radioisotope, 152Gd, with the isotope 15
8Gd being the most abundant (24.84% natural abundance). The predicted double bet
a decay of 160Gd has never been observed (the only lower limit on its half-life
of more than 1.31021 years has been set experimentally[14]).
Twenty-nine radioisotopes of gadolinium have been observed, with the most stable
being 152Gd (naturally occurring) with a half-life of about 1.081014 years, and
150Gd with a half-life of 1.79106 years. All of the remaining radioactive isotope
s have half-lives of less than 75 years. The majority of these have half-lives o
f less than 25 seconds. Gadolinium isotopes have four metastable isomers, with t
he most stable being 143mGd (t1/2=110 seconds), 145mGd (t1/2=85 seconds) and 141
mGd (t1/2=24.5 seconds).
The isotopes with atomic masses lower than the most abundant stable isotope, 158
Gd, primarily decay via electron capture to isotopes of europium. At higher atom
ic masses, the primary decay mode is beta decay, and the primary products are is
otopes of terbium.
History[edit]
Gadolinium is named from the mineral gadolinite, in turn named for Finnish chemi
st and geologist Johan Gadolin.[3] In 1880, the Swiss chemist Jean Charles Galis
sard de Marignac observed the spectroscopic lines from gadolinium in samples of
gadolinite (which actually contains relatively little gadolinium, but enough to
show a spectrum), and in the separate mineral cerite. The latter mineral proved
to contain far more of the element with the new spectral line, De Marignac event
ually separated a mineral oxide from cerite which he realized was the oxide of t
his new element. He named the oxide "gadolinia." Because he realized that "gadol
inia" was the oxide of a new element, he is credited with discovery of gadoliniu
m. The French chemist Paul mile Lecoq de Boisbaudran carried out the separation o
f gadolinium metal from gadolinia, in 1886.
Occurrence[edit]
Gadolinite
Gadolinium is a constituent in many minerals such as monazite and bastnsite, whic
h are oxides. The metal is too reactive to exist naturally. Ironically, as noted
above, the mineral gadolinite actually contains only traces of this element. Th
e abundance in the Earth's crust is about 6.2 mg/kg.[3] The main mining areas ar
e in China, the USA, Brazil, Sri Lanka, India, and Australia with reserves expec
ted to exceed one million tonnes. World production of pure gadolinium is about 4
00 tonnes per year. The only known mineral with essential gadolinium, lepersonni
te-(Gd), is very rare.[15][16]
Production[edit]
Gadolinium is produced both from monazite and bastnsite.
Crushed minerals are extracted with hydrochloric acid or sulfuric acid, which co
nverts the insoluble oxides into soluble chlorides or sulfates.
The acidic filtrates are partially neutralized with caustic soda to pH 3 4. Thoriu
m precipitates as its hydroxide, and is then removed.
The remaining solution is treated with ammonium oxalate to convert rare earths i
nto their insoluble oxalates. The oxalates are converted to oxides by heating.
The oxides are dissolved in nitric acid that excludes one of the main components
, cerium, whose oxide is insoluble in HNO3.
The solution is treated with magnesium nitrate to produce a crystallized mixture
of double salts of gadolinium, samarium and europium.
The salts are separated by ion exchange chromatography.
The rare earth ions are then selectively washed out by a suitable complexing age
nt.[3]
Gadolinium metal is obtained from its oxide or salts by heating it with calcium
at 1450 C in an argon atmosphere. Sponge gadolinium can be produced by reducing m
olten GdCl3 with an appropriate metal at temperatures below 1312 C (the melting p
oint of Gd) at a reduced pressure.[3]
Applications[edit]
Gadolinium has no large-scale applications, but it has a variety of specialized
uses.
Because 157Gd has a high neutron cross-section, it is used to target tumors in n
eutron therapy. This element is effective for use with neutron radiography and i
n shielding of nuclear reactors. It is used as a secondary, emergency shut-down
measure in some nuclear reactors, particularly of the CANDU reactor type.[3] Gad
olinium is also used in nuclear marine propulsion systems as a burnable poison.
Gadolinium possesses unusual metallurgic properties, with as little as one perce
nt of gadolinium improving the workability and resistance of iron, chromium, and
related alloys to high temperatures and oxidation.
Gadolinium is paramagnetic at room temperature, with a ferromagnetic Curie point
of 20 C.[5] Paramagnetic ions, such as gadolinium, enhance nuclear relaxation ra
tes, making gadolinium useful for magnetic resonance imaging (MRI). Solutions of
organic gadolinium complexes and gadolinium compounds are used as intravenous M
RI contrast agent to enhance images in medical magnetic resonance imaging and ma
gnetic resonance angiography (MRA) procedures. Magnevist is the most widespread
example.[17][18] Nanotubes packed with gadolinium, dubbed "gadonanotubes", are 4
0 times more effective than the usual gadolinium contrast agent.[19] Once inject
ed, gadolinium-based contrast agents accumulate in abnormal tissues of the brain
and body, which provides a greater image contrast between normal and abnormal t
issues, facilitating location of abnormal cell growths and tumors.
Gadolinium as a phosphor is also used in other imaging. In X-ray systems gadolin
ium is contained in the phosphor layer, suspended in a polymer matrix at the det
ector. Terbium-doped gadolinium oxysulfide (Gd2O2S: Tb) at the phosphor layer co
nverts the X-rays released from the source into light. This material emits green
light at 540 nm due to the presence of Tb3+, which is very useful for enhancing
the imaging quality. The energy conversion of Gd is up to 20%, which means that
one-fifth of the X-rays striking the phosphor layer can be converted into light
photons. Gadolinium oxyorthosilicate (Gd2SiO5, GSO; usually doped by 0.1 1% of Ce
) is a single crystal that is used as a scintillator in medical imaging such as
positron emission tomography or for detecting neutrons.[20]
Gadolinium compounds are also used for making green phosphors for color TV tubes
.
Gadolinium-153 is produced in a nuclear reactor from elemental europium or enric
hed gadolinium targets. It has a half-life of 24010 days and emits gamma radiatio
n with strong peaks at 41 keV and 102 keV. It is used in many quality assurance
applications, such as line sources and calibration phantoms, to ensure that nucl
ear medicine imaging systems operate correctly and produce useful images of radi
oisotope distribution inside the patient.[21] It is also used as a gamma ray sou
rce in X-ray absorption measurements or in bone density gauges for osteoporosis
screening, as well as in the Lixiscope portable X-ray imaging system.[22]
Gadolinium is used for making gadolinium yttrium garnet (Gd:Y3Al5O12); it has mi
crowave applications and is used in fabrication of various optical components an
d as substrate material for magneto-optical films.
Gadolinium gallium garnet (GGG, Gd3Ga5O12) was used for imitation diamonds and f
or computer bubble memory.[23]
Gadolinium can also serve as an electrolyte in solid oxide fuel cells (SOFCs). U
sing gadolinium as a dopant for materials like cerium oxide (in the form of gado
linium doped ceria) creates an electrolyte with both high ionic conductivity and
low operating temperatures that are optimal for cost-effective production of fu
el cells.
Research is being conducted on magnetic refrigeration near room temperature, whi
ch could provide significant efficiency and environmental advantages over conven
tional refrigeration methods. Gadolinium-based materials, such as Gd5(SixGe1-x)4
, are currently the most promising materials owing to their high Curie temperatu
re and giant magnetocaloric effect. Pure Gd itself exhibits a large magnetocalor
ic effect near its Curie temperature of 20 C, and this has sparked great interest
into producing Gd alloys with a larger effect and tunable Curie temperature. In
Gd5(SixGe1-x)4, Si and Ge compositions can be varied to adjust the Curie temper
ature. This technology is still very early in development and significant materi
al improvements still need to be made before it is commercially viable.[8]
Biological role[edit]
Gadolinium has no known native biological role, but its compounds are used as re
search tools in biomedicine. Gd3+ compounds are components of MRI contrast agent
s. It is used in various ion channel electrophysiology experiments to block sodi
um leak channels and stretch activated ion channels.[24]
Safety[edit]
Main articles: MRI contrast agent and Nephrogenic systemic fibrosis
As a free ion, gadolinium is reported often to be highly toxic, but MRI contrast
agents are chelated compounds and are considered safe enough to be used in most
persons. The toxicity of free gadolinium ions in animals is due to interference
with a number of calcium-ion channel dependent processes. The 50% lethal dose i
s about 100 200 mg/kg. Toxicities have not been reported following low dose exposu
re to gadolinium ions. Toxicity studies in rodents, however show that chelation
of gadolinium (which also improves its solubility) decreases its toxicity with r
egard to the free ion by at least a factor of 100 (i.e., the lethal dose for the
Gd-chelate increases by 100 times).[25] It is believed therefore that clinical
toxicity of gadolinium-based contrast agents (GBCAs[26]) in humans will depend o
n the strength of the chelating agent; however this research is still not comple
te.[when?] About a dozen different Gd-chelated agents have been approved as MRI
contrast agents around the world.[27][28][29]
GBCAs have proved safer than the iodinated contrast agents used in X-ray radiogr
aphy or computed tomography. Anaphylactoid reactions are rare, occurring in appr
oximately 0.03 0.1%.[30]
Although gadolinium agents are useful for patients with renal impairment, in pat
ients with severe renal failure requiring dialysis, there is a risk of a rare bu
t serious illness called nephrogenic systemic fibrosis (NSF)[31] or nephrogenic
fibrosing dermopathy,[32] that is linked to the use of MRI contrast agents conta
ining gadolinium. The disease resembles scleromyxedema and to some extent sclero
derma. It may occur months after a contrast agent has been injected. Its associa
tion with gadolinium and not the carrier molecule is confirmed by its occurrence
 with various contrast materials in which gadolinium is carried by very differen
t carrier molecules. Similar but not identical symptoms to NSF may occur in subj
ects with normal or near normal renal function within hours to 2 months followin
g the administration of GBCAs; the name "gadolinium deposition disease" (GDD) ha
s been proposed for this condition, which occurs in the absence of pre-existent
disease or subsequently developed disease of an alternate known process. The cau
sal relationship was being investigated as of May 2016; preliminary investigatio
n suggested a true disease process.[26][33]
Current guidelines in the United States are that dialysis patients should only r
eceive gadolinium agents where essential and to consider performing an iodinated
contrast-enhanced CT when feasible. If a contrast-enhanced MRI must be performe
d on a dialysis patient, it is recommended that certain high-risk contrast agent
s be avoided and that a lower dose be considered. The American College of Radiol
ogy recommends that contrast-enhanced MRI examinations be performed as closely b
efore dialysis as possible as a precautionary measure, although this has not bee
n proven to reduce the likelihood of developing NSF.[34]
References[edit]
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