Loading

Gadolinium

64 europiumgadolinium terbium
-

Gd

Cm
General
Name, Symbol, Number gadolinium, Gd, 64
Element category lanthanides
Group, Period, Block n/a, 6, f
Appearance silvery white
Standard atomic weight 157.25(3)  g·mol−1
Electron configuration [Xe] 4f7 5d1 6s2
Electrons per shell 2, 8, 18, 25, 9, 2
Physical properties
Phase solid
Density (near r.t.) 7.90  g·cm−3
Liquid density at m.p. 7.4  g·cm−3
Melting point 1585 K
(1312 °C, 2394 °F)
Boiling point 3546 K
(3273 °C, 5923 °F)
Heat of fusion 10.05  kJ·mol−1
Heat of vaporization 301.3  kJ·mol�����������1
Specific heat capacity (25 °C) 37.03  J·mol−1·K−1
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
Crystal structure hexagonal
Oxidation states 1, 2, 3
(mildly basic oxide)
Electronegativity 1.20 (Pauling scale)
Ionization energies
(more)
1st:  593.4  kJ·mol−1
2nd:  1170  kJ·mol−1
3rd:  1990  kJ·mol−1
Atomic radius 180pm
Covalent radius 196±6  pm
Miscellaneous
Magnetic ordering ferromagnetic/paramagnetic
transition at 292 K[1]
Electrical resistivity (r.t.) (α, poly)
1.310 µΩ·m
Thermal conductivity (300 K) 10.6  W·m−1·K−1
Thermal expansion (100 °C) (α, poly)
9.4 µm/(m·K)
Speed of sound (thin rod) (20 °C) 2680 m/s
Young's modulus (α form) 54.8  GPa
Shear modulus (α form) 21.8  GPa
Bulk modulus (α form) 37.9  GPa
Poisson ratio (α form) 0.259
Vickers hardness 570  MPa
CAS registry number 7440-54-2
Most-stable isotopes
Main article: Isotopes of gadolinium
iso NA half-life DM DE (MeV) DP
152Gd 0.20% 1.08×1014 y α 2.205 148Sm
154Gd 2.18% 154Gd is stable with 90 neutrons
155Gd 14.80% 155Gd is stable with 91 neutrons
156Gd 20.47% 156Gd is stable with 92 neutrons
157Gd 15.65% 157Gd is stable with 93 neutrons
158Gd 24.84% 158Gd is stable with 94 neutrons
160Gd 21.86% >1.3×1021y ββ 1.7 160Dy
References

Gadolinium (pronounced /ˌɡædəˈlɪniəm/) is a chemical element that has the symbol Gd and atomic number 64. It is a silvery-white, malleable and ductile rare-earth metal. Gadolinium has exceptionally high absorption of neutrons and therefore is used for shielding in neutron radiography and in nuclear reactors. Because of its paramagnetic properties, solutions of organic gadolinium complexes and gadolinium compounds are the most popular intravenous MRI contrast agents in medical magnetic resonance imaging.

Characteristics

Physical

Gadolinium is a silvery-white, malleable and ductile rare-earth metal. It crystallizes in hexagonal, close-packed alpha form at room temperature, but, when heated to temperatures above 1235 °C, it transforms into its beta form, which has a body-centered cubic structure.[2]

Gadolinium-157 has the highest thermal neutron capture cross-section of any known nuclide with the exception of xenon-135, 49,000 barns, but it also has a fast burn-out rate, limiting its usefulness as a nuclear control rod material.[3]

Gadolinium is strongly paramagnetic at room temperature, and exhibits ferromagnetic properties below room temperature. Gadolinium demonstrates a magnetocaloric effect whereby its temperature increases when it enters a magnetic field and decreases when it leaves the magnetic field. The effect is considerably stronger for the gadolinium alloy Gd5(Si2Ge2) [4].

Individual gadolinium atoms have been isolated by encapsulating them into fullerene molecules and visualized with transmission electron microscope.[5]. Individual Gd atoms and small Gd clusters have also been incorporated into carbon nanotubes.[6]

Chemical

Unlike other rare earth elements, gadolinium is relatively stable in dry air. However, it tarnishes quickly in moist air, forming a loosely-adhering oxide which spalls off, exposing more surface to oxidation.

4Gd + 3O2 → 2Gd2O3

Gadolinium is a strong reducing agent, which reduces oxides of several metals, such as Fe, Cr, Sn, Pb, Mn and Zr, into their elements.[2] Gadolinium is quite electropositive and reacts slowly with cold water and quite quickly with hot water to form gadolinium hydroxide:

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

Gadolinium metal reacts with all the halogens at temperature about 200 °C:

2Gd(s) + 3F2(g) → 2GdF3(s) [white]
2Gd(s) + 3Cl2(g) → 2GdCl3(s) [white]
2Gd(s) + 3Br2(g) → 2GdBr3(s) [white]
2Gd(s) + 3I2(g) → 2GdI3(s) [yellow]

Gadolinium dissolves readily in dilute sulphuric acid to form solutions containing the colorless Gd(III) ions, which exist as a [Gd(OH2)9]3+ complexes:[7]

2Gd(s) + 3H2SO4(aq) → 2Gd3+(aq) + 3SO42-(aq) + 3H2(g)

Gadolinium combines with nitrogen, carbon, sulfur, phosphorus, boron, selenium, silicon and arsenic at elevated temperatures, forming binary compounds.[2] In those compounds, Gd mostly exhibit oxidation state +3. Gadolinium(II) halogenides are obtained by annealing Gd(III) halogenides in presence of metallic Gd in tantalum containers. Gadolinium also form sesquichloride Gd2Cl3, which can be further reduced to GdCl by annealing at 800 °C. This gadolinium(I) chloride forms platelets with layered graphite-like structure.[8]

Compounds

Compounds of gadolinium include:

Isotopes

Naturally occurring gadolinium is composed of 6 stable isotopes, 154Gd, 155Gd, 156Gd, 157Gd, 158Gd and 160Gd, and 1 radioisotope, 152Gd, with 158Gd being the most abundant (24.84% natural abundance). The predicted double beta decay of 160Gd has never been observed (only lower limit on its half-life of more than 1.3×1021 years has been set experimentally [9]).

Twenty nine radioisotopes have been characterized, with the most stable being alpha-decaying 152Gd (naturally occurring) with a half-life of 1.08×1014 years, and 150Gd with a half-life of 1.79×106 years. All of the remaining radioactive isotopes have half-lives less than 74.7 years. The majority of these have half-lives less than 24.6 seconds. Gadolinium isotopes have 4 metastable isomers, with the most stable being 143mGd (T½=110 seconds), 145mGd (T½=85 seconds) and 141mGd (T½=24.5 seconds).

The primary decay mode at atomic masses lower than the most abundant stable isotope, 158Gd, is electron capture, and the primary mode at higher atomic masses is beta decay. The primary decay products for isotopes of weights lower than 158Gd are the element Eu (europium) isotopes and the primary products at higher weights are the element Tb (terbium) isotopes.

History

In 1880, Swiss chemist Jean Charles Galissard de Marignac observed spectroscopic lines due to gadolinium in samples of didymium and gadolinite; French chemist Paul Émile Lecoq de Boisbaudran separated gadolinia, the oxide of Gadolinium, from Mosander's yttria in 1886. The element itself was isolated only recently. Gadolinium, like the mineral gadolinite, is named after Finnish chemist and geologist Johan Gadolin. In older literature, the natural form of the element is often called an earth, meaning that the element came from Earth.[2]

Occurrence

Gadolinite

Gadolinium is never found in nature as the free element, but is contained in many rare minerals such as monazite and bastnäsite. It occurs only in trace amounts in the mineral gadolinite, which was also named after Johan Gadolin. The abundance in the earth crust is about 6.2 mg/kg.[2]

Production

Gadolinium is produced both from monazite and bastnäsite. Crushed minerals are attacked by hydrochloric or sulfuric acid that transforms insoluble rare-earth oxides into soluble chlorides or sulfates. The acidic filtrates are partially neutralized with caustic soda to pH 3-4. Thorium precipitates out of solution as hydroxide and is removed. After that the solution is treated with ammonium oxalate to convert rare earths in to their insoluble oxalates. The oxalates are converted to oxides by annealing. 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. In this process, rare-earth ions are sorbed onto suitable ion-exchange resin by exchange with hydrogen, ammonium or cupric ions present in the resin. The rare earth ions are then selectively washed out by suitable complexing agent.[2]

Gadolinium metal is obtained from its oxide or salts by heating with calcium at 1450 °C under argon atmosphere. Sponge gadolinium can be produced by reducing molten GdCl3 with an appropriate metal oxide at temperatures below 1312 °C (melting point of Gd) in a reduced pressure.[2]

Applications

Because of extremely high neutron cross-section of gadolinium, this element is very effective for use with neutron radiography and in shielding of nuclear reactors. It is used as a secondary, emergency shut-down measure in some nuclear reactors, particularly of the CANDU type.[2] Gadolinium is also used in nuclear marine propulsion systems as a burnable poison.

Gadolinium is an efficient catalyst used for decarboxylation of oxaloacetic acid, convertion of orto- to para-hydrogen and polymerization of ethylene.[2]

Gadolinium also possesses unusual metallurgic properties, with as little as 1% of gadolinium improving the workability and resistance of iron, chromium, and related alloys to high temperatures and oxidation.

Because of their paramagnetic properties, solutions of organic gadolinium complexes and gadolinium compounds are used as intravenous MRI contrast agent to enhance images in medical magnetic resonance imaging. Magnevist is the most widespread example.[10]

Gadolinium-153 helps calibrate positron emission tomography (PET) systems that are used in nuclear medicine for functional imaging. This PET image of the human brain shows the difference between a normal brain and the clinically depressed patient. The blue color indicates less glucose metabolism in a normal brain. The green, yellow, and red colors indicate areas of higher glucose metabolism characteristic of a depressed patient.[11]

Beside MRI, gadolinium (Gd) is also used in other imaging. In X-ray, gadolinium is contained in the phosphor layer, suspending in a polymer matrix at the detector. Terbium-doped gadolinium oxysulfide (Gd2O2S: Tb) at the phosphor layer is to convert the X-rays releasing 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 of the X-ray that is exposed to the photographic film. The energy conversion of Gd is up to 20%, which means, one-fifth of the X-ray striking on 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.[12]

Gadolinium-153 is produced in a nuclear reactor from elemental europium or enriched gadolinium targets. It has a half-life of 240±10 days and emits gamma radiation 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 nuclear medicine imaging systems operate correctly and produce useful images of radioisotope distribution inside the patient.[11] It is also used as a gamma ray source in X-ray absorption measurements or in bone density gauges for osteoporosis screening, as well as in the Lixiscope portable X-ray imaging system.[13]

Gadolinium is used for making gadolinium yttrium garnet (Gd3Ga5O12); it has microwave applications and is used in fabrication of various optical components and as substrate material for magneto–optical films. Gadolinium compounds are also used for making phosphors for colour TV tubes, compact discs and computer memory.[14]

Biological role

Gadolinium has no known native biological role, but in research on biological systems it has a few roles. It is used as a component of MRI contrast agents, as, in the 3+ oxidation state, the metal has 7 unpaired f electrons. This causes water around the contrast agent to relax quickly, enhancing the quality of the MRI scan. Second, as a member of the lanthanides, it is used in various ion channel electrophysiology experiments, where it is used to block sodium leak channels, as well as to stretch activated ion channels.[15]

Safety

As a free ion, gadolinium is highly toxic but is generally regarded as safe when administered as a chelated compound. The compounds can be classified by whether they are macro-cyclic or linear geometry and whether they are ionic or not. Cyclical ionic Gd compounds being considered the least likely to release the Gd ion and hence the most safe[16]. US Food and Drug Administration approved Gd chelated contrast agents include: Omniscan, Multihance, Magnevist, ProHance, Vasovist and OptiMARK.[17]

Gadolinium MRI contrast agents have proved safer than the iodinated contrast agents used in X-ray radiography or computed tomography. Anaphylactoid reactions are rare, occurring in approx. 0.03-0.1%.[18]

Although gadolinium agents have proved useful for patients with renal impairment, in patients with severe renal failure requiring dialysis there is a risk of a rare but serious illnesses, such as nephrogenic systemic fibrosis[19] and nephrogenic fibrosing dermopathy[20], that may be linked to the use of certain gadolinium-containing agents. Although a causal link has not been definitively established, current guidelines in the United States are that dialysis patients should only receive gadolinium agents where essential, and that dialysis should be performed as soon as possible after the scan is complete, in order to remove the agent from the body promptly.[21]

References

  1. ^ Charles Kittel (1996). Introduction to Solid State Physics. New York: Wiley. p. 449. 
  2. ^ a b c d e f g h i Patnaik, Pradyot (2003). Handbook of Inorganic Chemical Compounds. McGraw-Hill. pp. 302–306. ISBN 0070494398. http://books.google.com/books?id=Xqj-TTzkvTEC&pg=PA243. Retrieved on 2009-06-06. 
  3. ^ "Gadolinium". Neutron News (NIST) 3 (3): 29. 1992. http://www.ncnr.nist.gov/resources/n-lengths/elements/gd.html. Retrieved on 2009-06-06. 
  4. ^ Karl Gschneidner, Jr. and Kerry Gibson (2001-12-07). "Magnetic refrigerator successfully tested". Ames Laboratory. http://www.external.ameslab.gov/news/release/01magneticrefrig.htm. Retrieved on 2006-12-17. 
  5. ^ Suenaga, Kazu (2003). "Evidence for the Intramolecular Motion of Gd Atoms in a Gd2@C92 Nanopeapod". Nano Letters 3: 1395. doi:10.1021/nl034621c. 
  6. ^ Hashimoto, A; Yorimitsu, H; Ajima, K; Suenaga, K; Isobe, H; Miyawaki, J; Yudasaka, M; Iijima, S; Nakamura, E (Jun 2004). "Selective deposition of a gadolinium(III) cluster in a hole opening of single-wall carbon nanohorn" (Free full text). Proceedings of the National Academy of Sciences of the United States of America 101 (23): 8527–30. doi:10.1073/pnas.0400596101. ISSN 0027-8424. PMID 15163794. PMC: 423227. http://www.pnas.org/cgi/pmidlookup?view=long&pmid=15163794.  edit
  7. ^ "Chemical reactions of Gadolinium". Webelements. https://www.webelements.com/gadolinium/chemistry.html. Retrieved on 2009-06-06. 
  8. ^ Cotton (2007). Advanced inorganic chemistry, 6th ed. Wiley-India. p. 1128. ISBN 8126513381. http://books.google.com/books?id=U3MWRONWAmMC&pg=PA1128. 
  9. ^ F. A. Danevich et al., Quest for double beta decay of 160Gd and Ce isotopes. Nucl. Phys. A 694(2001)375.
  10. ^ Gary Liney (2006). MRI in clinical practice. Springer. pp. 13;30. ISBN 184628161X. http://books.google.com/books?id=xpCffxNrCXYC&pg=PA13. 
  11. ^ a b "Gadolinium-153". Pacific Northwest National Laboratory. http://radioisotopes.pnl.gov/gadolinium.stm. Retrieved on 2009-06-06. 
  12. ^ <Ryzhikov, V. D. (2005). "Use of gadolinium oxyorthosilicate scintillators in x-ray radiometers". Optical Engineering 44: 016403. doi:10.1117/1.1829713. 
  13. ^ "Lixi, Inc.". http://www.ndt.net/news/lixi.htm. Retrieved on 2009-06-06. 
  14. ^ C. R. Hammond (2000). The Elements, in Handbook of Chemistry and Physics 81th edition. CRC press. ISBN 0849304814. 
  15. ^ Yeung, Ew; Allen, Dg (Aug 2004). "Stretch-activated channels in stretch-induced muscle damage: role in muscular dystrophy.". Clinical and experimental pharmacology & physiology 31 (8): 551–6. doi:10.1111/j.1440-1681.2004.04027.x. ISSN 0305-1870. PMID 15298550. 
  16. ^ "Questions and Answers on Magnetic resonance imaging". http://www.ismrm.org/special/EMEA2.pdf. Retrieved on 2009-06-06. 
  17. ^ "Information on Gadolinium-Containing Contrast Agents". http://www.fda.gov/cder/drug/infopage/gcca/default.htm. 
  18. ^ Murphy KJ, Brunberg JA, Cohan RH (01 October 1996). "Adverse reactions to gadolinium contrast media: A review of 36 cases". AJR Am J Roentgenol 167 (4): 847–9. PMID 8819369. http://www.ajronline.org/cgi/pmidlookup?view=long&pmid=8819369. 
  19. ^ H.S. Thomsen, S.K. Morcos and P. Dawson (November 2006). "Is there a causal relation between the administration of gadolinium-based contrast media and the development of nephrogenic systemic fibrosis (NSF)?". Clinical Radiology 61 (11): 905–6. doi:10.1016/j.crad.2006.09.003. 
  20. ^ Grobner T. (2006-01-23). "Gadolinium — a specific trigger for the development of nephrogenic fibrosing dermopathy and nephrogenic systemic fibrosis?". Nephrology Dialysis Transplantation 21 (4): 1104–8. doi:10.1093/ndt/gfk062. PMID 16431890. 
  21. ^ "FDA Public Health Advisory: Gadolinium-containing Contrast Agents for Magnetic Resonance Imaging". http://www.fda.gov/cder/drug/advisory/gadolinium_agents.htm. Retrieved on 2009-06-06. 

External links

 

The content of this section is licensed under the GNU Free Documentation License (local copy). It uses material from the Wikipedia article "Gadolinium" modified July 23, 2009 with previous authors listed in its history.