Gadolinium(III) oxide

Last updated
Gadolinium(III) oxide
Gd2O3powder.jpg
Names
Other names
gadolinium sesquioxide, gadolinium trioxide
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.031.861 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 235-060-9
PubChem CID
RTECS number
  • LW4790000
UNII
  • InChI=1S/2Gd.3O/q2*+3;3*-2 Yes check.svgY
    Key: CMIHHWBVHJVIGI-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/2Gd.3O/q2*+3;3*-2
    Key: CMIHHWBVHJVIGI-UHFFFAOYAI
  • [Gd+3].[Gd+3].[O-2].[O-2].[O-2]
Properties
Gd2O3
Molar mass 362.50 g/mol
Appearancewhite odorless powder
Density 7.07 g/cm3 [1]
Melting point 2,420 °C (4,390 °F; 2,690 K)
insoluble
1.8×10−23
Solubility soluble in acid
+53,200·10−6 cm3/mol
Structure
cubic, cI80, Monoclinic
Ia-3, No. 206, C2/m, No. 12
Hazards
GHS labelling:
GHS-pictogram-exclam.svg GHS-pictogram-pollu.svg
Warning
H319, H410
P264, P273, P280, P305+P351+P338, P337+P313, P391, P501
Safety data sheet (SDS) External MSDS
Related compounds
Other anions
Gadolinium(III) chloride
Other cations
Europium(III) oxide, Terbium(III) oxide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Gadolinium(III) oxide (archaically gadolinia) is an inorganic compound with the formula Gd2O3. It is one of the most commonly available forms of the rare-earth element gadolinium, derivatives of which are potential contrast agents for magnetic resonance imaging.

Contents

Structure

Cubic Gd2O3 Tl2O3structure.jpg
Cubic Gd2O3
Monoclinic Gd2O3 (gadolinium atoms are green, oxygen atoms are red) Gd2O3structure.jpg
Monoclinic Gd2O3 (gadolinium atoms are green, oxygen atoms are red)

Gadolinium oxide adopts two structures. The cubic (cI80, Ia3), No. 206) structure is similar to that of manganese(III) oxide and heavy trivalent lanthanide sesquioxides. The cubic structure features two types of gadolinium sites, each with a coordination number of 6 but with different coordination geometries. The second polymorph is monoclinic (Pearson symbol mS30, space group C2/m, No. 12). [2] At room temperature, the cubic structure is more stable. The phase change to the monoclinic structure takes place at 1200 °C. Above 2100 °C to the melting point at 2420 °C, a hexagonal phase dominates. [3]

Preparation and chemistry

Gadolinium oxide can be formed by thermal decomposition of the hydroxide, nitrate, carbonate, or oxalates. [4] Gadolinium oxide forms on the surface of gadolinium metal.

Gadolinium oxide is a rather basic oxide, indicated by its ready reaction with carbon dioxide to give carbonates. It dissolves readily in the common mineral acids with the complication that the oxalate, fluoride, sulfate and phosphate are very insoluble in water and may coat the grains of oxide, thereby preventing the complete dissolution. [5]

Nanoparticles of Gd2O3

Several methods are known for the synthesis of gadolinium oxide nanoparticles, mostly based on precipitation of the hydroxide by the reaction of gadolinium ions with hydroxide, followed by thermal dehydration to the oxide. The nanoparticles are always coated with a protective material to avoid the formation of larger polycrystalline aggregates. [6] [7] [8]

Nanoparticles of gadolinium oxide is a potential contrast agent for magnetic resonance imaging (MRI). A dextran-coated preparation of 20–40 nm sized gadolinium oxide particles had a relaxivity of 4.8 s−1mM−1 per gadolinium ion at 7.05 T (an unusually high field compared to the clinically used MRI scanners which mostly range from 0.5 to 3 T). [6] Smaller particles, between 2 and 7 nm, were tested as an MRI agent. [7] [8]

Related Research Articles

<span class="mw-page-title-main">Dysprosium</span> Chemical element, symbol Dy and atomic number 66

Dysprosium is the chemical element with the symbol Dy and atomic number 66. It is a rare-earth element in the lanthanide series with a metallic silver luster. Dysprosium is never found in nature as a free element, though, like other lanthanides, it is found in various minerals, such as xenotime. Naturally occurring dysprosium is composed of seven isotopes, the most abundant of which is 164Dy.

<span class="mw-page-title-main">Erbium</span> Chemical element, symbol Er and atomic number 68

Erbium is a chemical element with the symbol Er and atomic number 68. A silvery-white solid metal when artificially isolated, natural erbium is always found in chemical combination with other elements. It is a lanthanide, a rare-earth element, originally found in the gadolinite mine in Ytterby, Sweden, which is the source of the element's name.

<span class="mw-page-title-main">Gadolinium</span> Chemical element, symbol Gd and atomic number 64

Gadolinium is a chemical element with the symbol Gd and atomic number 64. Gadolinium is a silvery-white metal when oxidation is removed. It is only slightly malleable and is a ductile rare-earth element. Gadolinium reacts with atmospheric oxygen or moisture slowly to form a black coating. Gadolinium below its Curie point of 20 °C (68 °F) is ferromagnetic, with an attraction to a magnetic field higher than that of nickel. Above this temperature it is the most paramagnetic element. It is found in nature only in an oxidized form. When separated, it usually has impurities of the other rare-earths because of their similar chemical properties.

<span class="mw-page-title-main">Lanthanum</span> Chemical element, symbol La and atomic number 57

Lanthanum is a chemical element with the symbol La and atomic number 57. It is a soft, ductile, silvery-white metal that tarnishes slowly when exposed to air. It is the eponym of the lanthanide series, a group of 15 similar elements between lanthanum and lutetium in the periodic table, of which lanthanum is the first and the prototype. Lanthanum is traditionally counted among the rare earth elements. Like most other rare earth elements, the usual oxidation state is +3, although some compounds are known with oxidation state +2. Lanthanum has no biological role in humans but is essential to some bacteria. It is not particularly toxic to humans but does show some antimicrobial activity.

<span class="mw-page-title-main">Lutetium</span> Chemical element, symbol Lu and atomic number 71

Lutetium is a chemical element with the symbol Lu and atomic number 71. It is a silvery white metal, which resists corrosion in dry air, but not in moist air. Lutetium is the last element in the lanthanide series, and it is traditionally counted among the rare earth elements; it can also be classified as the first element of the 6th-period transition metals.

The lanthanide or lanthanoid series of chemical elements comprises the 15 metallic chemical elements with atomic numbers 57–71, from lanthanum through lutetium. These elements, along with the chemically similar elements scandium and yttrium, are often collectively known as the rare-earth elements or rare-earth metals.

<span class="mw-page-title-main">Terbium</span> Chemical element, symbol Tb and atomic number 65

Terbium is a chemical element with the symbol Tb and atomic number 65. It is a silvery-white, rare earth metal that is malleable, and ductile. The ninth member of the lanthanide series, terbium is a fairly electropositive metal that reacts with water, evolving hydrogen gas. Terbium is never found in nature as a free element, but it is contained in many minerals, including cerite, gadolinite, monazite, xenotime and euxenite.

<span class="mw-page-title-main">Praseodymium</span> Chemical element, symbol Pr and atomic number 59

Praseodymium is a chemical element with the symbol Pr and the atomic number 59. It is the third member of the lanthanide series and is considered to be one of the rare-earth metals. It is a soft, silvery, malleable and ductile metal, valued for its magnetic, electrical, chemical, and optical properties. It is too reactive to be found in native form, and pure praseodymium metal slowly develops a green oxide coating when exposed to air.

<span class="mw-page-title-main">Iron(II,III) oxide</span> Chemical compound

Iron(II,III) oxide, or black iron oxide, is the chemical compound with formula Fe3O4. It occurs in nature as the mineral magnetite. It is one of a number of iron oxides, the others being iron(II) oxide (FeO), which is rare, and iron(III) oxide (Fe2O3) which also occurs naturally as the mineral hematite. It contains both Fe2+ and Fe3+ ions and is sometimes formulated as FeO ∙ Fe2O3. This iron oxide is encountered in the laboratory as a black powder. It exhibits permanent magnetism and is ferrimagnetic, but is sometimes incorrectly described as ferromagnetic. Its most extensive use is as a black pigment (see: Mars Black). For this purpose, it is synthesized rather than being extracted from the naturally occurring mineral as the particle size and shape can be varied by the method of production.

<span class="mw-page-title-main">Gadolinium(III) chloride</span> Chemical compound

Gadolinium(III) chloride, also known as gadolinium trichloride, is GdCl3. It is a colorless, hygroscopic, water-soluble solid. The hexahydrate GdCl3∙6H2O is commonly encountered and is sometimes also called gadolinium trichloride. Gd3+ species are of special interest because the ion has the maximum number of unpaired spins possible, at least for known elements. With seven valence electrons and seven available f-orbitals, all seven electrons are unpaired and symmetrically arranged around the metal. The high magnetism and high symmetry combine to make Gd3+ a useful component in NMR spectroscopy and MRI.

<span class="mw-page-title-main">Holmium(III) oxide</span> Chemical compound

Holmium(III) oxide, or holmium oxide is a chemical compound of a rare-earth element holmium and oxygen with the formula Ho2O3. Together with dysprosium(III) oxide (Dy2O3), holmium oxide is one of the most powerfully paramagnetic substances known. The oxide, also called holmia, occurs as a component of the related erbium oxide mineral called erbia. Typically, the oxides of the trivalent lanthanides coexist in nature, and separation of these components requires specialized methods. Holmium oxide is used in making specialty colored glasses. Glass containing holmium oxide and holmium oxide solutions have a series of sharp optical absorption peaks in the visible spectral range. They are therefore traditionally used as a convenient calibration standard for optical spectrophotometers.

MRI contrast agents are contrast agents used to improve the visibility of internal body structures in magnetic resonance imaging (MRI). The most commonly used compounds for contrast enhancement are gadolinium-based contrast agents (GBCAs). Such MRI contrast agents shorten the relaxation times of nuclei within body tissues following oral or intravenous administration.

<span class="mw-page-title-main">Californium compounds</span>

Few compounds of californium have been made and studied. The only californium ion that is stable in aqueous solutions is the californium(III) cation. The other two oxidation states are IV (strong oxidizing agents) and II (strong reducing agents). The element forms a water-soluble chloride, nitrate, perchlorate, and sulfate and is precipitated as a fluoride, oxalate or hydroxide. If problems of availability of the element could be overcome, then CfBr2 and CfI2 would likely be stable.

Praseodymium(III,IV) oxide is the inorganic compound with the formula Pr6O11 that is insoluble in water. It has a cubic fluorite structure. It is the most stable form of praseodymium oxide at ambient temperature and pressure.

An yttrium compound is a chemical compound containing yttrium. Among these compounds, yttrium generally has a +3 valence. The solubility properties of yttrium compounds are similar to those of the lanthanides. For example oxalates and carbonates are hardly soluble in water, but soluble in excess oxalate or carbonate solutions as complexes are formed. Sulfates and double sulfates are generally soluble. They resemble the "yttrium group" of heavy lanthanide elements.

Praseodymium compounds are compounds formed by the lanthanide metal praseodymium (Pr). In these compounds, praseodymium generally exhibits the +3 oxidation state, such as PrCl3, Pr(NO3)3 and Pr(CH3COO)3. However, compounds with praseodymium in the +2 and +4 oxidation states, and unlike other lanthanides, the +5 oxidation state, are also known.

<span class="mw-page-title-main">Europium compounds</span> Compounds with at least one europium atom

Europium compounds are compounds formed by the lanthanide metal europium (Eu). In these compounds, europium generally exhibits the +3 oxidation state, such as EuCl3, Eu(NO3)3 and Eu(CH3COO)3. Compounds with europium in the +2 oxidation state are also known. The +2 ion of europium is the most stable divalent ion of lanthanide metals in aqueous solution. Many europium compounds fluoresce under ultraviolet light due to the excitation of electrons to higher energy levels. Lipophilic europium complexes often feature acetylacetonate-like ligands, e.g., Eufod.

<span class="mw-page-title-main">Terbium compounds</span> Chemical compounds with at least one terbium atom

Terbium compounds are compounds formed by the lanthanide metal terbium (Tb). Terbium generally exhibits the +3 oxidation state in these compounds, such as in TbCl3, Tb(NO3)3 and Tb(CH3COO)3. Compounds with terbium in the +4 oxidation state are also known, such as TbO2 and BaTbF6. Terbium can also form compounds in the 0, +1 and +2 oxidation states.

Promethium compounds are compounds containing the element promethium, which normally take the +3 oxidation state. Promethium belongs to the cerium group of lanthanides and is chemically very similar to the neighboring elements. Because of its instability, chemical studies of promethium are incomplete. Even though a few compounds have been synthesized, they are not fully studied; in general, they tend to be pink or red in color. Treatment of acidic solutions containing Pm3+ ions with ammonia results in a gelatinous light-brown sediment of hydroxide, Pm(OH)3, which is insoluble in water. When dissolved in hydrochloric acid, a water-soluble yellow salt, PmCl3, is produced; similarly, when dissolved in nitric acid, a nitrate results, Pm(NO3)3. The latter is also well-soluble; when dried, it forms pink crystals, similar to Nd(NO3)3. The electron configuration for Pm3+ is [Xe] 4f4, and the color of the ion is pink. The ground state term symbol is 5I4. The sulfate is slightly soluble, like the other cerium group sulfates. Cell parameters have been calculated for its octahydrate; they lead to conclusion that the density of Pm2(SO4)3·8 H2O is 2.86 g/cm3. The oxalate, Pm2(C2O4)3·10 H2O, has the lowest solubility of all lanthanide oxalates.

Lutetium compounds are compounds formed by the lanthanide metal lutetium (Lu). In these compounds, lutetium generally exhibits the +3 oxidation state, such as LuCl3, Lu2O3 and Lu2(SO4)3. Aqueous solutions of most lutetium salts are colorless and form white crystalline solids upon drying, with the common exception of the iodide. The soluble salts, such as nitrate, sulfate and acetate form hydrates upon crystallization. The oxide, hydroxide, fluoride, carbonate, phosphate and oxalate are insoluble in water.

References

  1. Pradyot Patnaik. Handbook of Inorganic Chemicals. McGraw-Hill, 2002, ISBN   0-07-049439-8.
  2. Wells, A.F. (1984) Structural Inorganic Chemistry 5th edition Oxford Science Publications. ISBN   0-19-855370-6.
  3. Adachi, Gin-ya; Imanaka, Nobuhito (1998). "The Binary Rare Earth Oxides". Chemical Reviews. 98 (4): 1479–1514. doi:10.1021/cr940055h. PMID   11848940.
  4. Cotton, S. (2006) Lanthanide and Actinide Chemistry Wiley ISBN   0-470-01006-1 p. 6
  5. Yost, D.M, Russell, H. Jr., Garner, C.S. The Rare-Earth Elements and their Compounds, Wiley, 1947.
  6. 1 2 McDonald, M; Watkin, K (2006). "Investigations into the Physicochemical Properties of Dextran Small Particulate Gadolinium Oxide Nanoparticles". Academic Radiology. 13 (4): 421–27. doi:10.1016/j.acra.2005.11.005. PMID   16554221.
  7. 1 2 Bridot, Jean-Luc; Faure, Anne-Charlotte; Laurent, Sophie; Rivière, Charlotte; Billotey, Claire; Hiba, Bassem; Janier, Marc; Josserand, VéRonique; et al. (2007). "Hybrid Gadolinium Oxide Nanoparticles: Multimodal Contrast Agents for in Vivo Imaging". Journal of the American Chemical Society. 129 (16): 5076–84. doi:10.1021/ja068356j. PMID   17397154.
  8. 1 2 Engström, Maria; Klasson, Anna; Pedersen, Henrik; Vahlberg, Cecilia; Käll, Per-Olov; Uvdal, Kajsa (2006). "High proton relaxivity for gadolinium oxide nanoparticles". Magnetic Resonance Materials in Physics, Biology and Medicine. 19 (4): 180–86. doi:10.1007/s10334-006-0039-x. PMID   16909260. S2CID   23259790.