Lanthanum oxide

Last updated
Lanthanum(III) oxide
Oxyde de lanthane en poudre.jpg
La2O3structure.jpg
Names
IUPAC name
Lanthanum(III) oxide
Other names
Lanthanum sesquioxide
Lanthana
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.013.819 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 215-200-5
PubChem CID
RTECS number
  • OE5330000
UNII
  • InChI=1S/2La.3O/q2*+3;3*-2 Yes check.svgY
    Key: MRELNEQAGSRDBK-UHFFFAOYSA-N Yes check.svgY
  • [O-2].[O-2].[O-2].[La+3].[La+3]
Properties
La2O3
Molar mass 325.808 g·mol−1
AppearanceWhite powder, hygroscopic
Density 6.51 g/cm3, solid
Melting point 2,315 °C (4,199 °F; 2,588 K)
Boiling point 4,200 °C (7,590 °F; 4,470 K)
Insoluble
Band gap 4.3 eV
−78.0·10−6 cm3/mol
Structure
Hexagonal, hP5
P-3m1, No. 164
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Irritant
GHS labelling:
GHS-pictogram-exclam.svg [1]
Warning [1]
H315, H319, H335 [1]
P261, P280, P301+P310, P304+P340, P305+P351+P338, P405, P501 [1]
NFPA 704 (fire diamond)
NFPA 704.svgHealth 1: Exposure would cause irritation but only minor residual injury. E.g. turpentineFlammability (red): no hazard codeInstability (yellow): no hazard codeSpecial hazard W: Reacts with water in an unusual or dangerous manner. E.g. sodium, sulfuric acid
1
W
Flash point Non-flammable
Safety data sheet (SDS) External SDS
Related compounds
Other anions
Lanthanum(III) chloride
Other cations
Cerium(III) oxide
Actinium(III) oxide
Related compounds
Lanthanum aluminium oxide,
LaSrCoO4
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Lanthanum(III) oxide, also known as lanthana, chemical formula La2O3, is an inorganic compound containing the rare earth element lanthanum and oxygen. It is used in some ferroelectric materials, as a component of optical materials, and is a feedstock for certain catalysts, among other uses.

Contents

Properties

La2O3 powder La2O3powder.jpg
La2O3 powder

Lanthanum oxide is a white solid that is insoluble in water, but dissolves in acidic solutions. La2O3 absorbs moisture from air, converts to lanthanum hydroxide. [2] Lanthanum oxide has p-type semiconducting properties and a band gap of approximately 5.8 eV. [3] Its average room temperature resistivity is 10 kΩ·cm, which decreases with an increase in temperature. La2O3 has the lowest lattice energy of the rare earth oxides, with very high dielectric constant, ε = 27.

Structure

At low temperatures, La2O3 has an A-M2O3 hexagonal crystal structure. The La3+ metal atoms are surrounded by a 7 coordinate group of O2− atoms, the oxygen ions are in an octahedral shape around the metal atom and there is one oxygen ion above one of the octahedral faces. [4] On the other hand, at high temperatures lanthanum oxide converts to a C-M2O3 cubic crystal structure. The La3+ ion is surrounded by six O2− ions in a hexagonal configuration. [5] [6]

Synthesis

Lanthanum oxide can crystallize in at least three polymorphs. [2]

Hexagonal La2O3 has been produced by spray pyrolysis of lanthanum chloride. [7]

2 LaCl3 + 3 H2O → La(OH)3 + 3 HCl
2 La(OH)3 → La2O3 + 3 H2O

An alternative route to obtaining hexagonal La2O3 involves precipitation of nominal La(OH)3 from aqueous solution using a combination of 2.5% NH3 and the surfactant sodium dodecyl sulfate followed by heating and stirring for 24 hours at 80 °C:

2 LaCl3 + 3 H2O + 3 NH3 → La(OH)3 + 3 [NH4]Cl

Other routes include:

2 La2S3 + 3 CO2 → 2 La2O3 + 3 CS2

Reactions

Lanthanum oxide is used as an additive to develop certain ferroelectric materials, such as La-doped bismuth titanate (Bi4Ti3O12 - BLT). Lanthanum oxide is used in optical materials; often the optical glasses are doped with La2O3 to improve the glass' refractive index, chemical durability, and mechanical strength. [8]

3 B2O3 + La2O3 → 2 La(BO2)3[ clarification needed ]

The addition of the La2O3 to the glass melt leads to a higher glass transition temperature from 658 °C to 679 °C. The addition also leads to a higher density, microhardness, and refractive index of the glass.

Potential applications

Lanthanum oxide is most useful as a precursor to other lanthanum compounds. [9] Neither the oxide nor any of the derived materials enjoys substantial commercial value, unlike some of the other lanthanides. Many reports describe efforts toward practical applications of La2O3, as described below.

La2O3 forms glasses of high density, refractive index, and hardness. Together with oxides of tungsten, tantalum, and thorium, La2O3 improves the resistance of the glass to attack by alkali. La2O3 is an ingredient in some piezoelectric and thermoelectric materials.

La2O3 has been examined for the oxidative coupling of methane. [10]

Related Research Articles

<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">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.

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">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 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.

Neodymium(III) chloride or neodymium trichloride is a chemical compound of neodymium and chlorine with the formula NdCl3. This anhydrous compound is a mauve-colored solid that rapidly absorbs water on exposure to air to form a purple-colored hexahydrate, NdCl3·6H2O. Neodymium(III) chloride is produced from minerals monazite and bastnäsite using a complex multistage extraction process. The chloride has several important applications as an intermediate chemical for production of neodymium metal and neodymium-based lasers and optical fibers. Other applications include a catalyst in organic synthesis and in decomposition of waste water contamination, corrosion protection of aluminium and its alloys, and fluorescent labeling of organic molecules (DNA).

Sodium oxide is a chemical compound with the formula Na2O. It is used in ceramics and glasses. It is a white solid but the compound is rarely encountered. Instead "sodium oxide" is used to describe components of various materials such as glasses and fertilizers which contain oxides that include sodium and other elements.

In chemistry, an aluminate is a compound containing an oxyanion of aluminium, such as sodium aluminate. In the naming of inorganic compounds, it is a suffix that indicates a polyatomic anion with a central aluminium atom.

<span class="mw-page-title-main">Scandium oxide</span> Chemical compound

Scandium(III) oxide or scandia is a inorganic compound with formula Sc2O3. It is one of several oxides of rare earth elements with a high melting point. It is used in the preparation of other scandium compounds as well as in high-temperature systems (for its resistance to heat and thermal shock), electronic ceramics, and glass composition (as a helper material).

<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.

Lanthanum chloride is the inorganic compound with the formula LaCl3. It is a common salt of lanthanum which is mainly used in research. It is a white solid that is highly soluble in water and alcohols.

Germanium dioxide, also called germanium(IV) oxide, germania, and salt of germanium, is an inorganic compound with the chemical formula GeO2. It is the main commercial source of germanium. It also forms as a passivation layer on pure germanium in contact with atmospheric oxygen.

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

Neodymium(III) oxide or neodymium sesquioxide is the chemical compound composed of neodymium and oxygen with the formula Nd2O3. It forms very light grayish-blue hexagonal crystals. The rare-earth mixture didymium, previously believed to be an element, partially consists of neodymium(III) oxide.

Gallium lanthanum sulfide glass is the name of a family of chalcogenide glasses, referred to as gallium lanthanum sulfide (Ga-La-S) glasses. They are mixtures of La2S3, La2O3, and Ga2S3, which form the basic glass with other glass modifiers added as needed. Gallium-lanthanum-sulfide glasses have a wide range of vitreous formation centered around a 70% Ga2S3 : 30% La2S3 mixture, and readily accept other modifier materials into their structure. This means that Ga-La-S composition can be adjusted to give a wide variety of optical and physical properties.

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

Gallium(III) sulfide, Ga2S3, is a compound of sulfur and gallium, that is a semiconductor that has applications in electronics and photonics.

<span class="mw-page-title-main">Lanthanum hydroxide</span> Chemical compound

Lanthanum hydroxide is La(OH)
3
, a hydroxide of the rare-earth element lanthanum.

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

Aluminium (or aluminum) combines characteristics of pre- and post-transition metals. Since it has few available electrons for metallic bonding, like its heavier group 13 congeners, it has the characteristic physical properties of a post-transition metal, with longer-than-expected interatomic distances. Furthermore, as Al3+ is a small and highly charged cation, it is strongly polarizing and aluminium compounds tend towards covalency; this behaviour is similar to that of beryllium (Be2+), an example of a diagonal relationship. However, unlike all other post-transition metals, the underlying core under aluminium's valence shell is that of the preceding noble gas, whereas for gallium and indium it is that of the preceding noble gas plus a filled d-subshell, and for thallium and nihonium it is that of the preceding noble gas plus filled d- and f-subshells. Hence, aluminium does not suffer the effects of incomplete shielding of valence electrons by inner electrons from the nucleus that its heavier congeners do. Aluminium's electropositive behavior, high affinity for oxygen, and highly negative standard electrode potential are all more similar to those of scandium, yttrium, lanthanum, and actinium, which have ds2 configurations of three valence electrons outside a noble gas core: aluminium is the most electropositive metal in its group. Aluminium also bears minor similarities to the metalloid boron in the same group; AlX3 compounds are valence isoelectronic to BX3 compounds (they have the same valence electronic structure), and both behave as Lewis acids and readily form adducts. Additionally, one of the main motifs of boron chemistry is regular icosahedral structures, and aluminium forms an important part of many icosahedral quasicrystal alloys, including the Al–Zn–Mg class.

Lanthanide trichlorides are a family of inorganic compound with the formula LnCl3, where Ln stands for a lanthanide metal. The trichlorides are standard reagents in applied and academic chemistry of the lanthanides. They exist as anhydrous solids and as hydrates.

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">Lanthanum(III) iodide</span> Chemical compound

Lanthanum(III) iodide is an inorganic compound containing lanthanum and iodine with the chemical formula LaI
3
.

References

  1. 1 2 3 4 "Lanthanum Oxide". American Elements . Retrieved October 26, 2018.
  2. 1 2 Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN   978-0-08-037941-8.
  3. Shang, G.; Peacock, P. W.; Robertson, J. (2004). "Stability and band offsets of nitrogenated high-dielectric-constant gate oxides". Applied Physics Letters. 84 (1): 106–108. Bibcode:2004ApPhL..84..106S. doi:10.1063/1.1638896.
  4. Wells, A.F. (1984). Structural Inorganic Chemistry. Oxford: Clarendon Press. p. 546.
  5. Wyckoff, R. W.G. (1963). Crystal Structures: Inorganic Compounds RXn, RnMX2, RnMX3. New York: Interscience Publishers.
  6. Adachi, Gin-ya; Imanaka, Nobuhito (1998). "The Binary Rare Earth Oxides". Chemical Reviews. 98 (4): 1479–1514. doi:10.1021/cr940055h. PMID   11848940.
  7. Kale, S.S.; Jadhav, K.R.; Patil, P.S.; Gujar, T.P.; Lokhande, C.D. (2005). "Characterizations of spray-deposited lanthanum oxide (La2O3) thin films". Materials Letters. 59 (24–25): 3007–3009. doi:10.1016/j.matlet.2005.02.091.
  8. Vinogradova, N. N.; Dmitruk, L. N.; Petrova, O. B. (2004). "Glass Transition and Crystallization of Glasses Based on Rare-Earth Borates". Glass Physics and Chemistry. 30: 1–5. doi:10.1023/B:GPAC.0000016391.83527.44. S2CID   94177915.
  9. "Lanthanum has also found modest uses." Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 946. ISBN   978-0-08-037941-8.
  10. Manoilova, O.V.; et al. (2004). "Surface acidity and basicity of La2O3, LaOCl, and LaCl3 characterized by IR spectroscopy, TPD, and DFT calculations". J. Phys. Chem. B. 108 (40): 15770–15781. doi:10.1021/jp040311m.