Chemistry:Lanthanum oxide

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Short description: Chemical compound
Lanthanum(III) oxide
Lanthanum(III) oxide
La2O3structure.jpg
Names
IUPAC name
Lanthanum(III) oxide
Other names
Lanthanum sesquioxide
Lanthana
Identifiers
3D model (JSmol)
ChemSpider
EC Number
  • 215-200-5
RTECS number
  • OE5330000
UNII
Properties
La2O3
Molar mass 325.808 g·mol−1
Appearance White 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
Main hazards Irritant
Safety data sheet External SDS
GHS pictograms GHS07: Harmful[1]
GHS Signal word Warning[1]
H315, H319, H335[1]
P261, P280, P301+310, P304+340, P305+351+338, P405, P501[1]
NFPA 704 (fire diamond)
Flammability (red): no hazard codeHealth code 1: Exposure would cause irritation but only minor residual injury. E.g. turpentineReactivity (yellow): no hazard codeSpecial hazard W: Reacts with water in an unusual or dangerous manner. E.g. sodium, sulfuric acidNFPA 704 four-colored diamond
1
Flash point Non-flammable
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).
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Infobox references

Lanthanum(III) oxide, also known as lanthana, chemical formula La
2
O
3
, 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.

Properties

La
2
O
3
powder

Lanthanum oxide is a white solid that is insoluble in water, but dissolves in acidic solutions. La
2
O
3
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. La
2
O
3
has the lowest lattice energy of the rare earth oxides, with very high dielectric constant, ε = 27.

Structure

At low temperatures, La
2
O
3
has an A-M
2
O
3
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-M
2
O
3
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 La
2
O
3
has been produced by spray pyrolysis of lanthanum chloride.[7]

2 LaCl
3
+ 3 H
2
O → La(OH)
3
+ 3 HCl
2 La(OH)
3
→ La
2
O
3
+ 3 H
2
O

An alternative route to obtaining hexagonal La
2
O
3
involves precipitation of nominal La(OH)
3
from aqueous solution using a combination of 2.5% NH
3
and the surfactant sodium dodecyl sulfate followed by heating and stirring for 24 hours at 80 °C:

2 LaCl
3
+ 3 H
2
O + 3 NH
3
→ La(OH)
3
+ 3 [NH
4
]Cl

Other routes include:

2 La
2
S
3
+ 3 CO
2
→ 2 La
2
O
3
+ 3 CS
2

Reactions

Lanthanum oxide is used as an additive to develop certain ferroelectric materials, such as La-doped bismuth titanate (Bi
4
Ti
3
O
12
- BLT). Lanthanum oxide is used in optical materials; often the optical glasses are doped with La
2
O
3
to improve the glass' refractive index, chemical durability, and mechanical strength.[8]

3 B
2
O
3
+ La
2
O
3
→ 2 La(BO
2
)
3
[clarification needed]

The addition of the La
2
O
3
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 La
2
O
3
, as described below.

La
2
O
3
forms glasses of high density, refractive index, and hardness. Together with oxides of tungsten, tantalum, and thorium, La
2
O
3
improves the resistance of the glass to attack by alkali. La
2
O
3
is an ingredient in some piezoelectric and thermoelectric materials.

La
2
O
3
has been examined for the oxidative coupling of methane.[10]

References

  1. 1.0 1.1 1.2 1.3 "Lanthanum Oxide". American Elements. https://www.americanelements.com/lanthanum-oxide-1312-81-8. 
  2. 2.0 2.1 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. doi:10.1063/1.1638896. Bibcode2004ApPhL..84..106S. 
  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. 
  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. (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.