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Terbium(III,IV) oxide



Terbium(III,IV) oxide
General
Systematic name Tetraterbium heptaoxide
Other names Terbium(III,IV) oxide,
Terbium peroxide
Molecular formula Tb4O7
Molar mass 747.6972 g/mol
Appearance Dark brown-black
hygroscopic solid.
CAS number [12037-01-3]
Properties
Density and phase 7.3 g/cm3, solid.
Solubility in water Insoluble.
Melting point Decomposes to Tb2O3
Boiling point See above
Structure
Molecular shape  ?
Coordination
geometry
 ?
Crystal structure  ?
Dipole moment  ? D
Hazards
MSDS External MSDS
Main hazards Oxidising agent.
NFPA 704
0
1
0
 
Flash point Non-flammable.
R/S statement R: ?
S: S24/25, S37, S45, S28
RTECS number  ?
Supplementary data page
Structure and
properties
n, εr, etc.
Thermodynamic
data
Phase behaviour
Solid, liquid, gas
Spectral data UV, IR, NMR, MS
Related compounds
Other anions  ?
Other cations Terbium(III) oxide,
Terbium(IV) oxide
Related compounds Cerium(IV) oxide,
Praseodymium(III,IV) oxide
Except where noted otherwise, data are given for
materials in their standard state (at 25°C, 100 kPa)
Infobox disclaimer and references

Terbium(III,IV) oxide, occasionally called tetraterbium heptaoxide, has the formula Tb4O7, though some texts refer to it as TbO1.75. There is some debate as to whether it is a discrete compound, or simply one phase in an interstitial oxide system. Tb4O7 is one of the main commercial terbium compounds, and the only such product containing at least some Tb(IV) (terbium in the +4 oxidation state), along with the more stable Tb(III). It is produced by heating the metal oxalate, and it is used in the preparation of other terbium compounds. Terbium forms three other major oxides: Tb2O3, TbO2, and Tb6O11.

Additional recommended knowledge

Synthesis

Tb4O7 is most often produced by ignition of the oxalate at or the sulfate in air.[1] The oxalate (at 1000 °C) is generally preferred, since the sulfate requires a higher temperature, and it produces an almost black product contaminated with Tb6O11 or other oxygen-rich oxides.

Chemical properties

Terbium(III,IV) oxide loses O2 when heated at high temperatures; at more moderate temperatures (ca. 350 °C) it reversibly loses oxygen, as shown by exchange with 18O2. This property, also seen in Pr6O11 and V2O5, allows it to work like V2O5 as a redox catalyst in reactions involving oxygen. It was found as early as 1916 that hot Tb4O7 catalyses the reaction of coal gas (CO + H2) with air, leading to incandescence and often the mixture catches fire.[2]

Tb4O7 reacts with atomic oxygen to produce TbO2, but a more convenient preparation of TbO2 is by disproportionation of Tb4O7. This is performed by refluxing with an excess of an equal mixture of concentrated acetic acid and hydrochloric acids for 30 minutes.[3]

Tb4O7(s) + 6 HCl(aq) → 2 TbO2(s) + 2 TbCl3(aq) + 3 H2O(l)

Tb4O7 reacts with other hot concentrated acids to produce terbium(III) salts, for example sulfuric acid gives terbium(III) sulfate.


References

  1. ^  Handbook of Chemistry and Physics, 71st edition, CRC Press, Ann Arbor, Michigan, 1990.
  2. ^  J. W. Mellor, A Comprehensive Treatise on Inorganic and Theoretical Chemistry, pp 692-696, Longmans, Green & Co., London, 1967.
  3. ^ Gmelin SE C 1 39, p 397.
  4. ^  D. W. Bissel, C. James, J. Am. Chem. Soc 38, 873 (1916).
  5. ^  F. T. Edelmann, P. Poremba, in: Synthetic Methods of Organometallic and Inorganic Chemistry, (W. A. Herrmann, ed.), Vol. 6, Georg Thieme Verlag, Stuttgart, 1997. ISBN 3-13-103071-2.
 
This article is licensed under the GNU Free Documentation License. It uses material from the Wikipedia article "Terbium(III,IV)_oxide". A list of authors is available in Wikipedia.
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