Niobium pentoxide

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Niobium pentoxide
Kristallstruktur Niob(V)-oxid.png
Identifiers
CAS number 1313-96-8 YesY
PubChem 123105
Jmol-3D images Image 1
Properties
Molecular formula Nb2O5
Molar mass 265.81 g/mol
Appearance white orthogonal solid
Density 4.60 g/cm3
Melting point 1512 °C
Solubility in water insoluble
Solubility soluble in HF
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
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Infobox references

Niobium pentoxide is the inorganic compound with the formula Nb2O5. It is a colourless insoluble solid that is fairly unreactive. It is the main precursor to all materials made of niobium, the dominant application being alloys, but other specialized applications include capacitors, lithium niobate, and optical glasses.[1]

Structure[edit]

It has many polymorphic forms all based largely on octahedrally coordinated niobium atoms.[2][3] The polymorphs are identified with a variety of prefixes. [2] [3] The form most commonly encountered is monoclinic H-Nb2O5 which has a complex structure, with a unit cell containing 28 niobium atoms and 70 oxygen, where 27 of the niobium atoms are octahedrally coordinated and one tetrahedrally.[4] There is an uncharacterised solid hydrate, Nb2O5.nH2O, the so-called niobic acid (previously called columbic acid), which can be prepared by hydrolysis of a basic solution of niobium pentachloride or Nb2O5 dissolved in HF.[5]

Production[edit]

Nb2O5 is prepared by hydrolysis of alkali-metal niobates and alkoxides and the fluorides using base. Such ostensibly simple procedures afford hydrated oxides that are calcined.

Other routes[edit]

Given that Nb2O5 is the most common and robust compound of niobium, many methods, both practical and esoteric, exist for its formation. The oxide for example, arises when niobium metal is oxidised in air.[6] The oxidation of niobium dioxide, NbO2 in air forms the polymorph, L-Nb2O5.[7] Pure Nb2O5 can be prepared by hydrolysis of NbCl5:[8]

2 NbCl5 + 5 H2O → Nb2O5 + 10 HCl

A method of production via sol-gel techniques has been reported hydrolysing niobium alkoxides in the presence of acetic acid, followed by calcination of the gels to produce the polymorphic form, T-Nb2O5.[9]

Nano-sized niobium pentoxide particles have been synthesised by LiH reduction of NbCl5, followed by aerial oxidation as part of a synthesis of nano structured niobates.

Reactions[edit]

Nb2O5 is attacked by HF and dissolves in fused alkali.[5][6]

Reduction to the metal[edit]

The conversion of Nb2O5 is the main route for the industrial production of niobium metal. In the 1980s, about 15,000,000 kg of Nb2O5 were consumed annually for reduction to the metal.[10] The main method is reduction of this oxide with aluminium:

3 Nb2O5 + 10 Al → 6 Nb + 5 Al2O3

An alternative but less practiced route involves carbothermal reduction, which proceeds via reduction with carbon and forms the basis of the two stage Balke process:[11][12]

Nb2O5 + 7 C → 2 NbC + 5 CO (heated under vacuum at 1800 °C)
5 NbC + Nb2O5 → 7 Nb + 5 CO

Conversion to halides[edit]

Many methods are known for conversion of Nb2O5 to the halides. The main problem is incomplete reaction to give the oxyhalides. In the laboratory, the conversion can be effected with thionyl chloride:[13]

Nb2O5 + 5 SOCl2 → 2 NbCl5 + 5 SO2

Nb2O5 reacts with CCl4 to give niobium oxychloride NbOCl3.

Conversion to niobates[edit]

Treating Nb2O5 with aqueous NaOH at 200 °C can give crystalline sodium niobate, NaNbO3 whereas the reaction with KOH may yield soluble Lindqvist-type hexaniobates, Nb
6
O8−
19
.[14] Lithium niobates such as LiNbO3 and Li3NbO4 can be prepared by reaction lithium carbonate and Nb2O5.[15][16]

Conversion to reduced niobium oxides[edit]

High temperature reduction with H2 gives NbO2:[6]

Nb2O5 + H2 → 2 NbO2 + H2O

Niobium monooxide arises from a comproportionation using an arc-furnace:[17]

Nb2O5 + 3Nb → 5 NbO

The burgundy-coloured niobium(III) oxide, one of the first superconducting oxides, can be prepared again by an comproportionation:[16]

Li3NbO4 + 2 NbO → 3 LiNbO2

Uses[edit]

Niobium pentoxide is used mainly in the production of niobium metal,[10] but specialized applications exist for lithium niobate and as a component of optical glass.[1]

External links[edit]

  • Basic Niobium Information and Research Data
  • Thin films of Nb2O5 form the dielectric layers in solid electrolyte capacitors and these layers can be grown electrolytically on sintered bodies containing niobium monoxide.Katsuhiro Yoshida, Noriko Kuge (NEC Corporation), Sintered bodies based on niobium suboxide US patent 6215652, 2001.

References[edit]

  1. ^ a b Francois Cardarelli (2008) Materials Handbook Springer London ISBN 978-1-84628-668-1
  2. ^ a b C. Nico, et al. (2011). "Sintered NbO powders for electronic device applications". The Journal of Physical Chemistry C 115 (11): 4879–4886. doi:10.1021/jp110672u. 
  3. ^ a b Wells A.F. (1984) Structural Inorganic Chemistry 5th edition Oxford Science Publications ISBN 0-19-855370-6
  4. ^ The crystal structure of the high temperature form of niobium pentoxide B. M. Gatehouse and A. D. Wadsley Acta Cryst. (1964). 17, 1545-1554 doi:10.1107/S0365110X6400384X
  5. ^ a b D.A. Bayot and M.M. Devillers, Precursors routes for the preparation of Nb based multimetallic oxides in Progress in Solid State Chemistry Research, Arte M. Newman, Ronald W. Buckley, (2007),Nova Publishers, ISBN 1-60021-313-8
  6. ^ a b c Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 0080379419. 
  7. ^ Electrical properties of NbO2 and Nb2O5 at elevated temperature in air and flowing argon, G. C. Vezzoli Phys. Rev. B 26, 3954 - 3957 (1982)doi:10.1103/PhysRevB.26.3954
  8. ^ Process for the manufacture of niobium pentoxide or tantalum pentoxide, Kern, Therwil, Jacob, Hooper (CIBA Switzerland), US Patent number: 3133788, (1964)
  9. ^ Sol-gel route to niobium pentoxide, P Griesmar, G Papin, C Sanchez, J Livage - Chem. Mater.; 1991; 3(2); 335-339 doi:10.1021/cm00014a026
  10. ^ a b Joachim Eckert, Hermann C. Starck "Niobium and Niobium Compounds" Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH, Weinheim. doi:10.1002/14356007.a17_251
  11. ^ Alan E. Comyns (1999) Encyclopedic Dictionary of Named Processes in Chemical Technology CRC Press, ISBN 0-8493-1205-1
  12. ^ U.S. Environmental Protection Agency, Development Document for Effluent Limitations, Guidelines and Standards for the Nonferrous Metals Manufacturing Point Source Category, Volume VIII, Office of Water Regulations and Standards, May 1989
  13. ^ D. Brown "Niobium(V) Chloride and Hexachloroniobates(V)" Inorganic Syntheses, 1957 Volume 9, pp. 88–92.doi:10.1002/9780470132401.ch24
  14. ^ Studies on the hydrothermal synthesis of niobium oxides, I.C. M. S. Santos, L. H. Loureiro, M. F. P. Silva and Ana M. V. Cavaleiro, Polyhedron, 21, 20, (2002), 2009-2015, doi:10.1016/S0277-5387(02)01136-1
  15. ^ US Patent 5482001 - Process for producing lithium niobate single crystal,1996, Katoono T., Tominaga H.,
  16. ^ a b Margret J. Geselbracht, Angelica M. Stacy, "Lithium Niobium Oxide: LiNbo2 and Superconducting LiXNbO2" Inorganic Syntheses 1995, Volume 30, Pages: 222–226.doi:10.1002/9780470132616.ch42
  17. ^ T. B. Reed, E. R. Pollard "Niobium Monoxide" Inorganic Syntheses, 1995 Volume 30, pp. 108–110, 2007. doi:10.1002/9780470132616.ch22