Niobium pentoxide

Niobium pentoxide
Niobium pentoxide
Identifiers
CAS number 1313-96-8 YesY
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
 YesY pentoxide (verify) (what is: YesY/N?)
Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
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]

Contents

Structure

It has many polymorphic forms all based largely on octahedrally coordinated niobium atoms.[2] The polymorphs are identified with a variety of prefixes.[2] 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.[3] 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.[4]

Production

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

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.[5] The oxidation of niobium dioxide, NbO2 in air forms the polymorph, L-Nb2O5.[6] Pure Nb2O5 can be prepared by hydrolysis of NbCl5:[7]

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.[8]

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

Nb2O5 is attacked by HF and dissolves in fused alkali.[4][5]

Reduction to the metal

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.[9] 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:[10][11]

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

Conversion to halides

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:[12]

Nb2O5 + 5 SOCl2 → 2 NbCl5 + 5 SO2

Nb2O5 reacts with CCl4 to give niobium oxychloride NbOCl3.

Conversion to niobates

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, Nb6O8−
19
.[13] Lithium niobates such as LiNbO3 and Li3NbO4 can be prepared by reaction lithium carbonate and Nb2O5.[14][15]

Conversion to reduced niobium oxides

High temperature reduction with H2 gives NbO2:[5]

Nb2O5 + H2 → 2 NbO2 + H2O

Niobium monooxide arises from a comproportionation using an arc-furnace:[16]

Nb2O5 + 3Nb → 5 NbO

The burgundy-coloured niobium(III) oxide, one of the first superconducting oxides, can be prepared again by an comproportionation:[15]

Li3NbO4 + 2 NbO → 3 LiNbO2

Uses

Niobium pentoxide is used mainly in the production of niobium metal,[9] but specialized applications exist for lithium niobate and as a component of optical glass.[1]

External links

  • 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

  1. ^ a b Francois Cardarelli (2008) Materials Handbook Springer London ISBN 978-1-84628-668-1
  2. ^ a b Wells A.F. (1984) Structural Inorganic Chemistry 5th edition Oxford Science Publications ISBN 0-19-855370-6
  3. ^ 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
  4. ^ 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 1600213138
  5. ^ a b c Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Oxford: Butterworth-Heinemann. ISBN 0080379419. 
  6. ^ 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
  7. ^ Process for the manufacture of niobium pentoxide or tantalum pentoxide, Kern, Therwil, Jacob, Hooper (CIBA Switzerland), US Patent number: 3133788, (1964)
  8. ^ 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
  9. ^ 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
  10. ^ Alan E. Comyns (1999) Encyclopedic Dictionary of Named Processes in Chemical Technology CRC Press, ISBN 0849312051
  11. ^ 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
  12. ^ D. Brown "Niobium(V) Chloride and Hexachloroniobates(V)" Inorganic Syntheses, 1957 Volume 9, pp. 88–92.doi:10.1002/9780470132401.ch24
  13. ^ 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
  14. ^ US Patent 5482001 - Process for producing lithium niobate single crystal,1996, Katoono T., Tominaga H.,
  15. ^ 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
  16. ^ T. B. Reed, E. R. Pollard "Niobium Monoxide" Inorganic Syntheses, 1995 Volume 30, pp. 108–110, 2007. doi:10.1002/9780470132616.ch22

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