Chemistry:Technetium hexafluoride

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Technetium(VI) fluoride
Technetium-hexafluoride-2D.png
Identifiers
3D model (JSmol)
ChemSpider
Properties
TcF6
Molar mass 212 g/mol (98Tc)
Appearance golden-yellow crystals[1]
Density 3,58 g/cm3 (−140 °C), solid[2]
Melting point 37.4 °C (99.3 °F; 310.5 K)[1]
Boiling point 55.3 °C (131.5 °F; 328.4 K)[1]
Structure
cubic
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Technetium hexafluoride or technetium(VI) fluoride (TcF6) is a yellow inorganic compound with a low melting point. It was first identified in 1961.[3] In this compound, technetium has an oxidation state of +6, the highest oxidation state found in the technetium halides. In this respect, technetium differs from rhenium, which forms a heptafluoride, ReF7.[4] Technetium hexafluoride occurs as an impurity in uranium hexafluoride, as technetium is a fission product of uranium (spontaneous fission in natural uranium, possible contamination from induced fission inside the reactor in reprocessed uranium). The fact that the boiling point of the hexafluorides of uranium and technetium are very close to each other presents a problem in using fluoride volatility in nuclear reprocessing.

Preparation

Technetium hexafluoride is prepared by heating technetium metal with an excess of F2 at 400 °C.[3]

Tc + 3 F2 → TcF6

Description

Technetium hexafluoride is a golden-yellow solid at room temperature. Its melting point is 37.4 °C and its boiling point is 55.3 °C.[1]

Technetium hexafluoride undergoes a solid phase transition at −4.54 °C. Above this temperature (measured at 10 °C), the solid structure is cubic. Lattice parameters are a = 6.16 Å. There are two formula units (in this case, discrete molecules) per unit cell, giving a density of 3.02 g·cm−3. Below this temperature (measured at −19 °C), the solid structure is orthorhombic space group Pnma. Lattice parameters are a = 9.55 Å, b = 8.74 Å, and c = 5.02 Å. There are four formula units (in this case, discrete molecules) per unit cell, giving a density of 3.38 g·cm−3. At −140 °C, the solid structure is still orthothombic, but the lattice parameters are now a = 9.360 Å, b = 8.517 Å, and c = 4.934 Å, giving a density of 3.58 g·cm−3.[2]

The TcF6 molecule itself (the form important for the liquid or gas phase) has octahedral molecular geometry, which has point group (Oh). The Tc–F bond length is 1.812 Å.[2] Its magnetic moment has been measured to be 0.45 μB.[5]

Properties

Physical

TcF6 is octahedral, as shown by infrared and Raman spectra.[6][7] Its low-temperature orthorhombic form converts to the higher symmetry body-centred cubic form at room temperature, like other metal hexafluorides such as RhF6 and OsF6.[8] Preliminary measurements of magnetic moment yield a value of 0.45 µB, which is lower than expected for a d1 octahedral compound.[9]

Chemical

TcF6 reacts with alkaline chlorides in iodine pentafluoride (IF5) solution to form hexafluorotechnetates.[10][11] TcF6 disproportionates on hydrolysis with aqueous NaOH to form a black precipitate of TcO2.[3] In hydrogen fluoride solution, TcF6 reacts with hydrazinium fluoride to yield N2H6TcF6 or N2H6(TcF6)2.[12]

References

  1. ↑ 1.0 1.1 1.2 1.3 CRC Handbook of Chemistry and Physics, 90th Edition, CRC Press, Boca Raton, Florida, 2009, ISBN:978-1-4200-9084-0, Section 4, Physical Constants of Inorganic Compounds, p. 4-93.
  2. ↑ 2.0 2.1 2.2 Drews, T.; Supeł, J.; Hagenbach, A.; Seppelt, K. (2006). "Solid State Molecular Structures of Transition Metal Hexafluorides". Inorganic Chemistry 45 (9): 3782–3788. doi:10.1021/ic052029f. PMID 16634614. 
  3. ↑ 3.0 3.1 3.2 Selig, H.; Chernick, C.L.; Malm, J.G. (1961). "The Preparation and Properties of TcF6". Journal of Inorganic and Nuclear Chemistry 19 (3–4): 377–381. doi:10.1016/0022-1902(61)80132-2. 
  4. ↑ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8. 
  5. ↑ Selig, H.; Cafasso, F. A.; Gruen, D. M.; Malm, J. G. (1962). "Magnetic Susceptibility of ReF6". Journal of Chemical Physics 36 (12): 3440. doi:10.1063/1.1732477. Bibcode: 1962JChPh..36.3440S. 
  6. ↑ Howard H. Claassen; Henry Selig; John G. Malm (1962). "Vibrational Spectra of MoF6 and TcF6". Journal of Chemical Physics 36 (11): 2888–2890. doi:10.1063/1.1732396. Bibcode: 1962JChPh..36.2888C. 
  7. ↑ Howard H. Claassen; Gordon L. Goodman; John H. Holloway; Henry Selig (1970). "Raman Spectra of MoF6, TcF6, ReF6, UF6, SF6, SeF6, and TeF6 in the Vapor State". Journal of Chemical Physics 53 (1): 341–348. doi:10.1063/1.1673786. Bibcode: 1970JChPh..53..341C. 
  8. ↑ "X-Ray Diffraction Studies of Some Transition Metal Hexafluorides". Inorganic Chemistry 5 (12): 2187–2188. 1966. doi:10.1021/ic50046a025. 
  9. ↑ Selig, H; Cafasso, F A.; Gruen, D M.; Malm, J G. (1962). "Magnetic Susceptibility of ReF6". Journal of Chemical Physics 36 (12): 3440–3444. doi:10.1063/1.1732477. Bibcode: 1962JChPh..36.3440S. 
  10. ↑ Edwards, A. J.; Hugill, D.; Peacock, R. D. (1963). "New Fluorine Compounds of Technetium". Nature 200 (4907): 672. doi:10.1038/200672a0. Bibcode: 1963Natur.200..672E. 
  11. ↑ D. Hugill; R. D. Peacock (1966). "Some quinquevalent fluorotechnetates". Journal of the Chemical Society A: 1339–1341. doi:10.1039/J19660001339. 
  12. ↑ Frlec B; Selig H; Hyman H.H (1967). "Hydrazinium(+2) Hexafluorometalates(IV) and -(V) in the 4d and 5d Transition Series". Inorganic Chemistry 6 (10): 1775–1783. doi:10.1021/ic50056a004. 



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