Zirconium(III) chloride
| Names | |
|---|---|
| IUPAC name
Zirconium trichloride
| |
| Identifiers | |
| Properties | |
| ZrCl3 | |
| Molar mass | 197.583 g/mol |
| Appearance | blue-black crystals |
| Density | 2.20- 3.05 g/cm3 |
| Boiling point | 330 °C |
| hydrolysis | |
| Solubility | soluble in water |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
| |
Zirconium(III) chloride is a the inorganic compound with formula ZrCl3. It is a blue-black solid that is highly sensitive to air.
Preparation
The material was first claimed by Ruff and Wallstein who reduced zirconium tetrachloride with aluminium to give impure samples.[1] Subsequently, the problem with aluminium contamination was solved when it was prepared by reduction using zirconium metal:[2]
- Zr + 3 ZrCl4 → 4 ZrCl3
When aluminium is used as the reducing agent with zirconium tetrachloride, a series of choloroaluminates are formed, for example [Zr(AlCl4)2(AlCl4)2] and Zr(AlCl4)3.[3]
Since the trihalides, such as zirconium trichloride, are comparatively nonvolatile, contamination can be avoided by using a gaseous reductant. For example, zirconium trichloride can be prepared by reduction of zirconium tetrachloride with hydrogen.[4]
- ZrCl4 + 1/2H2 → ZrCl3 + HCl
Structure
ZrCl3 adopts a cubic close packed (ccp) structure in which Zr fills one third of the octahedral holes, similar to AlF3 and AlBr3. The Zr-Cl distance is 2.64 Å. Alternating strong and weak bonding between Zr centres is evidences by Zr-Zr distances of 303 and 342 pm.[5] The magnetic susceptibility of zirconium trichloride suggests metal-metal interactions of the unpaired electron on each Zr(III) center. The magnetic moment of ZrCl3 (0.4 BM) indicates considerable overlap of metal orbitals.[6]
References
- ^ Ruff, Otto; Wallstein, Richard (1923). "Reduktion anorganischer Halogenide III.1) Die Reduktion des Zirkontetrachlorids". Zeitschrift für anorganische und allgemeine Chemie. 128: 96. doi:10.1002/zaac.19231280110.
- ^ Hoffman, David M.; Lee, Samkeun (1992). "Synthesis of pyridine complexes of zirconium(III) chloride and the apparent oxidation to zirconium(IV) by a nitrile". Inorganic Chemistry. 31 (13): 2675. doi:10.1021/ic00039a002.
- ^ Larsen, E. M.; Moyer, James W.; Gil-Arnao, Francisco.; Camp, Michael J. (1974). "Synthesis of crystalline zirconium trihalides by reduction of tetrahalides in molten aluminum halides. Nonreduction of hafnium". Inorganic Chemistry. 13 (3): 574. doi:10.1021/ic50133a015.
- ^ Newnham, I. E.; Watts, J. A. (1960). "The Preparation of the Anhydrous Zirconium Trihalides". Journal of the American Chemical Society. 82 (9): 2113. doi:10.1021/ja01494a006.
- ^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
- ^ Wells, A.F. Structural Inorganic Chemistry. Oxford Science Publications, 1975, 5th ed, 417-420.