Zirconium(III) chloride
| Zirconium(III) Chloride | ||
|---|---|---|
 | ||
| IUPAC name Zirconium trichloride | ||
| Identifiers | ||
| CAS number | 10241-03-9 | |
| Properties | ||
| Molecular formula | ZrCl3 | |
| Molar mass | 197.583 g/mol | |
| Appearance | blue-black crystals | |
| Density | 2.20- 3.05 g/cm3 | |
| Boiling point | 330 °C | |
| Solubility in water | hydrolysis | |
| Solubility | soluble in water | |
 (verify) (what is: / ?)Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa) | ||
| Infobox references | ||
Zirconium(III) chloride is an 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 + ½ H2 → 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 0080379419.
- ↑ Wells, A.F. Structural Inorganic Chemistry. Oxford Science Publications, 1975, 5th ed, 417-420.