Zirconium perchlorate is an inorganic compound with the formula Zr(ClO4)4. It is a hygroscopic colorless solid that sublimes in a vacuum at 70 °C. These properties show that the compound is covalently bonded molecule, rather than a salt.[1] It is an example of a transition metal perchlorate complex.[2]
4.svg)
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| Identifiers | |
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3D model (JSmol)
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| Properties | |
| Cl4O16Zr | |
| Molar mass | 489.01 g·mol−1 |
| Appearance | white crystals, deliquescent |
| Melting point | 96 °C (205 °F; 369 K) |
| Boiling point | decomposition |
| decomposition | |
| Related compounds | |
Other anions
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Zirconium nitrate Zirconyl perchlorate |
Other cations
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Titanium perchlorate Hafnium perchlorate |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Synthesis and properties
editIt can be formed by treating zirconium tetrachloride with dichlorine hexoxide-perchloric acid mixture at - 35 °C.[1]
Zirconium perchlorate reacts irreversibly with most organic compounds but is inert towards carbon tetrachloride, chloroformide. With benzene at -10°C, crystals of Zr(ClO4)4•C6H6 are deposited.
Solid zirconium perchlorate undergoes a phase transition around 45 °C before melting between 95.5 and 96.0 °C. Thermolysis near 120 °C gives zirconyl perchlorate. Further heating around 290°C gives form zirconia and chlorine oxides.[1]
Structure
editIn the gas phase the Zr(ClO4)4 molecule has a D4 symmetry with eightfold square antiprism oxygen coordination. Each perchorate group is bidentate. The chlorine atoms are in a tetrahedral arrangement around the central zirconium.[3]
In the solid phase, Zr(ClO4)4 crystals are monoclinic with a=12.899, b=13.188, c=7.937 Å, β=107.91°. There are four molecules per unit cell.[4]
Related substances
editTitanium perchlorate and hafnium perchlorate are both known.[2]
Salts of perchloratozirconates and hexaperchloratozirconates have been claimed including the caesium perchloratozirconates CsZr(ClO4)5, Cs2Zr(ClO4)6, and Cs4Zr(ClO4)8.[5][6]
Zirconyl perchlorates have been claimed in older literature.[7]
References
edit- ^ a b c Babaeva, V. N.; Rosolovskii, V. Ya. (March 1977). "Anhydrous zirconium perchlorate". Bulletin of the Academy of Sciences of the USSR Division of Chemical Science. 26 (3): 445–449. doi:10.1007/BF01179439.
- ^ a b Pascal, Jean-Louis; Favier, Frédéric (1998). "Inorganic Perchlorato Complexes". Coordination Chemistry Reviews. 178–180: 865–902. doi:10.1016/S0010-8545(98)00102-7.
- ^ Lapshina, S.B.; Ermolaeva, L.I.; Girichev, G.V.; Spiridonov, V.P.; Golubinskii, A.V. (1999). "Electron Diffraction Study of the Molecular Structure of Zirconium Perchlorate in the Gas Phase". Russian Journal of Inorganic Chemistry. 44 (4): 485–488.
- ^ Genkina, E.A.; Babaeva, V.P.; Rosolovskij, V.Ya. (1984). "Molecular and crystal structure of anhydrous zirconium perchlorate". Koordinatsionnaya Khimiya. 10 (10): 1415–1419. ISSN 0132-344X.
- ^ Krivtsov, N. V.; Babaeva, V. P.; Rosolovskii, V. Ya. (April 1990). "A thermochemical study of cesium and nitrile perchloratozirconates". Bulletin of the Academy of Sciences of the USSR Division of Chemical Science. 39 (4): 817–820. doi:10.1007/BF00960355. S2CID 96641367.
- ^ Babaeva, V. P.; Rosolovski, V. Ya. (1978). "Synthesis and Properties of cesium perchloratozirconates". Zhurnal Neorganicheskoj Khimii. 23 (4): 955–959.
- ^ Murthy, P. Rama; Patel, C. C. (1961). "Zirconyl perchlorate". Die Naturwissenschaften. 48 (22): 693. Bibcode:1961NW.....48..693M. doi:10.1007/BF00595937. S2CID 34179500.