Chemistry:Zirconium perchlorate
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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). | |
| Infobox references | |
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]
Synthesis and properties
It 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
In 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
Titanium 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]. The very close analogues of zirconium perchlorate are zirconium pertechnetates and perrhenates, however, unlike it, they crystallize from an aqueous solution in the form of dimers of the composition [Zr2(MO4)6(μ-OH)2(H2O)6]..3H2O (M = Tc and Re).[7]
Zirconyl perchlorates have been claimed in older literature.[8]
References
- ↑ 1.0 1.1 1.2 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.
- ↑ 2.0 2.1 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. https://inis.iaea.org/search/search.aspx?orig_q=RN:17001696.
- ↑ 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.
- ↑ Babaeva, V. P.; Rosolovski, V. Ya. (1978). "Synthesis and Properties of cesium perchloratozirconates". Zhurnal Neorganicheskoj Khimii 23 (4): 955–959.
- ↑ Novikov, Anton P.; Zagidullin, Karim A.; Kuznetsov, Vitaly V.; Belova, Elena V.; Grigoriev, Mikhail S.; Volkov, Mikhail A.; Afanasiev, Andrey V.; German, Konstantin E. et al. (2025-08-15). "Speciation and Complex Formation of Zirconium(IV) with Tc(VII) and Re(VII) in Liquid–Liquid Extraction Systems". ACS Omega. doi:10.1021/acsomega.5c05158. PMC 12391960. https://doi.org/10.1021/acsomega.5c05158.
- ↑ Murthy, P. Rama; Patel, C. C. (1961). "Zirconyl perchlorate". Die Naturwissenschaften 48 (22): 693. doi:10.1007/BF00595937. Bibcode: 1961NW.....48..693M.
Compounds containing perchlorate group
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| HClO4 | He | ||||||||||||||||||
| LiClO4 | Be(ClO4)2 | B(ClO4)−4 B(ClO4)3 |
ROClO3 | N(ClO4)3 NH4ClO4 NOClO4 |
O | FClO4 | Ne | ||||||||||||
| NaClO4 | Mg(ClO4)2 | Al(ClO4)3 | Si | P | S | ClO−4 ClOClO3 Cl2O7 |
Ar | ||||||||||||
| KClO4 | Ca(ClO4)2 | Sc(ClO4)3 | Ti(ClO4)4 | VO(ClO4)3 VO2(ClO4) |
Cr(ClO4)3 | Mn(ClO4)2 | Fe(ClO4)3 | Co(ClO4)2, Co(ClO4)3 |
Ni(ClO4)2 | Cu(ClO4)2 | Zn(ClO4)2 | Ga(ClO4)3 | Ge | As | Se | Br | Kr | ||
| RbClO4 | Sr(ClO4)2 | Y(ClO4)3 | Zr(ClO4)4 | Nb(ClO5)4 | Mo | Tc | Ru | Rh(ClO4)3 | Pd(ClO4)2 | AgClO4 | Cd(ClO4)2 | In(ClO4)3 | Sn(ClO4)4 | Sb | TeO(ClO4)2 | I | Xe | ||
| CsClO4 | Ba(ClO4)2 | Hf(ClO4)4 | Ta(ClO5)5 | W | Re | Os | Ir | Pt | Au | Hg2(ClO4)2, Hg(ClO4)2 |
Tl(ClO4)3 | Pb(ClO4)2 | Bi(ClO4)3 | Po | At | Rn | |||
| FrClO4 | Ra | Rf | Db | Sg | Bh | Hs | Mt | Ds | Rg | Cn | Nh | Fl | Mc | Lv | Ts | Og | |||
| ↓ | |||||||||||||||||||
| La | Ce(ClO4)x | Pr | Nd | Pm | Sm(ClO4)3 | Eu(ClO4)3 | Gd(ClO4)3 | Tb(ClO4)3 | Dy(ClO4)3 | Ho(ClO4)3 | Er(ClO4)3 | Tm(ClO4)3 | Yb(ClO4)3 | Lu(ClO4)3 | |||||
| Ac | Th(ClO4)4 | Pa | UO2(ClO4)2 | Np | Pu | Am | Cm | Bk | Cf | Es | Fm | Md | No | Lr | |||||
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