Zirconium perchlorate

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Zirconium perchlorate
Identifiers
3D model (JSmol)
  • InChI=1S/4ClHO4.Zr/c4*2-1(3,4)5;/h4*(H,2,3,4,5);/q;;;;+4/p-4
    Key: MQGNWZLWQBTZJR-UHFFFAOYSA-J
  • [Zr](O[Cl](=O)(=O)=O)(O[Cl](=O)(=O)=O)(O[Cl](=O)(=O)=O)O[Cl](=O)(=O)=O
Properties
Cl4O16Zr
Molar mass 489.01 g·mol−1
Appearancewhite crystals,
deliquescent
Melting point 96 °C (205 °F; 369 K)
Boiling point decomposition
high
Related compounds
Other anions
Zirconium nitrate
Zirconyl perchlorate
Other cations
Titanium perchlorate
Hafnium perchlorate
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Zirconium perchlorate is a molecular substance containing zirconium and perchlorate groups with formula Zr(ClO4)4. Zr(ClO4)4 is a volatile crystalline product. It can be formed by reacting zirconium tetrachloride with dry perchloric acid at liquid nitrogen temperatures. Zr(ClO4)4 sublimes slowly in a vacuum at 70°C showing that the molecule is covalently bound rather than being ionic. [1] The reaction also forms some zirconyl perchlorate (or zirconium oxyperchlorate) ZrO(ClO4)2 as even apparently pure perchloric acid is in equilibrium with dichlorine heptoxide, hydronium ions and perchlorate ions. This side product can be minimised by adding more dichlorine heptoxide or doing the reaction as cold as possible. [1]

Contents

Properties

Zirconium perchlorate is very hydroscopic forming hydrates, and it is hydrolysed by water to yield zirconyl perchlorate, ZrO(ClO4)2. [1] Zirconium perchlorate reacts with vaseline, methyl nitrate or acetonitrile. Zirconium perchlorate is inert towards carbon tetrachloride, chloroform, and dimethylformamide. [1] Zirconium perchlorate reacts with benzene at 20°C, but at -10°C crystals of Zr(ClO4)4•C6H6 are deposited. [1] Zirconium perchlorate has solid state transition around 45°C, a melting point between 95.5 and 96.0°C and a decomposition point starting around 120°C. The zirconyl perchlorate formed in the heat decomposition, itself decomposes around 290°C to form zirconia, chlorine and oxygen. [1]

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. [2]

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. [3]

Double salts of zirconium perchlorate are called perchloratozirconates or hexaperchloratozirconates. Known salts include caesium perchloratozirconate (Cs2Zr(ClO4)6), and nitrile perchloratozirconate(sic) [4] ((NO2)2Zr(ClO4)6). [5] Other perchloratozirconates with varying numbers of perchlorate groups also include CsZr(ClO4)5, Cs3Zr(ClO4)7, and Cs4Zr(ClO4)8. [6]

Zirconyl perchlorate (CAS: 15607-09-7) is another perchlorate of zirconium with the formula ZrO(ClO4)2. It is synthesized by reacting Zr(OH)4 with HClO4, then the colorless crystals are formed by slow evaporation. [7]

Related Research Articles

<span class="mw-page-title-main">Chlorine</span> Chemical element, symbol Cl and atomic number 17

Chlorine is a chemical element with the symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between them. Chlorine is a yellow-green gas at room temperature. It is an extremely reactive element and a strong oxidising agent: among the elements, it has the highest electron affinity and the third-highest electronegativity on the revised Pauling scale, behind only oxygen and fluorine.

<span class="mw-page-title-main">Perchloric acid</span> Chemical compound

Perchloric acid is a mineral acid with the formula HClO4. Usually found as an aqueous solution, this colorless compound is a stronger acid than sulfuric acid, nitric acid and hydrochloric acid. It is a powerful oxidizer when hot, but aqueous solutions up to approximately 70% by weight at room temperature are generally safe, only showing strong acid features and no oxidizing properties. Perchloric acid is useful for preparing perchlorate salts, especially ammonium perchlorate, an important rocket fuel component. Perchloric acid is dangerously corrosive and readily forms potentially explosive mixtures.

<span class="mw-page-title-main">Chlorine oxide</span> Index of chemical compounds with the same name

Chlorine and oxygen can bond in many ways:

<span class="mw-page-title-main">Dichlorine heptoxide</span> Chemical compound

Dichlorine heptoxide is the chemical compound with the formula Cl2O7. This chlorine oxide is the anhydride of perchloric acid. It is produced by the careful distillation of perchloric acid in the presence of the dehydrating agent phosphorus pentoxide:

<span class="mw-page-title-main">Sodium perchlorate</span> Chemical compound

Sodium perchlorate is the inorganic compound with the chemical formula NaClO4. It is a white crystalline, hygroscopic solid that is highly soluble in water and in alcohol. It is usually encountered as the monohydrate. The compound is noteworthy as the most water-soluble of the common perchlorate salts.

<span class="mw-page-title-main">Zirconium(IV) chloride</span> Chemical compound

Zirconium(IV) chloride, also known as zirconium tetrachloride, is an inorganic compound frequently used as a precursor to other compounds of zirconium. This white high-melting solid hydrolyzes rapidly in humid air.

<span class="mw-page-title-main">Thorium(IV) chloride</span> Chemical compound

Thorium(IV) chloride describes a family of inorganic compounds with the formula ThCl4(H2O)n. Both the anhydrous and tetrahydrate (n = 4) forms are known. They are hygroscopic, water-soluble white salts.

<span class="mw-page-title-main">Zirconyl chloride</span> Chemical compound

Zirconyl chloride is the inorganic compound with the formula of [Zr4(OH)8(H2O)16]Cl8(H2O)12, more commonly written ZrOCl2·8H2O, and referred to as zirconyl chloride octahydrate. It is a white solid and is the most common water-soluble derivative of zirconium. A compound with the formula ZrOCl2 has not been characterized.

<span class="mw-page-title-main">Dichlorine hexoxide</span> Chemical compound

Dichlorine hexoxide is the chemical compound with the molecular formula Cl
2O
6, which is correct for its gaseous state. However, in liquid or solid form, this chlorine oxide ionizes into the dark red ionic compound chloryl perchlorate [ClO
2]+
[ClO
4]−
, which may be thought of as the mixed anhydride of chloric and perchloric acids.

<span class="mw-page-title-main">Chlorine perchlorate</span> Chemical compound

Chlorine perchlorate is a chemical compound with the formula Cl2O4. This chlorine oxide is an asymmetric oxide, with one chlorine atom in +1 oxidation state and the other +7, with proper formula ClOClO3. It is produced by the photodimerization of chlorine dioxide (ClO2) at room temperature by 436 nm ultraviolet light:

<span class="mw-page-title-main">Zirconium(III) chloride</span> Chemical compound

Zirconium(III) chloride is an inorganic compound with formula ZrCl3. It is a blue-black solid that is highly sensitive to air.

Chlorine tetroxide is an unstable chlorine oxide with the chemical formula ClO4.

Perchloratoborate is an anion of the form [B(ClO4)4]−. It can form partly stable solid salts with heavy alkali metals. They are more stable than nitratoborate salts. K[B(ClO4)4] decomposes at 35 °C, Rb[B(ClO4)4] is stable to 50 °C, and Cs[B(ClO4)4] can exist up to 80 °C.

Hexanitratoaluminate is an anion of aluminium and six nitrate groups with formula [Al(NO3)6]3− that can form salts called hexanitratoaluminates.

<span class="mw-page-title-main">Titanium perchlorate</span> Chemical compound

Titanium perchlorate is a molecular compound of titanium and perchlorate groups with formula Ti(ClO4)4. Anhydrous titanium perchlorate decomposes explosively at 130 °C and melts at 85 °C with a slight decomposition. It can sublime in a vacuum as low as 70 °C, and can form vapour at up to 120°. Titanium perchlorate is quite volatile. It has density 2.35. It decomposes to TiO2, ClO2 and dioxygen O2 Also TiO(ClO4)2 is formed during decomposition.

<span class="mw-page-title-main">Vanadyl perchlorate</span> Chemical compound

Vanadyl perchlorate or vanadyl triperchlorate is a golden yellow coloured liquid or crystalline compound of vanadium, oxygen and perchlorate group. The substance consists of molecules covalently bound and is quite volatile.

<span class="mw-page-title-main">Zirconium nitrate</span> Chemical compound

Zirconium nitrate is a volatile anhydrous transition metal nitrate salt of zirconium with formula Zr(NO3)4. It has alternate names of zirconium tetranitrate, or zirconium(IV) nitrate.

<span class="mw-page-title-main">Nickel(II) perchlorate</span> Compound of nickel

Nickel(II) perchlorate is a inorganic compound with the chemical formula of Ni(ClO4)2, and it is a strong oxidizing agent. Its colours are different depending on water. For example, the hydrate forms cyan crystals, the pentahydrate forms green crystals, but the hexahydrate (Ni(ClO4)2·6H2O) forms blue crystals.

<span class="mw-page-title-main">Lead(II) perchlorate</span> Chemical compound

Lead(II) perchlorate is a chemical compound with the formula Pb(ClO4)2·xH2O, where is x is 0,1, or 3. It is an extremely hygroscopic white solid that is very soluble in water.

References

  1. 1 2 3 4 5 6 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. ↑ 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.
  3. ↑ 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.
  4. ↑ dinitro perchloratozirconate
  5. ↑ 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.
  6. ↑ Babaeva, V.P.; Rosolovski, V.Ya. (1978). "Synthesis and properties of cesium perchloratozirconates". Zhurnal Neorganicheskoj Khimii. 23 (4): 955–959.
  7. ↑ Murthy, P. Rama; Patel, C. C. (1961). "Zirconyl perchlorate". Die Naturwissenschaften. 48 (22): 693. Bibcode:1961NW.....48..693M. doi:10.1007/BF00595937. S2CID   34179500.
Compounds containing perchlorate group
HClO4 He
LiClO4 Be(ClO4)2 B(ClO4)−4
B(ClO4)3 		ROClO3 N(ClO4)3
NH4ClO4
NOClO4 		H3OClO4 FClO4 Ne
NaClO4 Mg(ClO4)2 Al(ClO4)3
Al(ClO4)−4
Al(ClO4)2−5
Al(ClO4)3−6 		SiPS 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)2
Fe(ClO4)3 		Co(ClO4)2,
Co(ClO4)3 		Ni(ClO4)2 Cu(ClO4)2 Zn(ClO4)2 Ga(ClO4)3 GeAsSeBrKr
RbClO4 Sr(ClO4)2 Y(ClO4)3 Zr(ClO4)4 Nb(ClO4)5 MoTcRu Rh(ClO4)3 Pd(ClO4)2 AgClO4 Cd(ClO4)2 In(ClO4)3 Sn(ClO4)4 Sb TeO(ClO4)2 IXe
CsClO4 Ba(ClO4)2   Lu(ClO4)3 Hf(ClO4)4 Ta(ClO4)5
TaO(ClO4)3
TaO2ClO4 		WReOsIrPtAu Hg2(ClO4)2,
Hg(ClO4)2 		Tl(ClO4),
Tl(ClO4)3 		Pb(ClO4)2 Bi(ClO4)3 PoAtRn
FrClO4 Ra LrRfDbSgBhHsMtDsRgCnNhFlMcLvTsOg
↓
La Ce(ClO4)x Pr(ClO4)3 Nd(ClO4)3 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
Ac Th(ClO4)4 Pa UO2(ClO4)2 NpPuAmCmBkCfEsFmMdNo
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