Zirconium(III) chloride

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Zirconium(III) chloride
ZrCl3-polyhedral.png
Names
IUPAC name
Zirconium trichloride
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
  • InChI=1S/3ClH.Zr/h3*1H;/q;;;+3/p-3 X mark.svgN
    Key: PFXYQVJESZAMSV-UHFFFAOYSA-K X mark.svgN
  • Cl[Zr](Cl)Cl
Properties
Cl3Zr
Molar mass 197.57 g·mol−1
AppearanceBlue-black crystals
Density 3.05 g/cm3 [1]
Melting point 627 °C (1,161 °F; 900 K)
at 760 mmHg [1]
Reacts [1]
Solubility Soluble in benzene, CS2
Structure
Hexagonal, hP6 [2]
P63/mcm, No. 193 [2]
6/m 2/m 2/m [2]
a = 6.36 Å, c = 6.14 Å [2]
α = 90°, β = 90°, γ = 120°
Thermochemistry
96.21 J/mol·K [3]
Std molar
entropy
(S298)
145.79 J/mol·K [3]
−714.21 kJ/mol [3]
Related compounds
Other anions
Zirconium(III) bromide
Zirconium(III) iodide
Other cations
Titanium(III) chloride
Hafnium(III) chloride
Related compounds
Zirconium(IV) chloride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Zirconium(III) chloride is an inorganic compound with formula ZrCl3. It is a blue-black solid that is highly sensitive to air.

Contents

Preparation

The material was first claimed by Ruff and Wallstein who reduced zirconium tetrachloride with aluminium to give impure samples. [4] Subsequently, the problem with aluminium contamination was solved when it was prepared by reduction using zirconium metal: [5]

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. [6]

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. [7]

ZrCl4 + ½ H2 → ZrCl3 + HCl

Structure

Some zirconium halides (ZrCl3, ZrBr3, and ZrI3) have structures similar to HfI3. They also have similar space group (P63/mcm) and hexagonal structure with 2 molecules in the cell. [2] 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. [8]

Related Research Articles

<span class="mw-page-title-main">Titanium tetrachloride</span> Inorganic chemical compound

Titanium tetrachloride is the inorganic compound with the formula TiCl4. It is an important intermediate in the production of titanium metal and the pigment titanium dioxide. TiCl4 is a volatile liquid. Upon contact with humid air, it forms thick clouds of titanium dioxide and hydrochloric acid, a reaction that was formerly exploited for use in smoke machines. It is sometimes referred to as "tickle" or "tickle 4" due to the phonetic resemblance of its molecular formula to the word.

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

Aluminium chloride, also known as aluminium trichloride, is an inorganic compound with the formula AlCl3. It forms hexahydrate with the formula [Al(H2O)6]Cl3, containing six water molecules of hydration. Both are colourless crystals, but samples are often contaminated with iron(III) chloride, giving a yellow color.

<span class="mw-page-title-main">Hafnium tetrachloride</span> Chemical compound

Hafnium(IV) chloride is the inorganic compound with the formula HfCl4. This colourless solid is the precursor to most hafnium organometallic compounds. It has a variety of highly specialized applications, mainly in materials science and as a catalyst.

Boron trichloride is the inorganic compound with the formula BCl3. This colorless gas is a reagent in organic synthesis. It is highly reactive toward water.

<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.

Titanium(III) chloride is the inorganic compound with the formula TiCl3. At least four distinct species have this formula; additionally hydrated derivatives are known. TiCl3 is one of the most common halides of titanium and is an important catalyst for the manufacture of polyolefins.

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

Gallium(III) bromide (GaBr3) is a chemical compound, and one of four gallium trihalides.

<span class="mw-page-title-main">Gallium trichloride</span> Chemical compound

Gallium trichloride is the chemical compound with the formula GaCl3. Solid gallium trichloride exists as a dimer with the formula Ga2Cl6. It is colourless and soluble in virtually all solvents, even alkanes, which is truly unusual for a metal halide. It is the main precursor to most derivatives of gallium and a reagent in organic synthesis.

<span class="mw-page-title-main">Rhenium pentachloride</span> Chemical compound

Rhenium pentachloride is an inorganic compound of chlorine and rhenium. The compound has the formula Re2Cl10 but it is usually referred to as rhenium pentachloride. It is a red-brown solid.

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

Technetium(IV) chloride is the inorganic compound with the formula TcCl4. It was discovered in 1957 as the first binary halide of technetium. It is the highest oxidation binary chloride of technetium that has been isolated as a solid. It is volatile at elevated temperatures and its volatility has been used for separating technetium from other metal chlorides. Colloidal solutions of technetium(IV) chloride are oxidized to form Tc(VII) ions when exposed to gamma rays.

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

Niobium(IV) chloride, also known as niobium tetrachloride, is the chemical compound of formula NbCl4. This compound exists as dark violet crystals, is highly sensitive to air and moisture, and disproportiates into niobium(III) chloride and niobium(V) chloride when heated.

<span class="mw-page-title-main">Berkelium compounds</span> Any chemical compound having at least one berkelium atom

Berkelium forms a number of chemical compounds, where it normally exists in an oxidation state of +3 or +4, and behaves similarly to its lanthanide analogue, terbium. Like all actinides, berkelium easily dissolves in various aqueous inorganic acids, liberating gaseous hydrogen and converting into the trivalent oxidation state. This trivalent state is the most stable, especially in aqueous solutions, but tetravalent berkelium compounds are also known. The existence of divalent berkelium salts is uncertain and has only been reported in mixed lanthanum chloride-strontium chloride melts. Aqueous solutions of Bk3+ ions are green in most acids. The color of the Bk4+ ions is yellow in hydrochloric acid and orange-yellow in sulfuric acid. Berkelium does not react rapidly with oxygen at room temperature, possibly due to the formation of a protective oxide surface layer; however, it reacts with molten metals, hydrogen, halogens, chalcogens and pnictogens to form various binary compounds. Berkelium can also form several organometallic compounds.

<span class="mw-page-title-main">Metal bis(trimethylsilyl)amides</span>

Metal bis(trimethylsilyl)amides are coordination complexes composed of a cationic metal with anionic bis(trimethylsilyl)amide ligands and are part of a broader category of metal amides.

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

Molybdenum(III) chloride is the inorganic compound with the formula MoCl3. It forms purple crystals.

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

Tantalum(III) chloride or tantalum trichloride is non-stoichiometric with a range of composition from TaCl2.9 to TaCl3.1 Anionic and neutral clusters containing Ta(III) chloride include [Ta6Cl18]4− and [Ta6Cl14](H2O)4.

Dysprosium(II) chloride (DyCl2), also known as dysprosium dichloride, is an ionic chemical compound of dysprosium and chlorine. This salt is a reduced compound, as the normal oxidation state of dysprosium in dysprosium compounds is +3.

A chloride nitride is a mixed anion compound containing both chloride (Cl) and nitride ions (N3−). Another name is metallochloronitrides. They are a subclass of halide nitrides or pnictide halides.

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

Zirconium(III) bromide is an inorganic compound with the formula ZrBr3.

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

Zirconium(III) iodide is an inorganic compound with the formula ZrI3.

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

Hafnium(III) iodide is an inorganic compound of hafnium and iodine with the formula HfI3. It is a black solid.

References

  1. 1 2 3 Lide, David R., ed. (2009). CRC Handbook of Chemistry and Physics (90th ed.). Boca Raton, Florida: CRC Press. ISBN   978-1-4200-9084-0.
  2. 1 2 3 4 5 Douglas, Bodie E.; Ho, Shih-Ming (2007). Structure and Chemistry of Crystalline Solids. New York: Springer Science+Business Media, Inc. p. 101. ISBN   978-0-387-26147-8.
  3. 1 2 3 Zirconium chloride in Linstrom, Peter J.; Mallard, William G. (eds.); NIST Chemistry WebBook, NIST Standard Reference Database Number 69, National Institute of Standards and Technology, Gaithersburg (MD) (retrieved 2014-06-23)
  4. Ruff, Otto; Wallstein, Richard (1923). "Reduktion anorganischer Halogenide III.1) Die Reduktion des Zirkontetrachlorids". Zeitschrift für anorganische und allgemeine Chemie. 128: 96–116. doi:10.1002/zaac.19231280110.
  5. 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.
  6. 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.
  7. 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.
  8. Wells, A.F. Structural Inorganic Chemistry. Oxford Science Publications, 1975, 5th ed, 417-420.