Zirconium(IV) chloride

Names
IUPAC names

Zirconium tetrachloride
Zirconium(IV) chloride

Identifiers

CAS Number

* 10026-11-6 Y

3D model (JSmol)

* Interactive image

ChEBI |

* CHEBI:77566 N

ChemSpider |

* 23202 Y

EC Number |

* 233-058-2

PubChem CID

* 24817

UNII |

* Z88176T871 N

InChI

* InChI=1S/4ClH.Zr/h4*1H;/q;;;;+4/p-4 Y

Key: DUNKXUFBGCUVQW-UHFFFAOYSA-J Y

* InChI=1/4ClH.Zr/h4*1H;/q;;;;+4/p-4

Key: DUNKXUFBGCUVQW-XBHQNQODAQ

SMILES

* Cl[Zr](Cl)(Cl)Cl

Properties

Chemical formula

| ZrCl4
Molar mass | 233.04 g/mol
Appearance  | white crystals
Density | 2.80 g/cm3
Melting point |  437 °C (819 °F; 710 K) (triple point)
Boiling point |  331 °C (628 °F; 604 K) (sublimes)

Solubility in water

| hydrolysis
Solubility | concentrated HCl (with reaction)
Structure

Crystal structure

| Monoclinic, mP10

Space group

| P12/c1, No. 13
Thermochemistry

Heat capacity (C)

| 125.38 J K−1 mol−1

Std molar
entropy (S ~~o~~ 298)

| 181.41 J K−1 mol−1

Std enthalpy of
formation (ΔfH⦵298)

| −980.52 kJ/mol
Hazards
Safety data sheet | MSDS
GHS pictograms |
GHS Signal word | danger
NFPA 704 (fire diamond)  |

~~W~~

Flash point | Non-flammable
Lethal dose or concentration (LD, LC):

LD50 (median dose)

| 1488-1500 mg/kg (oral, rat)
655 mg/kg (mouse, oral)[1]
Related compounds

Other anions

| Zirconium(IV) fluoride
Zirconium(IV) bromide
Zirconium(IV) iodide

Other cations

| Titanium tetrachloride
Hafnium tetrachloride

Related compounds

| Zirconium(II) chloride, Zirconium(III) chloride

Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

N verify (what is YN ?)
Infobox references

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

## Contents

* 1 Structure
* 2 Synthesis
* 3 Applications
* 3.1 Precursor to Zr metal
* 3.2 Other uses
* 4 Properties and reactions
* 5 References

## Structure

Unlike molecular TiCl4, solid ZrCl4 adopts a polymeric structure wherein each Zr is octahedrally coordinated. This difference in structures is responsible for the disparity in their properties: TiCl4 is distillable, but ZrCl4 is a solid. In the solid state, ZrCl4 adopts a tape-like linear polymeric structure—the same structure adopted by HfCl4. This polymer degrades readily upon treatment with Lewis bases, which cleave the Zr-Cl-Zr linkages.[4]

## Synthesis

This conversion entails treatment of zirconium oxide with carbon in the presence of chlorine at high temperature:

ZrO2 \+ 2 C + 2 Cl2 → ZrCl4 \+ 2 CO

A laboratory scale process uses carbon tetrachloride in place of carbon and chlorine:[5]

ZrO2 \+ 2 CCl4 → ZrCl4 \+ 2 COCl2

## Applications

### Precursor to Zr metal

ZrCl4 is an intermediate in the conversion of zirconium minerals to metallic zirconium by the Kroll process. In nature, zirconium minerals invariably exist as oxides (reflected also by the tendency of all zirconium chlorides to hydrolyze). For their conversion to bulk metal, these refractory oxides are first converted to the tetrachloride, which can be distilled at high temperatures. The purified ZrCl4 can be reduced with Zr metal to produce zirconium(III) chloride.

### Other uses

ZrCl4 is the most common precursor for chemical vapor deposition of zirconium dioxide and zirconium diboride.[6]

In organic synthesis zirconium tetrachloride is used as a weak Lewis acid for the Friedel-Crafts reaction, the Diels-Alder reaction and intramolecular cyclisation reactions.[7] It is also used to make water-repellent treatment of textiles and other fibrous materials.

## Properties and reactions

Hydrolysis of ZrCl4 gives the hydrated hydroxy chloride cluster called zirconyl chloride. This reaction is rapid and virtually irreversible, consistent with the high oxophilicity of zirconium(IV). For this reason, manipulations of ZrCl4 typically require air-free techniques.

ZrCl4 is the principal starting compound for the synthesis of many organometallic complexes of zirconium.[8] Because of its polymeric structure, ZrCl4 is usually converted to a molecular complex before use. It forms a 1:2 complex with tetrahydrofuran: CAS [21959-01-3], mp 175–177 °C.[9] Sodium cyclopentadienide (NaC5H5) reacts with ZrCl4(THF)2 to give zirconocene dichloride, ZrCl2(C5H5)2, a versatile organozirconium complex.[10] One of the most curious properties of ZrCl4 is its high solubility in the presence of methylated benzenes, such as durene. This solubilization arises through the formation of π-complexes.[11]

The log (base 10) of the vapor pressure of zirconium tetrachloride (from 480 to 689 K) is given by the equation: log10(P) = −5400/T + 11.766, where the pressure is measured in torrs and temperature in kelvins. The log (base 10) of the vapor pressure of solid zirconium tetrachloride (from 710 to 741 K) is given by the equation log10(P) = −3427/T + 9.088. The pressure at the melting point is 14,500 torrs.[12]

## References

1. ↑ "Zirconium compounds (as Zr)". Immediately Dangerous to Life and Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH). https://www.cdc.gov/niosh/idlh/7440677.html.
2. ↑ GHS: PubChem
3. ↑ "New Environment Inc. - NFPA Chemicals". newenv.com. http://www.newenv.com/resources/nfpa_chemicals.
4. ↑ N. N. Greenwood & A. Earnshaw, Chemistry of the Elements (2nd ed.), Butterworth-Heinemann, Oxford, 1997.
5. ↑ Hummers, W. S.; Tyree, S. Y.; Yolles, S. (1953). "Zirconium and Hafnium Tetrachlorides". Inorganic Syntheses. IV. McGraw-Hill Book Company, Inc.. p. 121. doi:10.1002/9780470132357.ch41. ISBN 9780470132357.
6. ↑ Randich, E. (1 November 1979). "Chemical vapor deposited borides of the form (Ti,Zr)B2 and (Ta,Ti)B2". Thin Solid Films 63 (2): 309–313. doi:10.1016/0040-6090(79)90034-8. Bibcode: 1979TSF....63..309R.
7. ↑ Bora U. (2003). "Zirconium Tetrachloride". Synlett (7): 1073–1074. doi:10.1055/s-2003-39323.
8. ↑ Ilan Marek, ed (2005). New Aspects of Zirconium Containing Organic Compounds. Topics in Organometallic Chemistry. 10. Springer: Berlin, Heidelberg, New York. doi:10.1007/b80198. ISBN 978-3-540-22221-7.
9. ↑ L. E. Manzer; Joe Deaton (1982). Tetrahydrofuran Complexes of Selected Early Transition Metals. Inorganic Syntheses. 21. pp. 135–140. doi:10.1002/9780470132524.ch31. ISBN 978-0-470-13252-4.
10. ↑ Wilkinson, G.; Birmingham, J. G. (1954). "Bis-cyclopentadienyl Compounds of Ti, Zr, V, Nb and Ta". J. Am. Chem. Soc. 76 (17): 4281–4284. doi:10.1021/ja01646a008.
11. ↑ Musso, F.; Solari, E.; Floriani, C.; Schenk, K. (1997). "Hydrocarbon Activation with Metal Halides: Zirconium Tetrachloride Catalyzing the Jacobsen Reaction and Assisting the Trimerization of Alkynes via the Formation of η6-Arene-Zirconium(IV) Complexes". Organometallics 16 (22): 4889–4895. doi:10.1021/om970438g.
12. ↑ Palko, A. A.; Ryon, A. D.; Kuhn, D. W. (March 1958). "The Vapor Pressures of Zirconium Tetrachloride and Hafnium Tetrachloride". J. Phys. Chem. 62 (3): 319–322. doi:10.1021/j150561a017.

* v
* t
* e

Zirconium compounds

Zr(II)|

* ZrB2
* ZrH2
* ZrSi2

Zr(III)|

* ZrN
* ZrCl3

Zr(IV)|

* ZrBr4
* ZrC
* ZrCl4
* ZrF4
* ZrI4
* Zr(NO3)4
* ZrOCl2
* Zr(OH)4
* ZrO2
* ZrS2
* Zr(SO4)2
* ZrSiO4
* Zr(WO4)2

| Organozirconium(IV)|

* Zr(acac)4

|

* v
* t
* e

Salts and covalent derivatives of the chloride ion

HCl |  |  |  | He

|
|
|
|

LiCl | BeCl2 | BCl3
B2Cl4 | CCl4 | NCl3
ClN3 | Cl2O
ClO2
Cl2O7 | ClF
ClF3
ClF5 | Ne
NaCl | MgCl2 | AlCl
AlCl3 | SiCl4 | P2Cl4
PCl3
PCl5 | S2Cl2
SCl2
SCl4 | Cl2 | Ar
KCl | CaCl
CaCl2 | ScCl3 | TiCl2
TiCl3
TiCl4 | VCl2
VCl3
VCl4
VCl5 | CrCl2
CrCl3
CrCl4 | MnCl2 | FeCl2
FeCl3 | CoCl2
CoCl3 | NiCl2 | CuCl
CuCl2 | ZnCl2 | GaCl2
GaCl3 | GeCl2
GeCl4 | AsCl3
AsCl5 | Se2Cl2
SeCl4 | BrCl | KrCl
RbCl | SrCl2 | YCl3 | ZrCl3
ZrCl4 | NbCl4
NbCl5 | MoCl2
MoCl3
MoCl4
MoCl5
MoCl6 | TcCl4 | RuCl3 | RhCl3 | PdCl2 | AgCl | CdCl2 | InCl
InCl2
InCl3 | SnCl2
SnCl4 | SbCl3
SbCl5 | Te3Cl2
TeCl4 | ICl
ICl3 | XeCl
XeCl2
CsCl | BaCl2 |  | HfCl4 | TaCl5 | WCl2
WCl3
WCl4
WCl5
WCl6 | Re3Cl9
ReCl4
ReCl5
ReCl6 | OsCl4 | IrCl2
IrCl3
IrCl4 | PtCl2
PtCl4 | AuCl
AuCl3 | Hg2Cl2,
HgCl2 | TlCl | PbCl2,
PbCl4 | BiCl3 | PoCl2,
PoCl4 | AtCl  | RnCl2
FrCl | RaCl2 |  | Rf  | Db  | Sg  | Bh  | Hs  | Mt  | Ds  | Rg  | Cn  | Nh  | Fl  | Mc  | Lv  | Ts  | Og
| ↓  |  |
LaCl3 | CeCl3 | PrCl3 | NdCl2,
NdCl3 | PmCl3 | SmCl2,
SmCl3 | EuCl2,
EuCl3 | GdCl3 | TbCl3 | DyCl2,
DyCl3 | HoCl3 | ErCl3 | TmCl2
TmCl3 | YbCl2
YbCl3 | LuCl3
AcCl3 | ThCl4 | PaCl5 | UCl3
UCl4
UCl5
UCl6 | NpCl4 | PuCl3 | AmCl2
AmCl3 | CmCl3 | BkCl3 | CfCl3 | EsCl3 | Fm  | Md  | No  | LrCl3

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