| Revision as of 12:40, 15 February 2012 editBeetstra (talk | contribs)Edit filter managers, Administrators172,031 edits Saving copy of the {{chembox}} taken from revid 473548976 of page Zirconium(IV)_chloride for the Chem/Drugbox validation project (updated: ''). |
Latest revision as of 23:00, 26 July 2024 edit Rich Farmbrough (talk | contribs)Edit filter managers, Autopatrolled, Extended confirmed users, File movers, Pending changes reviewers, Rollbackers, Template editors1,725,189 edits Copyedit. Date formats. |
| Line 1: |
Line 1: |
|
{{ambox | text = This page contains a copy of the infobox ({{tl|chembox}}) taken from revid of page ] with values updated to verified values.}} |
|
|
{{chembox |
|
{{chembox |
|
|
|Verifiedfields = changed |
|
| verifiedrevid = 470637821 |
|
|
|
|Watchedfields = changed |
|
| ImageFile = Zirconium-tetrachloride-3D-balls-A.png |
|
|
|
|verifiedrevid = 476995548 |
|
| ImageFile1 = Zirconium-tetrachloride-3D-balls-B.png |
|
|
| Name = Zirconium(IV) chloride |
|
|ImageFile = Zirconium-tetrachloride-3D-balls-A.png |
|
| IUPACName = Zirconium tetrachloride<br/>Zirconium(IV) chloride |
|
|ImageFile1 = Zirconium-tetrachloride-3D-balls-B.png |
|
|
|ImageFile2 = Zirconium(IV) chloride.jpg |
|
| OtherNames = |
|
|
|
|Name = Zirconium(IV) chloride |
|
| Section1 = {{Chembox Identifiers |
|
|
|
|IUPACName = Zirconium tetrachloride<br/>Zirconium(IV) chloride |
|
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
|
|
|
|Section1={{Chembox Identifiers |
|
| ChemSpiderID = 23202 |
|
|
|
|PubChem = 24817 |
|
| InChI = 1/4ClH.Zr/h4*1H;/q;;;;+4/p-4 |
|
|
|
|ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
|
| InChIKey = DUNKXUFBGCUVQW-XBHQNQODAQ |
|
|
|
|ChemSpiderID = 23202 |
|
| SMILES = Cl(Cl)(Cl)Cl |
|
|
|
|ChEBI_Ref = {{ebicite|changed|EBI}} |
|
| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
|
|
|
|ChEBI = 77566 |
|
| StdInChI = 1S/4ClH.Zr/h4*1H;/q;;;;+4/p-4 |
|
|
|
|InChI = 1/4ClH.Zr/h4*1H;/q;;;;+4/p-4 |
|
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
|
|
| StdInChIKey = DUNKXUFBGCUVQW-UHFFFAOYSA-J |
|
|InChIKey = DUNKXUFBGCUVQW-XBHQNQODAQ |
|
|
|SMILES = Cl(Cl)(Cl)Cl |
|
| CASNo = 10026-11-6 |
|
|
| CASNo_Ref = {{cascite|correct|CAS}} |
|
|StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
|
|
|StdInChI = 1S/4ClH.Zr/h4*1H;/q;;;;+4/p-4 |
|
| EINECS = 233-058-2 |
|
|
|
|StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
|
}} |
|
|
|
|StdInChIKey = DUNKXUFBGCUVQW-UHFFFAOYSA-J |
|
| Section2 = {{Chembox Properties |
|
|
|
|CASNo = 10026-11-6 |
|
| Formula = ZrCl<sub>4</sub> |
|
|
|
|CASNo_Ref = {{cascite|correct|CAS}} |
|
| MolarMass = 233.04 g/mol |
|
|
|
|UNII_Ref = {{fdacite|changed|FDA}} |
|
| Appearance = white crystals <br> ] |
|
|
|
|UNII = Z88176T871 |
|
| Density = 2.80 g/cm<sup>3</sup> |
|
|
|
|EINECS = 233-058-2 |
|
| Solubility = hydrolysis |
|
|
| SolubleOther = soluble in ], ], concentrated ] |
|
|
| MeltingPt = 437 °C (triple point) |
|
|
| BoilingPt = 331 °C |
|
|
}} |
|
|
| Section3 = {{Chembox Structure |
|
|
| CrystalStruct = ], ] |
|
|
| SpaceGroup = P12/c1, No. 13 |
|
|
}} |
|
|
| Section4 = {{Chembox Thermochemistry |
|
|
| DeltaHf = −980.52 kJ/mol |
|
|
| Entropy = 181.41 J K<sup>−1</sup> mol<sup>−1</sup> |
|
|
| Cp = 125.38 J K<sup>−1</sup> mol<sup>−1</sup> |
|
|
}} |
|
|
| Section7 = {{Chembox Hazards |
|
|
| ExternalMSDS = |
|
|
| EUClass = |
|
|
| EUIndex = Not listed |
|
|
| MainHazards = |
|
|
| NFPA-H = |
|
|
| NFPA-F = |
|
|
| NFPA-R = |
|
|
| NFPA-O = |
|
|
| RPhrases = |
|
|
| SPhrases = |
|
|
| FlashPt = Non-flammable |
|
|
| PEL = |
|
|
| LD50 = 1688 mg/kg (oral, rat) |
|
|
}} |
|
|
| Section8 = {{Chembox Related |
|
|
| OtherAnions = ]<br/>]<br/>] |
|
|
| OtherCations = ]<br/>] |
|
|
}} |
|
|
}} |
|
}} |
|
|
|Section2={{Chembox Properties |
|
|
|Formula = ZrCl<sub>4</sub> |
|
|
|MolarMass = 233.04 g/mol |
|
|
|Appearance = white crystals |
|
|
|Density = 2.80 g/cm<sup>3</sup> |
|
|
|Solubility = hydrolysis |
|
|
|SolubleOther = concentrated ] (with reaction) |
|
|
|MeltingPtC = 437 |
|
|
|MeltingPt_notes = (triple point) |
|
|
|BoilingPtC = 331 |
|
|
|BoilingPt_notes = (sublimes) |
|
|
}} |
|
|
|Section3={{Chembox Structure |
|
|
|CrystalStruct = ], ] |
|
|
|SpaceGroup = P12/c1, No. 13 |
|
|
}} |
|
|
|Section4={{Chembox Thermochemistry |
|
|
|DeltaHf = −980.52 kJ/mol |
|
|
|Entropy = 181.41 J K<sup>−1</sup> mol<sup>−1</sup> |
|
|
|HeatCapacity = 125.38 J K<sup>−1</sup> mol<sup>−1</sup> |
|
|
}} |
|
|
|Section7={{Chembox Hazards |
|
|
|ExternalSDS = |
|
|
|MainHazards = |
|
|
|NFPA-H = 3 |
|
|
|NFPA-F = 0 |
|
|
|NFPA-R = 2 |
|
|
|NFPA-S = W |
|
|
|GHSPictograms = {{GHS05}} {{GHS07}} {{GHS08}} |
|
|
|GHSSignalWord = danger |
|
|
|HPhrases = {{HPhrases|H290|H302|H312|H314|H317|H332|H334}} |
|
|
|PPhrases = {{PPhrases|P234|P260| P261| P264| P270| P271| P272| P280| P285| P301+P312| P301+P330+P331| P302+P352| P303+P361+P353|P304+P312| P304+P340| P304+P341| P305+P351+P338|P310| P312| P321|P322| P330| P333+P313| P342+P311|P363|P390|P404|P405|P501}} |
|
|
|GHS_ref = <ref>GHS: </ref> |
|
|
|FlashPt = Non-flammable |
|
|
|LD50 = 1488-1500 mg/kg (oral, rat)<br/>655 mg/kg (mouse, oral)<ref>{{IDLH|7440677|Zirconium compounds (as Zr)}}</ref> |
|
|
}}<ref name="newenv">{{cite web|url=http://www.newenv.com/resources/nfpa_chemicals|publisher=newenv.com|title=New Environment Inc. - NFPA Chemicals|access-date=2017-04-26}}</ref> |
|
|
|Section8={{Chembox Related |
|
|
|OtherAnions = ]<br/>]<br/>] |
|
|
|OtherCations = ]<br/>] |
|
|
|OtherCompounds = ], ] |
|
|
}} |
|
|
}} |
|
|
'''Zirconium(IV) chloride''', also known as '''zirconium tetrachloride''', ({{chem2|auto=1|ZrCl4}}) is an ] frequently used as a precursor to other compounds of zirconium. This white high-melting solid hydrolyzes rapidly in humid air. |
|
|
|
|
|
==Structure== |
|
|
Unlike molecular ], solid ZrCl<sub>4</sub> adopts a polymeric structure wherein each Zr is octahedrally coordinated. This difference in structures is responsible for the disparity in their properties: {{chem|TiCl|4}} is distillable, but {{chem|ZrCl|4}} is a solid. In the solid state, ZrCl<sub>4</sub> adopts a tape-like linear polymeric structure—the same structure adopted by ]. This polymer degrades readily upon treatment with ]s, which cleave the Zr-Cl-Zr linkages.<ref>N. N. Greenwood & A. Earnshaw, ''Chemistry of the Elements'' (2nd ed.), Butterworth-Heinemann, Oxford, '''1997'''.</ref> |
|
|
|
|
|
==Synthesis== |
|
|
This conversion entails treatment of zirconium oxide with carbon in the presence of chlorine at high temperature: |
|
|
:ZrO<sub>2</sub> + 2 C + 2 Cl<sub>2</sub> → ZrCl<sub>4</sub> + 2 CO |
|
|
|
|
|
A laboratory scale process uses ] in place of carbon and chlorine:<ref>{{cite book |first1=W. S. |last1=Hummers |first2=S. Y. |last2=Tyree |first3=S. |last3=Yolles |chapter=Zirconium and Hafnium Tetrachlorides |title=Inorganic Syntheses |year=1953 |volume=IV |page=121 |doi=10.1002/9780470132357.ch41 |publisher=McGraw-Hill Book Company, Inc.|isbn=978-0-470-13235-7 }}</ref> |
|
|
:ZrO<sub>2</sub> + 2 CCl<sub>4</sub> → ZrCl<sub>4</sub> + 2 COCl<sub>2</sub> |
|
|
|
|
|
==Applications== |
|
|
===Precursor to zirconium metal=== |
|
|
ZrCl<sub>4</sub> is an intermediate in the conversion of zirconium minerals to metallic ] by the ]. In nature, zirconium minerals usually 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 ] at high temperatures. The purified ZrCl<sub>4</sub> can be reduced with Zr metal to produce ]. |
|
|
|
|
|
===Other uses=== |
|
|
ZrCl<sub>4</sub> is the most common precursor for ] of ] and ].<ref>{{cite journal |first=E.|last=Randich |title=Chemical vapor deposited borides of the form (Ti,Zr)B<sub>2</sub> and (Ta,Ti)B<sub>2</sub> |journal=Thin Solid Films |volume=63 |issue=2 |date=1 November 1979 |pages=309–313 |doi=10.1016/0040-6090(79)90034-8|bibcode = 1979TSF....63..309R }}</ref> |
|
|
|
|
|
In organic synthesis zirconium tetrachloride is used as a weak ] for the ], the ] and intramolecular cyclisation reactions.<ref>{{cite journal | author= Bora U. | title= Zirconium Tetrachloride | journal= ] | year= 2003 | pages= 1073–1074 |doi=10.1055/s-2003-39323 | issue= 7| doi-access= free }}</ref> It is also used to make water-repellent treatment of ]s and other fibrous materials. |
|
|
|
|
|
==Properties and reactions== |
|
|
Hydrolysis of ZrCl<sub>4</sub> gives the hydrated hydroxy chloride cluster called ]. This reaction is rapid and virtually irreversible, consistent with the high ] of zirconium(IV). For this reason, manipulations of ZrCl<sub>4</sub> typically require ]s. |
|
|
|
|
|
ZrCl<sub>4</sub> is the principal starting compound for the synthesis of many organometallic complexes of zirconium.<ref>{{cite book |title=New Aspects of Zirconium Containing Organic Compounds |series=Topics in Organometallic Chemistry |volume=10 |editor=Ilan Marek |publisher=Springer: Berlin, Heidelberg, New York |year=2005 |isbn=978-3-540-22221-7 |doi=10.1007/b80198 |issn=1436-6002}}</ref> Because of its polymeric structure, ZrCl<sub>4</sub> is usually converted to a molecular complex before use. It forms a 1:2 complex with ]: CAS , mp 175–177 °C.<ref>{{cite book |author1=L. E. Manzer |author2=Joe Deaton |chapter=31. Tetragtdrfuran Complexes of Selected Early Transition Metals | title = Inorganic Syntheses | year = 1982 | volume = 21 | pages = 135–140 | doi = 10.1002/9780470132524.ch31 | isbn = 978-0-470-13252-4}}</ref> ] (NaC<sub>5</sub>H<sub>5</sub>) reacts with ZrCl<sub>4</sub>(THF)<sub>2</sub> to give ], ZrCl<sub>2</sub>(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>, a versatile organozirconium complex.<ref>{{cite journal | author-link=Geoffrey Wilkinson |first1=G. |last1=Wilkinson |first2=J. G. |last2=Birmingham | year = 1954 | title = Bis-cyclopentadienyl Compounds of Ti, Zr, V, Nb and Ta | journal = ] | volume = 76 | issue = 17 | pages = 4281–4284 | doi = 10.1021/ja01646a008}}</ref> One of the most curious properties of ZrCl<sub>4</sub> is its high solubility in the presence of methylated benzenes, such as ]. This solubilization arises through the formation of π-complexes.<ref>{{cite journal |author1=Musso, F. |author2=Solari, E. |author3=Floriani, C. |author4=Schenk, K. | title = Hydrocarbon Activation with Metal Halides: Zirconium Tetrachloride Catalyzing the Jacobsen Reaction and Assisting the Trimerization of Alkynes via the Formation of η<sup>6</sup>-Arene-Zirconium(IV) Complexes | journal = ] | year = 1997 | volume = 16 | pages = 4889–4895 | doi = 10.1021/om970438g | issue = 22}}</ref> |
|
|
|
|
|
The log (base 10) of the vapor pressure of zirconium tetrachloride (from 480 to 689 K) is given by the equation: log<sub>10</sub>(P) = −5400/T + 11.766, where the pressure is measured in ]s and temperature in ]s. The log (base 10) of the vapor pressure of solid zirconium tetrachloride (from 710 to 741 K) is given by the equation log<sub>10</sub>(P) = −3427/T + 9.088. The pressure at the melting point is 14,500 torrs.<ref>{{cite journal |first1=A. A. |last1=Palko |first2=A. D. |last2=Ryon |first3=D. W. |last3=Kuhn |title=The Vapor Pressures of Zirconium Tetrachloride and Hafnium Tetrachloride |journal=J. Phys. Chem. |date=March 1958 |volume=62 |issue=3 |pages=319–322 |doi=10.1021/j150561a017|hdl=2027/mdp.39015086513051 |hdl-access=free}}</ref> |
|
|
|
|
|
{{commons category|Zirconium(IV) chloride|lcfirst=yes}} |
|
|
|
|
|
==References== |
|
|
{{reflist}} |
|
|
|
|
|
{{Zirconium compounds}} |
|
|
{{Chlorides}} |
|
|
{{Auth}} |
|
|
{{Use dmy dates|date=July 2024}} |
|
|
|
|
|
|
|
|
] |
|
|
] |
|
|
] |
|
|
] |