| Revision as of 01:34, 7 November 2010 editMystBot (talk | contribs)177,678 editsm robot Adding: ja:塩化ジルコニウム(III)← Previous edit |
Latest revision as of 21:31, 21 December 2022 edit undoBenjah-bmm27 (talk | contribs)Autopatrolled, Extended confirmed users, Pending changes reviewers, Rollbackers14,702 edits completed the related compounds section |
| (24 intermediate revisions by 18 users not shown) |
| Line 1: |
Line 1: |
|
{{chembox |
|
{{chembox |
|
|
| Verifiedfields = changed |
|
| Watchedfields = |
|
| Watchedfields = changed |
|
| verifiedrevid = |
|
| verifiedrevid = 395272655 |
|
| ImageFile = |
|
| ImageFile = ZrCl3-polyhedral.png |
|
| ImageFile1 = |
|
|
|
| ImageSize = 200px |
| ⚫ |
| Name = Zirconium(III) Chloride |
|
|
|
| ImageName = 3D model of zirconium(III) chloride |
| ⚫ |
| IUPACName = Zirconium trichloride |
|
|
⚫ |
| Name = Zirconium(III) chloride |
| ⚫ |
| OtherNames = |
|
|
⚫ |
| IUPACName = Zirconium trichloride |
| ⚫ |
| Section1 = {{Chembox Identifiers |
|
|
⚫ |
| OtherNames = |
|
| CASNo = 10241-03-9 |
|
|
⚫ |
|Section1={{Chembox Identifiers |
|
| CASNo_Ref = |
|
|
| EINECS = |
|
| CASNo = 10241-03-9 |
|
|
| CASNo_Ref = {{cascite|correct|CAS}} |
|
|
| SMILES = Cl(Cl)Cl |
|
|
| StdInChI_Ref = {{stdinchicite|changed|chemspider}} |
|
|
| StdInChI = 1S/3ClH.Zr/h3*1H;/q;;;+3/p-3 |
|
|
| StdInChIKey_Ref = {{stdinchicite|changed|chemspider}} |
|
|
| StdInChIKey = PFXYQVJESZAMSV-UHFFFAOYSA-K |
|
|
| PubChem = 144719 |
|
|
| ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}} |
|
|
| ChemSpiderID = 127679 |
|
}} |
|
}} |
|
| Section2 = {{Chembox Properties |
|
|Section2={{Chembox Properties |
|
|
| Zr=1 | Cl=3 |
|
| Formula = ZrCl<sub>3</sub> |
|
|
⚫ |
| Appearance = Blue-black crystals |
|
| MolarMass = 197.583 g/mol |
|
|
⚫ |
| Density = 3.05 g/cm<sup>3</sup><ref name=crc /> |
| ⚫ |
| Appearance = blue-black crystals |
|
|
|
| Solubility = Reacts<ref name=crc /> |
| ⚫ |
| Density = 2.20- 3.05 g/cm<sup>3</sup> |
|
|
|
| SolubleOther = Soluble in ], ] |
|
| Solubility = hydrolysis |
|
|
|
| MeltingPtC = 627 |
|
| SolubleOther = soluble in water |
|
|
|
| MeltingPt_notes = <br> at 760 mmHg<ref name=crc>{{CRC90}}</ref> |
|
| MeltingPt = |
|
|
| BoilingPt = 330 °C |
|
| BoilingPt = |
|
}} |
|
}} |
|
| Section3 = {{Chembox Structure |
|
|Section3={{Chembox Structure |
|
|
| CrystalStruct = ], ]<ref name=sccs>{{cite book|url = https://books.google.com/books?id=hYRCAAAAQBAJ&pg=PA101|title = Structure and Chemistry of Crystalline Solids|last1 = Douglas|first1 = Bodie E.|last2 = Ho|first2 = Shih-Ming|publisher = Springer Science+Business Media, Inc.|year = 2007|isbn = 978-0-387-26147-8|place = New York|page = 101}}</ref> |
|
| CrystalStruct = |
|
|
|
| SpaceGroup = P6<sub>3</sub>/mcm, No. 193<ref name=sccs /> |
|
| SpaceGroup = |
|
|
|
| PointGroup = 6/m 2/m 2/m<ref name=sccs /> |
|
|
| LattConst_a = 6.36 Å |
|
|
| LattConst_b = |
|
|
| LattConst_c = 6.14 Å<ref name=sccs /> |
|
|
| LattConst_alpha = |
|
|
| LattConst_beta = |
|
|
| LattConst_gamma = 120 |
|
}} |
|
}} |
|
| Section4 = {{Chembox Thermochemistry |
|
|Section4={{Chembox Thermochemistry |
|
|
| DeltaHf = −714.21 kJ/mol<ref name=nist>{{nist|name=Zirconium chloride|id=C10241039|accessdate=2014-06-23|mask=FFFF|units=SI}}</ref> |
|
| DeltaHf = |
|
|
|
| Entropy = 145.79 J/mol·K<ref name=nist /> |
|
| Entropy = |
|
|
|
| HeatCapacity = 96.21 J/mol·K<ref name=nist /> |
|
| Cp = |
|
|
}} |
|
}} |
|
| Section7 = {{Chembox Hazards |
|
|Section7={{Chembox Hazards |
|
| ExternalMSDS = |
|
| ExternalSDS = |
|
| EUClass = |
|
|
| EUIndex = |
|
|
| MainHazards = |
|
| MainHazards = |
|
| NFPA-H = |
|
| NFPA-H = |
|
| NFPA-F = |
|
| NFPA-F = |
|
| NFPA-R = |
|
| NFPA-R = |
|
| NFPA-O = |
|
| NFPA-S = |
|
| RPhrases = |
|
| HPhrases = |
|
| SPhrases = |
|
| PPhrases = |
|
|
| GHS_ref =<!-- no GHS data in PubChem Dec2021 --> |
|
| FlashPt = |
|
| FlashPt = |
|
| PEL = |
|
| PEL = |
|
| LD50 = |
|
| LD50 = |
|
}} |
|
}} |
|
| Section8 = {{Chembox Related |
|
|Section8={{Chembox Related |
|
|
| OtherCompounds = ] |
|
| OtherAnions = |
|
|
|
| OtherAnions = ]<br />] |
|
| OtherCations = |
|
|
|
| OtherCations = ]<br />] |
|
}}}} |
|
}} |
|
|
}} |
|
|
|
|
|
'''Zirconium(III) chloride''' is a the ] with formula ZrCl<sub>3</sub>. It is a blue-black solid that is ]. |
|
'''Zirconium(III) chloride''' is an ] with ] ZrCl<sub>3</sub>. It is a blue-black solid that is ]. |
|
|
|
|
|
==Preparation== |
|
==Preparation== |
|
] and Wallstein in 1923 reduced ] with ] to give impure samples of ZrCl<sub>3</sub>.<ref>{{cite journal | doi = 10.1002/zaac.19231280110 | title = Reduktion anorganischer Halogenide III.1) Die Reduktion des Zirkontetrachlorids | year = 1923 | last1 = Ruff | first1 = Otto | last2 = Wallstein | first2 = Richard | journal = Zeitschrift für anorganische und allgemeine Chemie | volume = 128 | pages = 96}}</ref> Larsen and Leddy eliminated the aluminium contamination by using zirconium as the reductant.<ref name="a002">{{cite journal | doi =10.1021/ic00039a002 | title =Synthesis of pyridine complexes of zirconium(III) chloride and the apparent oxidation to zirconium(IV) by a nitrile | year =1992 | last1 =Hoffman | first1 =David M. | last2 =Lee | first2 =Samkeun | journal =Inorganic Chemistry | volume =31 | pages =2675}}</ref> |
|
The material was first claimed by ] and Wallstein who reduced ] with ] to give impure samples.<ref>{{cite journal | doi = 10.1002/zaac.19231280110 | title = Reduktion anorganischer Halogenide III.1) Die Reduktion des Zirkontetrachlorids | year = 1923 | last1 = Ruff | first1 = Otto | last2 = Wallstein | first2 = Richard | journal = Zeitschrift für anorganische und allgemeine Chemie | volume = 128 | pages = 96–116}}</ref> Subsequently, the problem with aluminium contamination was solved when it was prepared by reduction using zirconium metal:<ref name="a002">{{cite journal | doi =10.1021/ic00039a002 | title =Synthesis of pyridine complexes of zirconium(III) chloride and the apparent oxidation to zirconium(IV) by a nitrile | year =1992 | last1 =Hoffman | first1 =David M. | last2 =Lee | first2 =Samkeun | journal =Inorganic Chemistry | volume =31 | pages =2675 | issue =13}}</ref> |
|
|
|
|
A simplified equation is: |
|
|
|
|
|
:Zr + 3 ZrCl<sub>4</sub> → 4 ZrCl<sub>3</sub> |
|
:Zr + 3 ZrCl<sub>4</sub> → 4 ZrCl<sub>3</sub> |
|
|
|
|
|
When aluminium is used as the reducing agent with zirconium tetrachloride, a series of choloroaluminates are formed, for example and Zr(Cl<sub>2</sub>AlCl<sub>2</sub>)<sub>3</sub>.<ref name="a015">{{cite journal | doi =10.1021/ic50133a015 | title =Synthesis of crystalline zirconium trihalides by reduction of tetrahalides in molten aluminum halides. Nonreduction of hafnium | year =1974 | last1 =Larsen | first1 =E. M. | last2 =Moyer | first2 =James W. | last3 =Gil-Arnao | first3 =Francisco. | last4 =Camp | first4 =Michael J. | journal =Inorganic Chemistry | volume =13 | pages =574}}</ref> |
|
When aluminium is used as the reducing agent with zirconium tetrachloride, a series of choloroaluminates are formed, for example and Zr(AlCl<sub>4</sub>)<sub>3</sub>.<ref name="a015">{{cite journal | doi =10.1021/ic50133a015 | title =Synthesis of crystalline zirconium trihalides by reduction of tetrahalides in molten aluminum halides. Nonreduction of hafnium | year =1974 | last1 =Larsen | first1 =E. M. | last2 =Moyer | first2 =James W. | last3 =Gil-Arnao | first3 =Francisco. | last4 =Camp | first4 =Michael J. | journal =Inorganic Chemistry | volume =13 | pages =574 | issue =3}}</ref> |
|
|
|
|
|
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 dihydrogen.<ref>{{cite journal | doi =10.1021/ja01494a006 | year =1960 | last1 =Newnham | first1 =I. E. | last2 =Watts | first2 =J. A. | journal =Journal of the American Chemical Society | volume =82 | pages =2113}}</ref> |
|
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.<ref>{{cite journal | doi =10.1021/ja01494a006 | year =1960 | last1 =Newnham | first1 =I. E. | last2 =Watts | first2 =J. A. | title = The Preparation of the Anhydrous Zirconium Trihalides| journal =Journal of the American Chemical Society | volume =82 | pages =2113 | issue =9}}</ref> |
|
⚫ |
:ZrCl<sub>4</sub> + ½ H<sub>2</sub> → ZrCl<sub>3</sub> + HCl |
|
|
|
| ⚫ |
:ZrCl<sub>4</sub><sub>(s)</sub> + 1/2H<sub>2</sub><sub>(g)</sub> → ZrCl<sub>3</sub><sub>(s)</sub> + HCl<sub>(g)</sub> |
|
|
|
|
|
|
==Structure== |
|
==Structure== |
|
⚫ |
Some zirconium halides (ZrCl<sub>3</sub>, ], and ]) have structures similar to ]. They also have similar ] (P6<sub>3</sub>/mcm) and hexagonal structure with 2 molecules in the cell.<ref name=sccs /> The ] of zirconium trichloride suggests metal-metal interactions of the unpaired electron on each Zr(III) center. The magnetic moment of ZrCl<sub>3</sub> (0.4 ]) indicates considerable overlap of metal orbitals.<ref>Wells, A.F. Structural Inorganic Chemistry. Oxford Science Publications, 1975, 5th ed, 417-420.</ref> |
|
ZrCl<sub>3</sub> can be viewed as a ] (ccp) structure in which Zr fills one third of the octahedral holes, similar to AlF<sub>3</sub> and AlBr<sub>3</sub>. The Zr-Cl distance is 2.64 Å. Strong metallic bonding is evidence by Zr-Zr distances of 303 pm and 342 pm.<ref>Greenwood N.N., Earnshaw A. "Chemistry of the Elements". Pergamon Press, ""1984"", 1st ed, 1123-1126.</ref> |
|
|
|
|
|
==Properties== |
|
|
On the basis of its ], ZrCl<sub>3</sub> has a hexagonal ] with dimension a = 6.36 Å, c = 6.14 Å.<ref name="a002"/> |
|
|
|
|
| ⚫ |
The ] of zirconium trichloride suggests some type of cooperative metal-metal interaction of the unpaired electron on each Zr(III) center. The magnetic moment of ZrCl<sub>3</sub> (0.4 ]) indicates considerable overlap of metal orbitals.<ref>Wells, A.F. Structural Inorganic Chemistry. Oxford Science Publications, 1975, 5th ed, 417-420.</ref> |
|
|
<ref>Miessler, G. L., Tarr, D. A. Inorganic Chemistry. Prentice Hall, 1991, 340-342.</ref> |
|
|
|
|
|
==Main reactions== |
|
|
Zirconium trichloride forms adducts with a wide variety of ]s. Zirconium(III) reduces ] to a radical anion which then reacts further to give organic products.<ref name="a015"/> |
|
|
|
|
|
|
==References== |
|
==References== |
|
{{reflist}} |
|
{{reflist}} |
|
|
|
|
|
{{Zirconium compounds}} |
|
|
{{Chlorides}} |
|
|
|
|
|
{{DEFAULTSORT:Zirconium(Iii) Chloride}} |
|
{{DEFAULTSORT:Zirconium(Iii) Chloride}} |
|
] |
|
] |
|
] |
|
] |
|
|
] |
|
|
|
|
] |
|