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| verifiedrevid = 363167143 |
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| Name = Iridium(III) chloride |
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| verifiedrevid = 443643874 |
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| ImageFile = Aluminium-trichloride-crystal-3D-balls.png |
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| ImageName = Iridium(III) chloride |
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| Name = Iridium(III) chloride |
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| ImageFile3 = IrCl3(aq)x.jpg |
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| OtherNames = Iridium trichloride |
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| ImageCaption3 = Trihydrate |
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| Name = Iridium(III) chloride |
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| ImageName3 = Iridium(III) chloride trihydrate |
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| Section1 = {{Chembox Identifiers |
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| OtherNames = Iridium trichloride |
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| CASNo = 10025-83-9 |
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| Section1 = {{Chembox Identifiers |
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| EINECS = 233-044-6 |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| RTECS = |
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| CASNo = 10025-83-9 |
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}} |
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| CASNo_Comment =(anhydrous) |
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| Section2 = {{Chembox Properties |
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| CASNo1 = 14996-61-3 |
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| Formula = IrCl<sub>3</sub> |
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| CASNo1_Comment = (hydrate) |
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| MolarMass = 298.58 g/mol (''anhydrous'') |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| Appearance = dark green solid<br />] |
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| UNII = 20278OEG45 |
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| Density = 5.30 g/cm<sup>3</sup>, solid |
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| EINECS = 233-044-6 |
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| Solubility = soluble |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| MeltingPt = 763 °C (''decomp.'') |
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| ChemSpiderID = 23837 |
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}} |
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| RTECS = |
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| Section3 = {{Chembox Structure |
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| PubChem = 82301 |
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| CrystalStruct = ], ] |
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| StdInChI=1S/3ClH.Ir/h3*1H;/q;;;+3/p-3 |
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| SpaceGroup = C12/m1, No. 12 |
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| StdInChIKey = DANYXEHCMQHDNX-UHFFFAOYSA-K |
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| SMILES = ... |
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| Section4 = {{Chembox Thermochemistry |
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| Section2 = {{Chembox Properties |
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| Formula = IrCl<sub>3</sub> |
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| DeltaHf = -257 kJ/mol |
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| MolarMass = 298.58 g/mol (anhydrous) |
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316.60 g/mol (hydrate) |
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| Section7 = {{Chembox Hazards |
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| Appearance = brown solid (α-anhydrous)<br />red solid (β-anhydrous)<br />dark green solid (trihydrate) |
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| EUClass = not listed |
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| Density = 5.30 g/cm<sup>3</sup>, solid<ref name="crc">{{cite book |editor1-last=Haynes |editor1-first=William |title=CRC Handbook of Chemistry and Physics |date=2014 |publisher=CRC Press |isbn=9781482208689 |page=4-68 |language=en}}</ref> |
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| FlashPt = non-flammable |
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| Solubility = insoluble (anhydrous IrCl<sub>3</sub>), soluble (hydrated derivative)<ref name="crc" /> |
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| SolubleOther = Insoluble in ] and ]<ref name="crc" /> |
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| Section8 = {{Chembox Related |
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| MeltingPtC = 763 |
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| OtherAnions = ]<br />]<br />] |
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| MeltingPt_notes = (decomposes) |
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| OtherCations =] |
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| MeltingPt_ref = <ref name="crc" /><ref name="therm" /> |
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| OtherCpds = ]<br />]}} |
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| MagSus = −14.4·10<sup>−6</sup> cm<sup>3</sup>/mol }} |
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| Section3 = {{Chembox Structure |
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| CrystalStruct = ], ] |
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| SpaceGroup = C12/m1, No. 12 |
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}} |
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| Section4 = {{Chembox Thermochemistry |
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| DeltaHf = -257 kJ/mol |
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}} |
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| Section7 = {{Chembox Hazards |
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| GHS_ref=<ref>{{cite web |title=C&L Inventory |url=https://echa.europa.eu/information-on-chemicals/cl-inventory-database/-/discli/details/95579 |website=echa.europa.eu |access-date=23 December 2021}}</ref> |
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| GHSPictograms = {{GHS07}}{{GHS09}} |
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| GHSSignalWord = Warning |
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| HPhrases = {{H-phrases|302|411}} |
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| PPhrases = {{P-phrases|}} |
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| FlashPt = non-flammable |
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}} |
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| Section8 = {{Chembox Related |
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| OtherAnions = |
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| OtherCations = ] |
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| OtherCompounds = ]}} |
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'''Iridium(III) chloride''' is the ] with the ] IrCl<sub>3</sub>. This material is relatively rare, but the related ] is useful for preparing other ] compounds. The anhydrous salt is a dark green ] solid. More commonly encountered is the trihydrate IrCl<sub>3</sub>(H<sub>2</sub>O)<sub>3</sub> (] ). |
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'''Iridium(III) chloride''' is the ] with the ] IrCl<sub>3</sub>. The ] compound is relatively rare, but the related ] is much more commonly encountered. The anhydrous salt has two ], α and β, which are brown and red colored respectively. More commonly encountered is the ] dark green trihydrate IrCl<sub>3</sub>(H<sub>2</sub>O)<sub>3</sub> which is a common starting point for iridium chemistry.<ref name="housecroft" /> |
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==Preparation== |
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==Preparation== |
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Iridium is separated from the other ] as crystalline ammonium hexachloroiridate(IV), (NH<sub>4</sub>)<sub>2</sub> (] ), which can be reduced to iridium metal in a stream of ]. The spongy Ir thus produced reacts with ] at 300-400 °C to produce iridium(III) chloride. Like the related rhodium compound, IrCl3 adopts the structure seen for ].<ref>{{Greenwood&Earnshaw}}</ref> |
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Iridium is separated from the other ] as crystalline ], (NH<sub>4</sub>)<sub>2</sub>, which can be reduced to iridium metal in a stream of ]. The spongy Ir thus produced reacts with ] at 650 °C to give iridium(III) chloride.<ref name="encyclo">{{cite journal |author1=Hermann Renner |title=Platinum Group Metals and Compounds |journal=Ullmann's Encyclopedia of Industrial Chemistry |date=2018 |pages=1–73 |doi=10.1002/9783527306732.a21_075.pub2 |isbn=9783527303854 |s2cid=94472506 |language=en}}</ref> |
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The hydrated form is obtained by heating hydrated iridium(III) oxide with ]. |
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Hydrated iridium trichloride is obtained by heating hydrated ] with ].<ref name="greenwood" /> |
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==Uses== |
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==Structure== |
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Like the related rhodium compound, IrCl<sub>3</sub> adopts the structure seen for ].<ref name="greenwood">{{Greenwood&Earnshaw}}</ref> This is the ] α ].<ref name="a cry">{{ cite journal | first1 = K. | last1 = Brodersen | first2 = F. | last2 = Moers | first3 = H. G. | last3 = Schnering | title = Zur Struktur des Iridium(III)- und des Ruthenium(III)-chlorids | journal = ] | year = 1965 | volume = 52 | issue = 9 | pages = 205–206 | doi = 10.1007/BF00626459 | s2cid = 43351743 }}</ref> A ] β polymorph also exists. Both polymorphs have effectively the same anion lattice but differ in the octahedral interstices the iridium ions occupy.<ref name="b cry">{{ cite journal | first1 = A. | last1 = Meisel | first2 = G. | last2 = Leonhardt | title = Die Kristallstruktur von β-Iridium(III)-Chlorid | journal = ] | year = 1965 | volume = 339 | issue = 1–2 | pages = 57–66 | doi = 10.1002/zaac.19653390109 }}</ref> The α polymorph converts to the β polymorph when heated to around 650 °C.<ref name="housecroft" /> |
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Hydrated iridium(III) chloride is used in the laboratory for the preparation of other iridium compounds such as ], ''trans''-.<ref>Vaska, L.; & DiLuzio, J. W. (1961) ''J. Am. Chem. Soc.'' 83:2784. Girolami, G.S.; Rauchfuss, T.B.; Angelici, R.J. (1999). ''Synthesis and Technique in Inorganic Chemistry (3rd Edn.)''. Sausalito:University Science Books.</ref> ] complexes such as the dimeric {Ir(])Cl}<sub>2</sub><ref name = winkhaus>Winkhaus, G.; & Singer, H. (1966). Iridium(I)-Olefinkomplexe. ''Chem. Ber.'' 99:3610–18.</ref><sup>,</sup><ref name="senoffcod">Herde, J. L.; Lambert, J. C.; & Senoff, C. V. (1974). Cyclooctene and 1,5-Cyclooctadiene Complexes of Iridium(I). ''Inorg. Synth.'' 1974, volume 15, pages 18–20. {{DOI|10.1002/9780470132463.ch5}}.</ref> and {Ir(cycloctene)<sub>2</sub>Cl}<sub>2</sub><ref name="senoffcod" /><sup></sup><ref name = winkhaus/> can also be prepared by heating the trichloride with the appropriate alkene in water/alcohol mixtures. Industrially, most iridium complexes are generated from H<sub>2</sub>IrCl<sub>6</sub> or (NH<sub>4</sub>)<sub>2</sub>IrCl<sub>6</sub> as these salts are the most common commercial forms of iridium chlorides, being directly obtained in the purification of iridium. |
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{{multiple image |
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| align = center |
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| width = 200 |
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| footer = Structures of the forms of iridium(III) chloride |
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| image1 = Alpha-iridium(III)-chloride-xtal-viewed-down-b-axis-3D-bs-17.png |
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| alt1 = |
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| caption1 = α-IrCl<sub>3</sub> |
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| image2 = Beta-iridium(III)-chloride-xtal-viewed-down-ab-diagonal-3D-bs-17-raw.png |
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| alt2 = |
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| caption2 = β-IrCl<sub>3</sub>}} |
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{| class="wikitable plainrowheaders" |
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|+ Crystallographic data for the 2 polymorphs of iridium(III) chloride |
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!Compound |
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!α-IrCl<sub>3</sub><ref name="a cry" /> |
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!β-IrCl<sub>3</sub><ref name="b cry" /> |
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!Crystal Structure |
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|] |
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|] |
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!Space Group |
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|C2/m |
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|Fddd |
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!Lattice constant a (Å) |
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|5.99 |
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|6.95 |
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!Lattice constant b (Å) |
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|10.37 |
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|9.81 |
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!Lattice constant c (Å) |
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|5.99 |
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|20.82 |
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|- |
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!''β'' |
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|109.4° |
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!Calculated density (g/cm<sup>3</sup>) |
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|5.33 |
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|5.34 |
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The structure of the trihydrate has not been elcudated yet. |
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==Reactions and uses== |
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Industrially, most iridium complexes are generated from ] or the related chloroiridic acid (H<sub>2</sub>IrCl<sub>6</sub>). The ], source of most of the world's ] relies on such catalysts. |
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Hydrated iridium(III) chloride is used in the for the preparation of other iridium complexes such as ], ''trans''-.<ref>Vaska, L.; & DiLuzio, J. W. (1961) ''J. Am. Chem. Soc.'' 83:2784. Girolami, G.S.; Rauchfuss, T.B.; Angelici, R.J. (1999). ''Synthesis and Technique in Inorganic Chemistry (3rd Edn.)''. Sausalito: University Science Books.</ref> With the presence of the chloride anion, it forms ], and produces hexachloroiridate(IV) in ]. The trihydrate react with ] to form ]es, such as pentaamminechloroiridium(III) chloride, formulated Cl<sub>2</sub>. It also reacts with concentrated ] at 150 °C to form the fully ammoniated complex, Cl<sub>3</sub>. The hydrate can also form complexes upon reaction with ], ], and ].<ref name="housecroft">C. E. Housecroft and A. G. Sharpe ''Inorganic Chemistry'', p. 849.</ref> |
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] complexes such as ]<ref name = winkhaus>Winkhaus, G.; & Singer, H. (1966). Iridium(I)-Olefinkomplexe. ''Chem. Ber.'' 99:3610–18.</ref><ref name="senoffcod">Herde, J. L.; Lambert, J. C.; & Senoff, C. V. (1974). Cyclooctene and 1,5-Cyclooctadiene Complexes of Iridium(I). ''Inorg. Synth.'' 1974, volume 15, pages 18–20. {{doi|10.1002/9780470132463.ch5}}.</ref> and ]<ref name="senoffcod" /><ref name = winkhaus/> can also be prepared by heating the hydrate with the appropriate alkene in water/alcohol mixtures. |
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===Decomposition=== |
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The trihydrate decomposes to the anhydrous form at 200 °C, which then oxidizes in air at 763 °C to ], which then decomposes to iridium metal at 1070 °C. However, under ], it is directly reduced at 190 °C to iridium metal:<ref name="therm">{{cite journal |author1=A.E. Newkirk |author2=D.W. McKee |title=Thermal decomposition of rhodium, iridium, and ruthenium chlorides |journal=Journal of Catalysis |date=1968 |volume=11 |issue=4 |pages=370–377 |doi=10.1016/0021-9517(68)90061-4 |language=en}}</ref><ref>{{cite journal |author1=W. B. Rowston |author2=J. M. Ottaway |title=Determination of noble metals by carbon furnace atomic-absorption spectrometry. Part 1. Atom formation processes |journal=Analyst |date=1979 |volume=104 |issue=1240 |pages=645–659 |doi=10.1039/AN9790400645 |bibcode=1979Ana...104..645R |language=en}}</ref><ref>{{cite journal |author1=R. K. Kawar |author2=P. S. Chigare |author3=P. S. Patil |title=Substrate temperature dependent structural, optical and electrical properties of spray deposited iridium oxide thin films |journal=Applied Surface Science |date=2003 |volume=206 |issue=1–4 |pages=90–101 |doi=10.1016/S0169-4332(02)01191-1 |bibcode=2003ApSS..206...90K |language=en}}</ref> |
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:2 IrCl<sub>3</sub> + 3 H<sub>2</sub> → 2 Ir + 6 HCl |
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==Safety== |
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==Safety== |
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Iridium(III) chloride is not listed under Annex I of ], but is listed in the inventory of the ] (TSCA). It is also known as a mild skin and eye-irritating agent.<ref>{{cite book|title=Encyclopaedia of Occupational Health and Safety|first=J.|last=Mager Stellman|chapter=Iridium|isbn=978-92-2-109816-4|date=1998|publisher=International Labour Organization|pages=|chapter-url=https://books.google.com/books?id=nDhpLa1rl44C&pg=PT125|oclc=35279504|url=https://archive.org/details/encyclopaediaofo0003unse/page/63}}</ref> |
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Iridium(III) chloride is not listed under Annex I of ], but is usually classified as ], '''R36/37/38''': ''Irritating to eyes, respiratory system and skin''. It is listed in the inventory of the ] (TSCA). |
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==References== |
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==References== |
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{{Iridium compounds}} |
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{{Iridium compounds}} |
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{{Chlorides}} |
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{{DEFAULTSORT:Iridium(Iii) Chloride}} |
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{{DEFAULTSORT:Iridium(Iii) Chloride}} |
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