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| verifiedrevid = 402139527 |
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| verifiedrevid = 447576762 |
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| Name = Germanium tetrachloride |
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| Name = |
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| ImageFileL1 = Germanium-tetrachloride-2D.png |
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| ImageFileL1 = Germanium-tetrachloride-2D.png |
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| ImageSizeL1 = |
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| ImageNameL1 = Germanium tetrachloride - structural formula |
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| ImageFileR1 = Germanium-tetrachloride-3D-vdW.png |
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| ImageNameL1 = Germanium tetrachloride - structural formula |
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| ImageFileR1 = Germanium-tetrachloride-3D-vdW.png |
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| ImageSizeR1 = |
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| ImageNameR1 = Germanium tetrachloride - space-filling model |
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| IUPACName = Germanium tetrachloride<br/>Tetrachlorogermane<br/>Tetrachloridogermanium |
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| ImageNameR1 = Germanium tetrachloride - space-filling model |
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| OtherNames = Germanium(IV) chloride<br/>Germanium chloride |
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| ImageFile = Germanium(IV)-chlorid in einem Schlenkrohr..jpg |
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| IUPACName = Germanium tetrachloride<br/>Tetrachlorogermane<br/>Tetrachloridogermanium |
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| Section1 = {{Chembox Identifiers |
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| OtherNames = Germanium(IV) chloride<br/>Neutral germanium chloride (1:4) |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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|Section1={{Chembox Identifiers |
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| ChemSpiderID = 10606631 |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| InChI = 1/4ClH.Ge/h4*1H;/q;;;;+4/p-4 |
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| ChemSpiderID = 59611 |
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| SMILES = .... |
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| InChI = InChI=1S/Cl4Ge/c1-5(2,3)4 |
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| InChIKey = FFARMWUPSQHFHM-XBHQNQODAX |
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| SMILES = Cl(Cl)(Cl)Cl |
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| InChIKey = IEXRMSFAVATTJX-UHFFFAOYSA-N |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChI = 1S/4ClH.Ge/h4*1H;/q;;;;+4/p-4 |
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| StdInChI = InChI=1S/Cl4Ge/c1-5(2,3)4 |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey = FFARMWUPSQHFHM-UHFFFAOYSA-J |
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| StdInChIKey = IEXRMSFAVATTJX-UHFFFAOYSA-N |
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| CASNo = 10038-98-9 |
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| CASNo = 10038-98-9 |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| PubChem = 66226 |
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| RTECS = LY5220000 |
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| UNII = YSV1R803C0 |
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| PubChem = 66226 |
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| RTECS = LY5220000 |
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| Section2 = {{Chembox Properties |
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|Section2={{Chembox Properties |
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| Formula = GeCl<sub>4</sub> |
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| Formula = GeCl<sub>4</sub> |
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| MolarMass = 214.40 g/mol |
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| MolarMass = 214.40 g/mol |
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| Appearance = colourless liquid |
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| Appearance = Colourless liquid |
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| Density = 1.879 g/cm<sup>3</sup> (20 °C) <br> 1.844 g/cm<sup>3</sup> (30 °C) <ref>Pradyot Patnaik. ''Handbook of Inorganic Chemicals''. McGraw-Hill, 2002, ISBN 0070494398</ref> |
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| Density = 1.879 g/cm<sup>3</sup> (20 °C) <br> 1.844 g/cm<sup>3</sup> (30 °C)<ref name=Brauer>{{cite book|author=P.W. Schenk|chapter=Germanium(IV) Chloride|title=Handbook of Preparative Inorganic Chemistry, 2nd Ed. |editor=G. Brauer|publisher=Academic Press|year=1963|place=NY, NY|volume=1|pages=715–716}}</ref> |
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| Solubility = decomp. |
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| Solubility = Soluble, hydrolyses |
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| SolubleOther = soluble in ], ], ], ] <br> insoluble in ], ] |
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| SolubleOther = Soluble in ], ], ], ] <br> Very soluble in ], dilute ] |
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| MeltingPtC = -49.5 |
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| MeltingPtC = −49.5 |
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| BoilingPtC = 86.5 |
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| BoilingPtC = 86.5 |
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| Viscosity = |
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| Viscosity = |
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| RefractIndex = 1.464 |
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| RefractIndex = 1.464 |
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| MagSus = −72.0·10<sup>−6</sup> cm<sup>3</sup>/mol |
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| Section3 = {{Chembox Structure |
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|Section3={{Chembox Structure |
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| MolShape = tetrahedral<ref>{{ cite journal | title = Germanium(IV) chloride at 193 K | first1 = K. | last1 = Merz | first2 = M. | last2 = Driess | journal = ] | year = 2002 | volume = 58 | issue = Pt 7 | pages = i101–i102 | doi = 10.1107/S0108270102010351 | pmid = 12094027 }}</ref> |
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| MolShape = tetrahedral |
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| Dipole = |
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| Dipole = |
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| Section7 = {{Chembox Hazards |
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| Section4 = {{Chembox Thermochemistry |
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| Thermochemistry_ref = <ref>{{Cite book |url=https://www.worldcat.org/oclc/930681942 |title=CRC handbook of chemistry and physics : a ready-reference book of chemical and physical data. |date=2016 |others=William M. Haynes, David R. Lide, Thomas J. Bruno |isbn=978-1-4987-5428-6 |edition=2016-2017, 97th |location=Boca Raton, Florida |oclc=930681942}}</ref> |
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| ExternalMSDS = |
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| HeatCapacity = |
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| EUIndex = Not listed |
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| Entropy = 245.6 J·mol<sup>−1</sup>·K<sup>−1</sup> |
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| MainHazards = Reacts slowly with water to form HCl and GeO<sub>2</sub>, corrosive, lachrymator |
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| DeltaHform = −531.8 kJ·mol<sup>−1</sup> |
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| NFPA-H = 3 |
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| DeltaGfree = −462.7 kJ·mol<sup>−1</sup> |
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| NFPA-F = 0 |
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| DeltaHcombust = |
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| NFPA-R = 2 |
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| NFPA-O = W |
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| DeltaHfus = |
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| DeltaHvap = |
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| FlashPt = Not flammable |
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| RPhrases = |
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| DeltaHsublim = |
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| HHV = |
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|Section7={{Chembox Hazards |
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| ExternalSDS = |
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| MainHazards = Reacts slowly with water to form HCl and GeO<sub>2</sub>, corrosive, lachrymator |
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| NFPA-H = 3 |
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| NFPA-F = 0 |
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| NFPA-R = 2 |
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| NFPA-S = W |
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| FlashPt = Non-flammable |
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}} |
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| Section8 = {{Chembox Related |
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|Section8={{Chembox Related |
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| OtherAnions = ]<br/>]<br/>] |
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| OtherAnions = ]<br/>]<br/>] |
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| OtherCations = ]<br/>]<br/>]<br/>] |
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| OtherCations = ]<br/>]<br/>]<br/>] |
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'''Germanium tetrachloride''' is a colourless, fuming liquid<ref>{{Greenwood&Earnshaw2nd|page=377}}</ref> with a peculiar, acidic odour. It is used as an intermediate in the production of purified ] metal. In recent years, GeCl<sub>4</sub> usage has increased substantially due to its use as a reagent for ] production. |
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'''Germanium tetrachloride''' is a colourless liquid used as an intermediate in the production of purified ] metal. In recent years, GeCl<sub>4</sub> usage has increased substantially due to its use as a reagent for ] production. |
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==Production== |
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==Production== |
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Most commercial production of ] is from treating flue-dusts of zinc- and copper-ore smelters, although a significant source is also found in the ash from the combustion of certain types of coal called ]. Germanium tetrachloride is an intermediate for the purification of germanium metal or its oxide, GeO<sub>2</sub>.<ref name=USGS>"Germanium" Mineral Commodity Profile, U.S. Geological Survey, 2005.</ref> |
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Most commercial production of ] is from treating flue-dusts of zinc- and copper-ore smelters, although a significant source is also found in the ash from the combustion of certain types of coal called ]. Germanium tetrachloride is an intermediate for the purification of germanium metal or its oxide, GeO<sub>2</sub>.<ref name=USGS>"Germanium" Mineral Commodity Profile, U.S. Geological Survey, 2005.</ref> |
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Germanium tetrachloride can be generated directly from GeO<sub>2</sub> by dissolution of the oxide in concentrated hydrchloric acid. The resulting mixture is fractionally distilled to purify and separate the germanium tetrachloride from other products and impurities.<ref name=CRC>"The Elements" C.R. Hammond, David R. Lide, ed. CRC Handbook of Chemistry and Physics, Edition 85 (CRC Press, Boca Raton, FL) (2004)</ref> The GeCl<sub>4</sub> can be rehydrolyzed with deionized water to produce pure GeO<sub>2</sub>, which is then reduced under hydrogen to produce germanium metal.<ref name="USGS"/><ref name="CRC"/> |
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Germanium tetrachloride can be generated directly from GeO<sub>2</sub> (]) by dissolution of the oxide in concentrated hydrochloric acid. The resulting mixture is fractionally distilled to purify and separate the germanium tetrachloride from other products and impurities.<ref name=CRC>"The Elements" C. R. Hammond, David R. Lide, ed. ''CRC Handbook of Chemistry and Physics'', Edition 85 (CRC Press, Boca Raton, Florida) (2004)</ref> The GeCl<sub>4</sub> can be rehydrolysed with deionized water to produce pure GeO<sub>2</sub>, which is then reduced under hydrogen to produce germanium metal.<ref name="USGS"/><ref name="CRC"/> |
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Production of GeO<sub>2</sub>, however, is dependent on the oxidized form of germanium extracted from the ore. Copper-lead-sulfide and zinc-sulfide ores will produce GeS<sub>2</sub>, which is subsequently oxidized to GeO<sub>2</sub> with an oxidizer such as ]. Zinc-ores are roasted and sintered and can produce the GeO<sub>2</sub> directly. The oxide is then processed as discussed above.<ref name="USGS"/> |
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Production of GeO<sub>2</sub>, however, is dependent on the oxidized form of germanium extracted from the ore. Copper-lead-sulfide and zinc-sulfide ores will produce ], which is subsequently oxidized to GeO<sub>2</sub> with an oxidizer such as ]. Zinc-ores are roasted and sintered and can produce the GeO<sub>2</sub> directly. The oxide is then processed as discussed above.<ref name="USGS"/> |
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The classic synthesis from chlorine and germanium metal at elevated temperatures is also possible.<ref>{{Cite web|publisher=Technische Universitä Ilmenau|title=GeCl4 synthesis|url=https://organic-btc-ilmenau.jimdo.com/kleine-synthese-ecke/|access-date=2020-09-22|website=account.e.jimdo.com}}</ref><ref name=Brauer/> Additionally, a ] has been developed, giving a less energy intensive and more environmentally friendly alternative synthesis for germanium precursors. |
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==Application== |
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==Application== |
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Germanium tetrachloride is used almost exclusively as an intermediate for several optical processes. GeCl<sub>4</sub> can be directly hydrolyzed to GeO<sub>2</sub>, an oxide glass with several unique properties and applications, described below: |
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Germanium tetrachloride is used almost exclusively as an intermediate for several optical processes. GeCl<sub>4</sub> can be directly hydrolysed to GeO<sub>2</sub>, an oxide glass with several unique properties and applications, described below and in linked articles: |
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===Fiber Optics=== |
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===Fiber optics=== |
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Most notable of GeO<sub>2</sub> is its high index of ] and low optical dispersion, used for wide camera lens, microscopy, and for the core of fiber-optic lines.<ref name="CRC"/> See ] for specifics on the manufacturing process. Overall, ], SiCl<sub>4</sub> and germanium tetrachloride, GeCl<sub>4</sub> are introduced with ] into a hollow glass preform, which is carefully heated to allow for oxidation of the reagents to their respective oxides and formation of a glass mixture. The GeO<sub>2</sub> has a high index of refraction, so by varying the flowrate of germanium tetrachloride the overall index of refraction of the optical fiber can be specifically controlled. The GeO<sub>2</sub> is about 4% by weight of the glass.<ref name="USGS"/> |
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A notable derivative of GeCl<sub>4</sub> is ]. In the manufacture of ], ], SiCl<sub>4</sub>, and germanium tetrachloride, GeCl<sub>4</sub>, are introduced with ] into a hollow glass preform, which is carefully heated to allow for oxidation of the reagents to their respective oxides and formation of a glass mixture. The GeO<sub>2</sub> has a high index of refraction, so by varying the flow rate of germanium tetrachloride the overall ] of the optical fiber can be specifically controlled. The GeO<sub>2</sub> is about 4% by weight of the glass.<ref name="USGS"/> |
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===Infrared=== |
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Germanium and its glass oxide, GeO<sub>2</sub> are transparent to the infrared spectrum. The glass can be manufactured into IR windows and lenses, used for night-vision technology in the military and luxury vehicles.<ref name="CRC"/> GeO<sub>2</sub> is preferred over other IR transparent glasses because it is mechanically strong and therefore preferred for rugged military usage.<ref name="USGS"/> |
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==Future== |
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As of the year 2000, about 15% of ] consumption of germanium is used for infrared optics technology and 50% for fiber-optics. Over the past 20 years, infrared use has consistently decreased; fiber optic demand, however, is slowly increasing. There is discussion on the over-production of fiber-optic networks and that 30-50% of current lines are unused ], suggesting a future reduction in demand. Worldwide, demand is increasing dramatically as countries such as China are expanding fiber-optic based telecommunication throughout the country.<ref name="USGS"/> |
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==References== |
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==References== |
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