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{{Redirect|PCl5|the printer protocol|Printer Command Language}} |
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{{chembox |
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{{Chembox |
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| Watchedfields = changed |
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| verifiedrevid = 415592234 |
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| verifiedrevid = 455252348 |
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| Name = Phosphorus pentachloride |
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| Name = Phosphorus pentachloride |
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| ImageFile = Phosphorus-pentachloride-2D-dimensions.png |
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| ImageFile = Phosphorus-pentachloride-2D-dimensions.png |
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| ImageSize = |
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| ImageSize = 100px |
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| ImageName = Phosphorus pentachloride (gas phase structure) |
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| ImageName = Phosphorus pentachloride (gas phase structure) |
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| ImageFile1 = Phosphorus-pentachloride-3D-balls.png |
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| ImageFileL1 = Phosphorus-pentachloride-3D-balls.png |
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| ImageSize1 = |
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| ImageSizeL1 = 100px |
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| ImageName1 = Phosphorus pentachloride |
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| ImageNameL1 = Phosphorus pentachloride |
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| ImageFile2 = Phosphorus pentachloride ampoule.jpg |
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| ImageFileR1 = Phosphorus-pentachloride-3D-vdW.png |
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| ImageSizeR1 = 100px |
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| IUPACName = Phosphorus pentachloride<br />Phosphorus(V) chloride |
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| ImageFile2 = Phosphorus pentachloride ampoule.jpg |
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| OtherNames = Pentachlorophosphorane |
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| IUPACName = Phosphorus pentachloride<br> Pentachloro-λ<sup>5</sup>-phosphane |
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| Section1 = {{Chembox Identifiers |
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| OtherNames = Pentachlorophosphorane |
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| SMILES = ClP(Cl)(Cl)(Cl)Cl |
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|Section1={{Chembox Identifiers |
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| CASNo = 10026-13-8 |
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| SMILES = ClP(Cl)(Cl)(Cl)Cl |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}} |
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| PubChem = 24819 |
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| ChemSpiderID = 23204 |
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| EINECS = 233-060-3 |
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| InChI = 1/Cl5P/c1-6(2,3,4)5 |
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| RTECS = TB6125000 |
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| InChIKey = UHZYTMXLRWXGPK-UHFFFAOYAP |
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| UNNumber = 1806 |
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| StdInChI_Ref = {{stdinchicite|changed|chemspider}} |
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}} |
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| StdInChI = 1S/Cl5P/c1-6(2,3,4)5 |
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| Section2 = {{Chembox Properties |
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| StdInChIKey_Ref = {{stdinchicite|changed|chemspider}} |
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| Formula = PCl<sub>5</sub> |
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| StdInChIKey = UHZYTMXLRWXGPK-UHFFFAOYSA-N |
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| MolarMass = 208.24 g/mol |
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| CASNo = 10026-13-8 |
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| Appearance = colourless crystals |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| Density = 2.1 g/cm<sup>3</sup> |
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| UNII_Ref = <!-- {{fdite|correct|FDA}} no such template:fdite--> |
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| Solubility = decomposition (exothermic) |
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| UNII = 0EX753TYDU |
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| SolubleOther = soluble in ], ], ] |
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| PubChem = 24819 |
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| MeltingPt = 166.8 °C, 440.0 K, 332.2 °F |
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| EINECS = 233-060-3 |
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| BoilingPtC = 160 |
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| RTECS = TB6125000 |
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| Boiling_notes = sublimation |
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| UNNumber = 1806 |
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}} |
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}} |
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| Section3 = {{Chembox Structure |
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|Section2={{Chembox Properties |
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| Coordination = trigonal bipyramidal |
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| P=1 | Cl=5 |
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| CrystalStruct = tetragonal |
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| Appearance = yellowish white crystals |
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| Dipole = 0 ] |
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| Odor = pungent, unpleasant<ref name=PGCH/> |
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| Coordination = D<sub>3h</sub> |
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| Density = 2.1 g/cm<sup>3</sup> |
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}} |
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| Solubility = reacts |
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| Section7 = {{Chembox Hazards |
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| SolubleOther = soluble in ], ], ] |
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| ExternalMSDS = |
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| MeltingPtC = 160.5 |
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| EUIndex = 015-008-00-X |
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| BoilingPtC = 166.8 |
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| EUClass = Very toxic ('''T+''') |
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| BoilingPt_notes = sublimation |
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| RPhrases = {{R14}}, {{R22}}, {{R26}}, {{R34}}, {{R48/20}} |
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| VaporPressure = 1.11 kPa (80 °C)<br> 4.58 kPa (100 °C)<ref name=nist>{{nist|name=Phosphorus pentachloride|id=C10026138|accessdate=2014-05-15|mask=FFFF|units=SI}}</ref> |
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| SPhrases = {{S1/2}}, {{S7/8}}, {{S26}}, {{S36/37/39}}, {{S45}} |
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}} |
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| NFPA-H = 3 |
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|Section3={{Chembox Structure |
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| NFPA-F = 0 |
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| Coordination = ''D''<sub>3h</sub> (]) |
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| NFPA-R = 2 |
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| CrystalStruct = tetragonal |
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| NFPA-O = W |
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| Dipole = 0 ] |
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| FlashPt = Non-flammable |
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}} |
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| LD50 = 660 mg/kg |
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|Section4={{Chembox Thermochemistry |
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}} |
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| HeatCapacity = 111.5 J/mol·K<ref name=nist /> |
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| Section8 = {{Chembox Related |
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| Entropy = 364.2 J/mol·K<ref name=nist /> |
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| OtherAnions = |
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| OtherCations = |
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| DeltaHf = |
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| DeltaGf = |
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| OtherFunctn = ]<br />]<br />] |
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| DeltaHc = |
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| Function = phosphorus pentahalides |
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}} |
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| OtherCpds = ]<br />] |
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|Section7={{Chembox Hazards |
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}} |
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| GHSPictograms = {{GHS05}}{{GHS06}}{{GHS08}}<ref name="sigma"></ref> |
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| GHSSignalWord = Danger |
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| HPhrases = {{H-phrases|302|314|330|373}}<ref name="sigma" /> |
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| PPhrases = {{P-phrases|260|280|284|305+351+338|310}}<ref name="sigma" /> |
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| ExternalSDS = |
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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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| LD50 = 660 mg/kg (rat, oral)<ref name=IDLH/> |
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| IDLH = 70 mg/m<sup>3</sup><ref name=PGCH>{{PGCH|0509}}</ref> |
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| LC50 = 205 mg/m<sup>3</sup> (rat)<ref name=IDLH>{{IDLH|10026138|Phosphorus pentachloride}}</ref> |
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| REL = TWA 1 mg/m<sup>3</sup><ref name=PGCH/> |
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| PEL = TWA 1 mg/m<sup>3</sup><ref name=PGCH/> |
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| LCLo = 1020 mg/m<sup>3</sup> (mouse, 10 min)<ref name=IDLH/> |
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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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| OtherFunction = ]<br />]<br />] |
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| OtherFunction_label = phosphorus pentahalides |
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| OtherCompounds = ]<br />] |
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}} |
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'''Phosphorus pentachloride''' is the ] with the formula PCl<sub>5</sub>. It is one of the most important phosphorus chlorides, others being ] and ]. PCl<sub>5</sub> finds use as a chlorinating ]. It is a colourless, water-sensitive ], although commercial samples can be yellowish and contaminated with ]. |
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'''Phosphorus pentachloride''' is the ] with the formula PCl<sub>5</sub>. It is one of the most important ] chlorides/oxychlorides, others being ] and ]. PCl<sub>5</sub> finds use as a ] reagent. It is a colourless, water-sensitive ], although commercial samples can be yellowish and contaminated with ]. |
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==Structure== |
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==Structure== |
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The structures for the phosphorus chlorides are invariably consistent with ] theory. The structure of PCl<sub>5</sub> depends on its environment. Gaseous and molten PCl<sub>5</sub> is a neutral molecule with trigonal bipyramidal (''D''<sub>3h</sub>) ]. The ] nature of this species (as well as for PCl{{su|b=6|p=−}}, see below) can be explained with ]ing model. This trigonal bipyramidal structure persists in non-polar solvents, such as ] and ].<ref>D. E. C. Corbridge "Phosphorus: An Outline of its Chemistry, Biochemistry, and Technology" 5th Edition Elsevier: Amsterdam 1995. ISBN 0-444-89307-5.</ref> In the solid state PCl<sub>5</sub> is ionic, formulated PCl{{su|b=4|p=+}}PCl{{su|b=6|p=−}}.<ref name="Holleman">Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN 0-12-352651-5.</ref> |
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The structures for the phosphorus chlorides are invariably consistent with ]. The structure of PCl<sub>5</sub> depends on its environment. Gaseous and molten PCl<sub>5</sub> is a neutral molecule with ] geometry and (''D''<sub>3h</sub>) ]. The ] nature of this species (as well as of {{chem|PCl|6|-}}, see below) can be explained with the inclusion of non-bonding ]s (]) or ] (]). This trigonal bipyramidal structure persists in nonpolar solvents, such as ] and ].<ref>{{cite book| first = D. E. C. | last=Corbridge| title = Phosphorus: An outline of its chemistry, biochemistry, and uses| year = 1995| publisher = Elsevier Science | isbn = 0-444-89307-5 }}</ref> In the solid state PCl<sub>5</sub> is an ] called tetrachlorophosphonium hexachlorophosphate formulated {{chem|PCl|4|+|PCl|6|-}}.<ref name="Holleman">{{cite book| first1= A. F.|last1= Holleman|first2=E.|last2= Wiber |first3=N.|last3= Wiberg | title = Inorganic Chemistry| year = 2001| publisher = Academic Press| isbn = 978-0-12-352651-9 }}</ref> |
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] |
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In solutions of polar solvents, PCl<sub>5</sub> undergoes "autoionization".<ref>{{cite journal | author = Suter, R. W.; Knachel, H. C.; Petro, V. P.; Howatson, J. H.; S. G. Shore, S. G. | title = Nature of Phosphorus(V) Chloride in Ionizing and Nonionizing Solvents | journal = ] | volume = 95 | year = 1973 | pages = 1474–1479 | doi = 10.1021/ja00786a021}}</ref> Dilute solutions dissociate according to the following equilibrium: |
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In solutions of polar solvents, PCl<sub>5</sub> undergoes self-].<ref>{{cite journal | last1= Suter |first1=R. W.|last2= Knachel |first2=H. C. |last3=Petro |first3=V. P. |last4=Howatson |first4=J. H. |last5= Shore|first5= S. G. |name-list-style=amp | title = Nature of Phosphorus(V) Chloride in Ionizing and Nonionizing Solvents | journal = ] | volume = 95 | year = 1978 | pages = 1474–1479 | doi = 10.1021/ja00786a021 | issue = 5}}</ref> Dilute solutions dissociate according to the following equilibrium: |
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:PCl<sub>5</sub> {{eqm}} Cl<sup>−</sup> |
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:PCl<sub>5</sub> {{eqm}} {{chem|PCl|4|+}} + Cl<sup>−</sup> |
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At higher concentrations, a second equilibrium becomes more important: |
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At higher concentrations, a second equilibrium becomes more prevalent: |
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:2 PCl<sub>5</sub> {{eqm}} |
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:2 PCl<sub>5</sub> {{eqm}} {{chem|PCl|4|+}} + {{chem|PCl|6|-}} |
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The cation PCl{{su|b=4|p=+}} and the anion PCl{{su|b=6|p=−}} are tetrahedral and octahedral, respectively. At one time, PCl<sub>5</sub> in solution was thought to form a dimeric structure, P<sub>2</sub>Cl<sub>10</sub>, but this suggestion is not supported by ] measurements. |
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The cation {{chem|PCl|4|+}} and the anion {{chem|PCl|6|-}} are ] and ], respectively. At one time, PCl<sub>5</sub> in solution was thought to form a dimeric structure, P<sub>2</sub>Cl<sub>10</sub>, but this suggestion is not supported by ] measurements. |
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] and ] also adopt trigonal bipyramidal structures. The relevant bond distances are 211 (As-Cl<sub>eq</sub>), 221 (As-Cl<sub>eq</sub>), 227 (Sb-Cl<sub>eq</sub>), and 233.3 pm (Sb-Cl<sub>ax</sub> ).<ref>{{cite journal | author = Haupt, S.; Seppelt, K. | title = Solid State Structures of AsCl<sub>5</sub> and SbCl<sub>5</sub> | journal = ] | year = 2002 | volume = 628 |pages = 729–734 | doi = 10.1002/1521-3749(200205)628:4<729::AID-ZAAC729>3.0.CO;2-E}}</ref> At low temperatures, SbCl<sub>5</sub> converts to the dimer, bioctahedral Sb<sub>2</sub>Cl<sub>10</sub>, structurally related to ]. |
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===Related pentachlorides=== |
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] and ] also adopt trigonal bipyramidal structures. The relevant bond distances are 211 pm (As−Cl<sub>eq</sub>), 221 pm (As−Cl<sub>ax</sub>), 227 pm (Sb−Cl<sub>eq</sub>), and 233.3 pm (Sb−Cl<sub>ax</sub>).<ref>{{cite journal |last1=Haupt |first1=S. |last2=Seppelt |first2=K. | title = Solid State Structures of AsCl<sub>5</sub> and SbCl<sub>5</sub> | journal = ] | year = 2002 | volume = 628 |pages = 729–734 | doi = 10.1002/1521-3749(200205)628:4<729::AID-ZAAC729>3.0.CO;2-E | issue = 4| doi-access = free }}</ref> At low temperatures, SbCl<sub>5</sub> converts to the dimer, dioctahedral Sb<sub>2</sub>Cl<sub>10</sub>, structurally related to ]. |
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==Preparation== |
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==Preparation== |
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PCl<sub>5</sub> is prepared by the ] of PCl<sub>3</sub>. This reaction was used to produce ca. 10,000,000 kg of PCl<sub>5</sub> in 2000.<ref name="Holleman" /> |
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PCl<sub>5</sub> is prepared by the ] of PCl<sub>3</sub>.<ref>{{cite book|first=R. N.|last=Maxson|chapter=Phosphorus Pentachloride|date=1939|volume=1|pages=99–100|doi=10.1002/9780470132326.ch34|title=Inorganic Syntheses|isbn=9780470132326}}</ref> This reaction is used to produce around 10,000 tonnes of PCl<sub>5</sub> per year (as of 2000).<ref name="Holleman" /> |
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:PCl<sub>3</sub> + Cl<sub>2</sub> {{eqm}} PCl<sub>5</sub> (ΔH = −124 kJ/mol) |
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:PCl<sub>3</sub> + Cl<sub>2</sub> {{eqm}} PCl<sub>5</sub> {{pad|3em}} (Δ''H'' = −124 kJ/mol) |
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PCl<sub>5</sub> exists in equilibrium with PCl<sub>3</sub> and ], and at 180 °C the degree of dissociation is ca. 40%.<ref name="Holleman" /> Because of this equilibrium, samples of PCl<sub>5</sub> often contain chlorine, which imparts a greenish colouration. |
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PCl<sub>5</sub> exists in equilibrium with PCl<sub>3</sub> and ], and at 180 °C the degree of dissociation is about 40%.<ref name="Holleman" /> Because of this equilibrium, samples of PCl<sub>5</sub> often contain chlorine, which imparts a greenish coloration. |
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==Reactions== |
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==Reactions== |
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===Hydrolysis=== |
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===Hydrolysis=== |
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In its most characteristic reaction, PCl<sub>5</sub> ] upon contact with ] to release ] and give phosphorus oxides. |
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In its most characteristic reaction, PCl<sub>5</sub> ] upon contact with ] to release ] and give phosphorus oxides. The first hydrolysis product is ]: |
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:PCl<sub>5</sub> + H<sub>2</sub>O → POCl<sub>3</sub> + 2 HCl |
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The first hydrolysis product is ]: |
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:PCl<sub>5</sub> + H<sub>2</sub>O → POCl<sub>3</sub> + 2 HCl |
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In hot water, hydrolysis proceeds completely to ''ortho''-]: |
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In hot water, hydrolysis proceeds completely to ]: |
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:PCl<sub>5</sub> + 4 H<sub>2</sub>O → H<sub>3</sub>PO<sub>4</sub> + 5 HCl</center> |
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:PCl<sub>5</sub> + 4 H<sub>2</sub>O → H<sub>3</sub>PO<sub>4</sub> + 5 HCl |
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===Lewis acidity=== |
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PCl<sub>5</sub> is most often used for chlorinations of organic and inorganic compounds.<ref name="Burks">Burks, Jr., J. E. “Phosphorus(V) Chloride” in Encyclopedia of Reagents for Organic Synthesis (Ed: L. Paquette) 2004, J. Wiley & Sons, New York. DOI: 10.1002/047084289.</ref> |
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Phosphorus pentachloride is a Lewis acid. This property underpins many of its characteristic reactions, autoionization, chlorinations, hydrolysis. A well studied adduct is PCl<sub>5</sub>(pyridine).<ref>{{cite journal|title=Neutral Six-Coordinate Phosphorus|first1=Chih Y.|last1=Wong|first2=Dietmar K.|last2=Kennepohl|first3=Ronald G.|last3=Cavell|journal=Chemical Reviews|year=1996|volume=96|issue=6|pages=1917–1952|doi=10.1021/cr9410880|pmid=11848816}}</ref> |
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===Chlorination of organic compounds=== |
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===Chlorination of organic compounds=== |
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In synthetic chemistry, two classes of chlorination are usually of interest. Oxidative chlorinations entail the transfer of Cl<sub>2</sub> from the reagent to the substrate. Substitutive chlorinations entail replacement of O or OH groups with chloride. PCl<sub>5</sub> can be used for both processes. |
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In synthetic chemistry, two classes of chlorination are usually of interest: oxidative chlorinations and substitutive chlorinations. Oxidative chlorinations entail the transfer of Cl<sub>2</sub> from the reagent to the substrate. Substitutive chlorinations entail replacement of O or OH groups with chloride. PCl<sub>5</sub> can be used for both processes. |
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PCl<sub>5</sub> will convert ]s to the corresponding ]<ref>{{OrgSynth | author = ], R.; Jenkins, R. L. | title = ''p''-Nitrobenzoyl chloride | collvol = 1 | collvolpages = 394 | prep = cv1p0394 | year = 1941}}</ref> as well as ]s to ]. ] is more commonly used in the laboratory because the SO<sub>2</sub> is more easily separated from the organic products than is POCl<sub>3</sub>. |
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Upon treatment with PCl<sub>5</sub>, ]s convert to the corresponding ].<ref>{{OrgSynth | authorlink = Roger Adams|last1=Adams |first1=R. |last2=Jenkins |first2=R. L. | title = ''p''-Nitrobenzoyl chloride | collvol = 1 | collvolpages = 394 | prep = cv1p0394 | year = 1941}}</ref> The following mechanism has been proposed:<ref>{{cite book|last=Clayden|first=Jonathan|title=Organic chemistry|year=2005|publisher=Oxford University Press|location=Oxford|isbn=978-0-19-850346-0|edition=Reprinted|url-access=registration|url=https://archive.org/details/organicchemistry00clay_0}}</ref> |
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:] |
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It also converts ]s to ]. ] is more commonly used in the laboratory because the resultant ] is more easily separated from the organic products than is POCl<sub>3</sub>. |
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PCl<sub>5</sub> and PCl<sub>3</sub> bear some resemblance to ], as both serve often as sources of Cl<sub>2</sub>. Again for oxidative chlorinations on the laboratory scale, ] is often preferred over PCl<sub>5</sub> since the gaseous SO<sub>2</sub> by-product is readily separated. |
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PCl<sub>5</sub> reacts with a tertiary amides, such as ], to give dimethylchloromethyleneammonium chloride, which is called the ], Cl. More typically, a related salt is generated from the reaction of DMF and POCl<sub>3</sub>. Such reagents are useful in the preparation of derivatives of ] by formylation and for the conversion of C-OH groups into C-Cl groups.<ref name="Burks" /> |
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PCl<sub>5</sub> reacts with a tertiary amides, such as ] (DMF), to give dimethylchloromethyleneammonium chloride, which is called the ], Cl. More typically, a related salt is generated from the reaction of DMF and POCl<sub>3</sub>. Such reagents are useful in the preparation of derivatives of ] by formylation and for the conversion of C−OH groups into C−Cl groups.<ref name="Burks">{{cite encyclopedia|last=Burks Jr. |first=J. E. |title=Encyclopedia of Reagents for Organic Synthesis |chapter=Phosphorus(V) chloride |editor-first=L. |editor-last=Paquette |date=2004 |publisher=J. Wiley & Sons |location=New York, NY |doi=10.1002/047084289X.rp158|isbn=0471936235 }}</ref> |
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In contrast to PCl<sub>3</sub>, the pentachloride replaces allylic and benzylic CH bonds and is especially renowned for the conversion of C=O groups to CCl<sub>2</sub> groups.<ref>{{OrgSynth | author = Gross, H.; Rieche, A.; Höft, E.; Beyer, E. | title = Dichloromethyl Methyl Ether | collvol = 5 | collvolpages = 365 | prep = cv5p0365 | year = 1973}}</ref> |
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It is especially renowned for the conversion of ] groups to CCl<sub>2</sub> groups.<ref>{{OrgSynth | last1= Gross |first1=H. |last2=Rieche |first2=A. |last3=Höft |first3=E. |last4=Beyer |first4=E. | title = Dichloromethyl methyl ether | collvol = 5 | collvolpages = 365 | prep = cv5p0365 | year = 1973}}</ref> For example, ] and phosphorus pentachloride react to give the ]:<ref name="Spaggiari2007">{{cite journal|last1=Spaggiari|first1=A.|first2=D. |last2=Vaccari |first3=P. |last3=Davoli |first4=G. |last4=Torre |first5=F. |last5=Prati |year=2007|title=A Mild Synthesis of Vinyl Halides and ''gem''-Dihalides Using Triphenyl Phosphite−Halogen-Based Reagents|journal=The Journal of Organic Chemistry|volume=72|issue=6|pages=2216–2219|issn=0022-3263|pmid=17295542|doi=10.1021/jo061346g}}</ref> |
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:(C<sub>6</sub>H<sub>5</sub>)<sub>2</sub>CO + PCl<sub>5</sub> → (C<sub>6</sub>H<sub>5</sub>)<sub>2</sub>CCl<sub>2</sub> + POCl<sub>3</sub> |
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The ] character of PCl<sub>5</sub> is highlighted by its reaction with ] to give, after ], phosphonic acid derivatives.<ref>{{OrgSynth | author = Schmutzler, R. | title = Styrylphosphonic dichloride | collvol = 5 | collvolpages = 1005 | prep = cv5p1005 | year = 1973}}</ref> |
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The ] character of PCl<sub>5</sub> is highlighted by its reaction with ] to give, after ], ] derivatives.<ref>{{OrgSynth | last= Schmutzler |first=R. | title = Styrylphosphonic dichloride | collvol = 5 | collvolpages = 1005 | prep = cv5p1005 | year = 1973}}</ref> |
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===Comparison with related reagents=== |
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Both PCl<sub>3</sub> and PCl<sub>5</sub> convert R<sub>3</sub>COH groups to the chloride R<sub>3</sub>CCl. The pentachloride is however a source of chlorine in many reactions. It chlorinates allylic and ] CH bonds. PCl5 bears a greater resemblance to ], also a source of Cl<sub>2</sub>. For oxidative chlorinations on the laboratory scale, sulfuryl chloride is often preferred over PCl<sub>5</sub> since the gaseous SO<sub>2</sub> by-product is readily separated. |
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===Chlorination of inorganic compounds=== |
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===Chlorination of inorganic compounds=== |
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As for the reactions with organic compounds, the use of PCl<sub>5</sub> has been superseded by SO<sub>2</sub>Cl<sub>2</sub>. The reaction of ] and PCl<sub>5</sub> produces ]:<ref>F. A. Cotton, G. Wilkinson, C. A. Murillo, and M. Bochmann (April 1999). Advanced Inorganic Chemistry, 6th Edition. Wiley-VCH. ISBN 0-471-19957-5</ref> |
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As for the reactions with organic compounds, the use of PCl<sub>5</sub> has been superseded by SO<sub>2</sub>Cl<sub>2</sub>. The reaction of ] and PCl<sub>5</sub> produces ] :<ref>{{cite book| first= Frank Albert|last= Cotton| title = Advanced Inorganic Chemistry| year = 1999| publisher = Wiley-Interscience| isbn = 978-0-471-19957-1 }}</ref>{{page needed|date=September 2017}} |
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:6 PCl<sub>5</sub> + P<sub>4</sub>O<sub>10</sub> → 10 POCl<sub>3</sub></center> |
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:6 PCl<sub>5</sub> + P<sub>4</sub>O<sub>10</sub> → 10 POCl<sub>3</sub> |
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PCl<sub>5</sub> chlorinates ] to form ] chloride: |
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PCl<sub>5</sub> chlorinates ] to form unstable ]: |
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:PCl<sub>5</sub> + 2 NO<sub>2</sub> → PCl<sub>3</sub> + 2 NO<sub>2</sub>Cl |
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:PCl<sub>5</sub> + 2 NO<sub>2</sub> → PCl<sub>3</sub> + 2 NO<sub>2</sub>Cl |
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:2 NO<sub>2</sub>Cl → 2 NO<sub>2</sub> + Cl<sub>2</sub> |
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PCl<sub>5</sub> is a precursor for ], LiPF<sub>6</sub>, an ] in ]. {{chem|LiPF|6}} is produced by the reaction of {{chem|PCl|5}} with ], with ] as a side-product: |
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PCl<sub>5</sub> is a precursor for ], LiPF<sub>6</sub>. Lithium hexafluorophosphate is a commonly employed salt in ]s in ].<ref name="Dobrov-2017">{{cite journal |last1=Bushkova |first1=O. V. |last2=Yaroslavtseva |first2=T. V. |last3=Dobrovolsky |first3=Yu. A. |title=New lithium salts in electrolytes for lithium-ion batteries (Review) |journal=Russian Journal of Electrochemistry |date=4 August 2017 |volume=53 |issue=7 |pages=677–699 |doi=10.1134/S1023193517070035|s2cid=103854243 }}</ref> {{chem|LiPF|6}} is produced by the reaction of {{chem|PCl|5}} with ], with ] as a side product: |
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:PCl<sub>5</sub> + 6 LiF → LiPF<sub>6</sub> + 5 LiCl |
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:PCl<sub>5</sub> + 6 LiF → LiPF<sub>6</sub> + 5 LiCl |
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==Safety== |
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==Safety== |
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PCl<sub>5</sub> is a dangerous substance as it reacts violently with water. |
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PCl<sub>5</sub> is a dangerous substance as it reacts violently with water. It is also corrosive when in contact with skin and can be fatal when inhaled. |
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== History == |
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Phosphorus pentachloride was first prepared in 1808 by the English chemist ].<ref>{{cite journal|last1=Davy|first1=Humphry|title=The Bakerian Lecture. An account of some new analytical researches on the nature of certain bodies, particularly the alkalies, phosphorus, sulphur, carbonaceous matter, and the acids hitherto undecomposed; with some general observations on chemical theory|journal=Philosophical Transactions of the Royal Society of London|date=1809|volume=99|pages=39–104|url=https://babel.hathitrust.org/cgi/pt?id=mdp.39015034564347;view=1up;seq=53|doi=10.1098/rstl.1809.0005|s2cid=98814859}} On pp. 94–95, Davy mentioned that when he burned phosphorus in chlorine gas ("oxymuriatic acid gas"), he obtained a clear liquid (phosphorus trichloride) and a white solid (phosphorus pentachloride).</ref> Davy's analysis of phosphorus pentachloride was inaccurate;<ref>{{cite journal|last1=Davy|first1=Humphry|title=Researches on the oxymuriatic acid , its nature and combinations; and on the elements of the muriatic acid . With some experiments on sulphur and phosphorus, made in the laboratory of the Royal Institution|journal=Philosophical Transactions of the Royal Society of London|date=1810|volume=100|pages=231–257|url=https://babel.hathitrust.org/cgi/pt?id=mdp.39015034564339;view=1up;seq=301|doi=10.1098/rstl.1810.0016|doi-access=|s2cid=95219058 }} On p. 257, Davy presented his empirical formula for phosphorus pentachloride: 1 portion of phosphorus to 3 portions of "oxymuriatic gas" (chlorine).</ref> the first accurate analysis was provided in 1816 by the French chemist ].<ref>{{cite journal|last1=Dulong|title=Extrait d'un mémoire sur les combinaisons du phosphore avec l'oxigène|journal=Annales de Chimie et de Physique|date=1816|volume=2|pages=141–150|url=https://babel.hathitrust.org/cgi/pt?id=hvd.hx3dvb;view=1up;seq=147|series=2nd series|trans-title=Extract from a memoir on the compounds of phosphorus with oxygen|language=fr}} On p. 148, Dulong presented the correct analysis of phosphorus pentachloride (which is 14.9% phosphorus and 85.1% chlorine by weight, vs. Dulong's values of 15.4% and 84.6%, respectively).</ref> |
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==See also== |
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==See also== |
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==References== |
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==References== |
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{{reflist}} |
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==External links== |
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==External links== |
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{{Commons category|Phosphorus pentachloride}} |
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