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{{short description|Chemical compound}} |
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{{Distinguish|potassium ferrocyanide}} |
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{{redirect|Prussian red|pigment based on ]|Venetian red}} |
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{{chembox |
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{{chembox |
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| Verifiedfields = changed |
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| verifiedrevid = 444993061 |
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| Watchedfields = changed |
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| Name = Potassium ferricyanide |
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| verifiedrevid = 451578816 |
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| ImageFile = Potassium ferricyanide crystals.jpg |
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| Name = Potassium ferricyanide |
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| ImageSize = 230px |
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| ImageName = Potassium ferricyanide |
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| ImageFile = Potassium ferricyanide2.jpg |
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| ImageSize = |
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| ImageFile1 = Potassium-ferricyanide-sample.jpg |
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| ImageSize1 = 230px |
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| ImageSize1 = |
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| ImageName1 = Crystals of potassium ferricyanide |
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| ImageFile1 = Structure of potassium ferricyanide.png |
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| ImageSize2 = |
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| IUPACName = Potassium hexacyanoferrate(III) |
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| OtherNames = Red prussiate<br/>Prussian red<br/>Potassium ferricyanide |
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| ImageName2 = Crystals of potassium ferricyanide |
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| IUPACName = Potassium hexacyanoferrate(III) |
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| Section1 = {{Chembox Identifiers |
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| OtherNames = Red prussiate of Potash,<br/>Prussian red,<br/>Potassium ferricyanide |
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| Section1 = {{Chembox Identifiers |
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| CASNo = 13746-66-2 |
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| CASNo = 13746-66-2 |
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| CASNo_Ref = {{cascite}} |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| UNII = U4MAF9C813 |
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| PubChem = 26250 |
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| PubChem = 26250 |
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| RTECS = LJ8225000 |
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| RTECS = LJ8225000 |
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| EC_number = 237-323-3 |
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| ChEBI = 30060 |
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| Gmelin = 21683 |
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| InChI = 1S/6CN.Fe.3K/c6*1-2;;;;/q6*-1;+3;3*+1 |
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| SMILES = ..N#C(C#N)(C#N)(C#N)(C#N)C#N. |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID = 24458 |
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| InChIKey = BYGOPQKDHGXNCD-UHFFFAOYAG |
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| StdInChI_Ref = {{stdinchicite|changed|chemspider}} |
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| StdInChI = 1S/6CN.Fe.3K/c6*1-2;;;;/q6*-1;+3;3*+1 |
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| StdInChIKey_Ref = {{stdinchicite|changed|chemspider}} |
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| StdInChIKey = BYGOPQKDHGXNCD-UHFFFAOYSA-N |
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}} |
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}} |
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| Section2 = {{Chembox Properties |
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| Section2 = {{Chembox Properties |
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| Formula = C<sub>6</sub>N<sub>6</sub>FeK<sub>3</sub> |
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| Formula = K<sub>3</sub> |
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| MolarMass = 329.24 g/mol |
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| MolarMass = 329.24 g/mol |
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| Appearance = deep red crystals |
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| Appearance = deep red crystals, sometimes small pellets, orange to dark red powder |
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| Density = 1.89 g/cm<sup>3</sup>, solid |
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| Density = 1.89 g/cm<sup>3</sup>, solid |
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| Solubility = 330 g/L ("cold water")<br />464 g/L (20°C)<br/>775 g/L ("hot water")<ref>Kwong, H.-L. "Potassium Ferricyanide" 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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| Solubility = 330 g/L ("cold water")<br />464 g/L (20 °C)<br/>775 g/L ("hot water")<ref>{{ cite encyclopedia | author = Kwong, H.-L. |title = Potassium Ferricyanide | encyclopedia = Encyclopedia of Reagents for Organic Synthesis | editor = Paquette, L. | year = 2004 | publisher = J. Wiley & Sons | location = New York | doi = 10.1002/047084289X| hdl = 10261/236866 |isbn = 9780471936237|url = https://hal.archives-ouvertes.fr/hal-02922790| hdl-access = free }}</ref> |
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| SolubleOther = slightly soluble in ] <br> soluble in ]<br />soluble in water |
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| SolubleOther = slightly soluble in ] <br> soluble in ]<br />soluble in water |
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| MeltingPtC = 300 |
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| MeltingPtC = 300 |
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| BoilingPt = ''decomp.'' |
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| BoilingPt = decomposes |
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| MagSus = +2290.0·10<sup>−6</sup> cm<sup>3</sup>/mol |
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}} |
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}} |
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| Section3 = {{Chembox Structure |
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| Section3 = {{Chembox Structure |
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| Coordination = ] at Fe |
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| Coordination = ] at Fe |
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| CrystalStruct = ] |
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| CrystalStruct = ] |
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}} |
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}} |
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| Section7 = {{Chembox Hazards |
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| Section7 = {{Chembox Hazards |
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| ExternalMSDS = |
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| ExternalSDS = |
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| MainHazards = |
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| EUIndex = Not listed |
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| MainHazards = |
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| NFPA-F = 0 |
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| NFPA-H = 1 |
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| RPhrases = {{R20}}, {{R21}}, {{R22}}, {{R32}} |
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| NFPA-R = 0 |
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| SPhrases = {{S26}}, {{S36}} |
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| LD50 = 2970 mg/kg (mouse, oral) |
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| GHSPictograms = {{GHS07}} |
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| GHSSignalWord = Warning |
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| HPhrases = {{H-phrases|302|315|319|332|335}} |
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| PPhrases = {{P-phrases|261|264|270|271|280|301+312|302+352|304+312|304+340|305+351+338|312|321|330|332+313|337+313|362|403+233|405|501}} |
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| FlashPt = Non-flammable |
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| FlashPt = Non-flammable |
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}} |
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}} |
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| Section8 = {{Chembox Related |
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| Section8 = {{Chembox Related |
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| OtherAnions = ] |
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| OtherAnions = ] |
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| OtherCations = ] |
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| OtherCations = ] |
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}} |
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}} |
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}} |
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] |
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'''Potassium ferricyanide''' is the ] with the formula K<sub>3</sub>. This bright red salt contains the ]ly ] <sup>3−</sup>]] ion.<ref>{{ cite book | author = Sharpe, A. G. | title = The Chemistry of Cyano Complexes of the Transition Metals | publisher = Academic Press | location = London | year = 1976 }}</ref> It is soluble in water and its solution shows some green-yellow ]. It was discovered in 1822 by ].<ref>{{cite journal |last1=Gmelin |first1=Leopold |title=Ueber ein besonderes Cyaneisenkalium, and über eine neue Reihe von blausauren Eisensalzen |journal=Journal für Chemie und Physik |date=1822 |volume=34 |pages=325–346 |url=https://babel.hathitrust.org/cgi/pt?id=nyp.33433069069148&view=1up&seq=347 |trans-title=On a particular potassium iron cyanate, and on a new series of iron salts of cyanic acid |language=German}}</ref><ref>{{cite book|last1=Ihde|first1=A.J.|title=The Development of Modern Chemistry|date=1984|publisher=Dover Publications|location=New York|page=153|edition=2nd}}</ref> |
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'''Potassium ferricyanide''' is the ] with the formula K<sub>3</sub>. This bright red salt contains the ]ly ] <sup>3−</sup>]] ion.<ref>Sharpe, A. G., The Chemistry of Cyano Complexes of the Transition Metals, Academic Press: London, 1976</ref> It is soluble in water and its solution shows some green-yellow ]. |
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<div style="float:right;margin-left:0.5em;"> |
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<big>3 K<sup>+</sup></big> ] |
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</div> |
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==Preparation== |
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==Preparation== |
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Potassium ferricyanide is manufactured by passing ] through a ] of ]. Potassium ferricyanide separates from the solution: |
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Potassium ferricyanide is manufactured by passing ] through a ] of ]. Potassium ferricyanide separates from the solution: |
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:2 K<sub>4</sub> + Cl<sub>2</sub> → 2 K<sub>3</sub> + 2 KCl |
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:2 K<sub>4</sub> + Cl<sub>2</sub> → 2 K<sub>3</sub> + 2 KCl |
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==Structure== |
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Like other metal cyanides, solid potassium ferricyanide has a complicated polymeric structure. The polymer consists of octahedral <sup>3−</sup> centers crosslinked with K<sup>+</sup> ions that are bound to the CN ]s.<ref>{{cite journal | doi=10.1098/rspa.1969.0031 | title=The crystallography and paramagnetic anisotropy of potassium ferricyanide | journal=Proceedings of the Royal Society of London. A. Mathematical and Physical Sciences | year=1969 | volume=309 | issue=1496 | pages=91–118 | bibcode=1969RSPSA.309...91F | last1=Figgis | first1=B. N. | last2=Gerloch | first2=M. | last3=Mason | first3=R. | s2cid=96689342 }}</ref> The K<sup>+</sup>---NCFe linkages break when the solid is dissolved in water. |
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==Applications== |
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==Applications== |
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The compound is also used to ] ] and ], in ], ]ing ], as a ] ], and as a mild ] in ]. |
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In 19th century, it was used for reading ]s and old manuscripts.<ref></ref> |
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===Photography=== |
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The compound has widespread use in ] drawing and in ] (] process). ] and ] ] involve the use of potassium ferricyanide. Potassium ferricyanide is used as an ] to remove ] from negatives and positives, a process called dot etching. In ], potassium ferricyanide is used to reduce the size of color dots without reducing their number, as a kind of manual color correction. The compound is also used to ] ] and ], in ], ]ing ], as a ] ], and as a mild ] in ]. |
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==== Blueprint, cyanotype, toner ==== |
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It is also used in black-and-white photography with ] (hypo)<ref>{{cite book|author1=Leslie Stroebel|author2=Richard D. Zakia|title=The Focal encyclopedia of photography|url=http://books.google.com/books?id=CU7-2ZLGFpYC&pg=PA297|accessdate=1 June 2011|year=1993|publisher=Focal Press|isbn=9780240514178|pages=297–}}</ref> to reduce the density of a ] or ] where the mixture is known as Farmer's reducer; this can help offset problems from ] of the negative, or brighten the highlights in the print. |
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The compound has widespread use in ] drawing and in ] (] process). Several ] processes involve the use of potassium ferricyanide.It is often used as a mild bleach in a concentration of 10g/L to reduce film or print density. |
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==== Bleaching ==== |
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Potassium ferricyanide is also one of two compounds present in ] (along with ]) which turns blue (]) in the presence of Fe<sup>2+</sup> ions, and which can therefore be used to detect metal oxidation that will lead to rust. It is possible to calculate the number of moles of Fe<sup>2+</sup> ions by using a ], because of the very intense color of ] Fe<sub>4</sub><sub>3</sub>. |
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Potassium ferricyanide was used as an ] to remove ] from color negatives and positives during processing, a process called bleaching. Because potassium ferricyanide bleaches are environmentally unfriendly, short-lived, and capable of releasing hydrogen cyanide gas if mixed with high concentrations and volumes of acid, bleaches using ferric ] have been used in color processing since the 1972 introduction of the Kodak ]. In ], potassium ferricyanide is used to reduce the size of color dots without reducing their number, as a kind of manual color correction called dot etching. |
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==== Farmer's reducer ==== |
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Potassium ferricyanide is often used in physiology experiments as a means of increasing a solution's ] (E°' ~ 436 mV at pH 7). ] is usually used as a reducing chemical in such experiments (E°' ~ −420 mV at pH 7). |
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Ferricyanide is also used in black-and-white photography with ] (hypo) to reduce the density of a ] or ] where the mixture is known as Farmer's reducer; this can help offset problems from ] of the negative, or brighten the highlights in the print.<ref>{{ cite encyclopedia | author1 = Stroebel, L. | author2 = Zakia, R. D. | title = Farmer's Reducer | encyclopedia = The Focal Encyclopedia of Photography | url = https://books.google.com/books?id=CU7-2ZLGFpYC&pg=PA297 | year = 1993 | publisher = Focal Press | isbn = 978-0-240-51417-8 | page = 297 }}</ref> |
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===Reagent in organic synthesis=== |
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Potassium ferricyanide is used in many amperometric ]s as an ] agent replacing an enzyme's natural electron transfer agent such as ] as with the ] ]. It is used as this ingredient in many commercially available blood ]s for use by ]. |
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Potassium ferricyanide is a used as an oxidant in organic chemistry.<ref>{{cite journal|first1=E. A.|last1=Prill|first2=S. M.|last2=McElvain |doi=10.15227/orgsyn.015.0041|title=1-Methyl-2-Pyridone|journal=Organic Syntheses|year=1935|volume=15|page=41}}</ref><ref>{{cite journal |first1=Hendryk|last1=Würfel|first2= Dörthe|last2=Jakobi|doi=10.15227/orgsyn.095.0177|title=Syntheses of Substituted 2-Cyano-benzothiazoles|year=2018|journal=Organic Syntheses|volume=95|pages=177–191|doi-access=free}}</ref> It is an oxidant for catalyst regeneration in ]s.<ref>{{cite journal|first1=Javier|last1=Gonzalez|first2= Christine|last2=Aurigemma|first3=Larry|last3=Truesdale|doi=10.15227/orgsyn.079.0093|title= Synthesis of (+)-(1S,2R)- and (−)-(1R,2S)-''trans''-2-Phenylcyclohexanol via Sharpless Asymmetric Dihydroxylation (AD)|journal=Organic Syntheses|year=2002|volume=79|page=93}}</ref><ref>{{cite journal|first1=Ryu|last1=Oi|first2=K. Barry|last2=Sharpless |doi=10.15227/orgsyn.073.0001|title=3-[(1S)-1,2-Dihydroxyethyl]-1,5-Dihydro-3H-2,4-Benzodioxepine|journal=Organic Syntheses|year=1996|volume=73|page=1}}</ref> |
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===Sensors and indicators=== |
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Potassium ferricyanide is the main component of Murakami's etchant for cemented carbides. |
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Potassium ferricyanide is also one of two compounds present in ] (along with ]) that turns blue (]) in the presence of Fe<sup>2+</sup> ions, and which can therefore be used to detect metal oxidation that will lead to rust. It is possible to calculate the number of moles of Fe<sup>2+</sup> ions by using a ], because of the very intense color of ]. |
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In physiology experiments potassium ferricyanide provides a means increasing a solution's ] (E°' ~ 436 mV at pH 7). As such, it can oxidize reduced cytochrome c (E°' ~ 247 mV at pH 7) in isolated mitochondria. ] is usually used as a reducing chemical in such experiments (E°' ~ −420 mV at pH 7). |
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Potassium ferricyanide is used to determine the ferric reducing power potential of a sample (extract, chemical compound, etc.).<ref>Nakajima, Y., Sato, Y., & Konishi, T. (2007). Antioxidant Small Phenolic Ingredients in |
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Inonotus obliquus (persoon) Pilat (Chaga). Chemical & Pharmaceutical Bulletin, 55(8), 1222–1276.</ref> Such a measurement is used to determine of the ] property of a sample. |
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Potassium ferricyanide is a component of amperometric ]s as an ] agent replacing an enzyme's natural electron transfer agent such as ] as with the ] ]. It is an ingredient in commercially available blood ]s for use by ]. |
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===Other=== |
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Potassium ferricyanide is combined with ] (or ] as a substitute) and water to formulate Murakami's etchant. This etchant is used by metallographers to provide contrast between binder and carbide phases in cemented carbides. |
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==Prussian blue== |
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==Prussian blue== |
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], the deep blue pigment in blue printing, is generated by the reaction of K<sub>3</sub> with ferrous (Fe<sup>2+</sup>) ions.<ref>Dunbar, K. R.; Heintz, R. A., "Chemistry of Transition Metal Cyanide Compounds: Modern Perspectives", Progress in Inorganic Chemistry, 1997, volume 45, pp. 283–391 {{doi|10.1002/9780470166468.ch4}}.</ref> |
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], the deep blue pigment in blue printing, is generated by the reaction of K<sub>3</sub> with ferrous (Fe<sup>2+</sup>) ions as well as K<sub>4</sub> with ferric salts.<ref>{{ cite book |author1=Dunbar, K. R. |author2=Heintz, R. A. | chapter = Chemistry of Transition Metal Cyanide Compounds: Modern Perspectives | title = Progress in Inorganic Chemistry | year = 1997 | volume = 45 | pages = 283–391 | doi = 10.1002/9780470166468.ch4 |series=Progress in Inorganic Chemistry |isbn=9780470166468 }}</ref> |
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In ], potassium ferricyanide is used to detect ferrous iron in biological tissue, as the stain ]. In this reaction, potassium ferricyanide reacts with ferrous iron in acidic solution to produce an insoluble blue pigment, and both the stain and the pigment are commonly referred to as ]. To detect ferric (Fe<sup>3+</sup>) iron, potassium ''ferrocyanide'' is used instead; the stain and pigment produced are commonly known as Prussian blue.<ref>Carson, Freida L. (1997). ''Histotechnology: A Self-Instructional Text'' (2nd ed.), pp. 209–211. Chicago: American Society of Clinical Pathologists. ISBN 0-89189-411-X.</ref> It has been found that the compound formed in the Turnbull's blue reaction and the compound formed in the Prussian blue reaction are the same unique compound, ].<ref>{{cite journal|doi=10.3390/i4060362|author=Tafesse, F. |year=2003|url=http://www.mdpi.org/ijms/papers/i4060362.pdf|title= Comparative studies on Prussian blue or diaquatetraamine-cobalt(III) promoted hydrolysis of 4-nitrophenylphosphate in microemulsions|journal=International Journal of Molecular Sciences|volume=4|issue=6|pages=362–370}}</ref><ref>{{cite journal|author=Verdaguer, M., Galvez, N., Garde, R., and Desplanches, C. |year=2002|title= Electrons at work in Prussian blue analogues|journal=Electrochemical Society Interface|volume=11|issue=3|pages=28–32|doi=10.1002/chin.200304218|url=http://www.electrochem.org/dl/interface/fal/fal02/IF8-02-Pages28-32.pdf}}</ref> |
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In ], potassium ferricyanide is used to detect ferrous iron in biological tissue. Potassium ferricyanide reacts with ferrous iron in acidic solution to produce the insoluble blue pigment, commonly referred to as Turnbull's blue or ]. To detect ferric (Fe<sup>3+</sup>) iron, potassium ''ferrocyanide'' is used instead in the ] staining method.<ref>{{ cite book | author = Carson, F. L. | year = 1997 | title = Histotechnology: A Self-Instructional Text | edition = 2nd | pages = 209–211 | location = Chicago | publisher = American Society of Clinical Pathologists | isbn = 978-0-89189-411-7 }}</ref> The material formed in the Turnbull's blue reaction and the compound formed in the Prussian blue reaction are the same.<ref>{{ cite journal | author = Tafesse, F. | title = Comparative Studies on Prussian Blue or Diaquatetraamine-Cobalt(III) Promoted Hydrolysis of 4-Nitrophenylphosphate in Microemulsions | journal = International Journal of Molecular Sciences | year = 2003 | volume = 4 | issue = 6 | pages = 362–370 | doi = 10.3390/i4060362 | url = http://www.mdpi.org/ijms/papers/i4060362.pdf | doi-access = free }}</ref><ref>{{ cite journal |author1=Verdaguer, M. |author2=Galvez, N. |author3=Garde, R. |author4=Desplanches, C. | title = Electrons at Work in Prussian Blue Analogues | journal = Electrochemical Society Interface | year = 2002 | volume = 11 | issue = 3 | pages = 28–32 | doi = 10.1002/chin.200304218 | url = http://www.electrochem.org/dl/interface/fal/fal02/IF8-02-Pages28-32.pdf }}</ref> |
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==Safety== |
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==Safety== |
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Potassium ferricyanide has low toxicity, its main hazard being that it is a mild irritant to the eyes and skin. However, under very strongly acidic conditions, highly toxic ] gas is evolved, according to the equation: |
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:6 H<sup>+</sup> + <sup>3−</sup> → 6 HCN + Fe<sup>3+</sup><ref>{{ cite web | url = http://www.labchem.com/tools/msds/msds/LC19040.pdf | title = MSDS for potassium ferricyanide }}</ref> |
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Potassium ferricyanide has very low toxicity, its main hazard being that it is a mild irritant to the eyes and skin. However, under very strongly acidic conditions, highly toxic ] gas is evolved, according to the equation: |
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For example, it will react with diluted sulfuric acid under heating forming ], ] and hydrogen cyanide. |
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:6 H<sup>+</sup> + <sup>3−</sup> → 6 HCN + Fe<sup>3+</sup><ref></ref> |
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:2 K<sub>3</sub> + 6 H<sub>2</sub>SO<sub>4</sub> → 3 K<sub>2</sub> SO<sub>4</sub> + Fe<sub>2</sub> (SO<sub>4</sub>)<sub>3</sub> + 12 HCN |
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The reaction with ] is as follows: |
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This won't occour with concentrated sulfuric acid as hydrolysis to ] and dehydration to ] will take place instead.<ref>{{ cite web | url = https://pubs.rsc.org/en/content/articlelanding/1924/ct/ct9242501358 | title = The hydrolysis of potassium ferricyanide and potassium cobalticyanide by sulfuric acid}}</ref> |
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:6 HCl + K<sub>3</sub> → 6 HCN + FeCl<sub>3</sub> + 3 KCl |
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:2 K<sub>3</sub> Fe(CN)<sub>6</sub> + 12 H<sub>2</sub> SO<sub>4</sub> + 12 H<sub>2</sub>O → 3 K<sub>2</sub>SO<sub>4</sub> + 6 (NH<sub>4</sub>)<sub>2</sub> SO<sub>4</sub> + Fe<sub>2</sub> (SO<sub>4</sub>)<sub>3</sub> + 12 CO |
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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|30em}} |
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{{reflist}} |
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== Further reading == |
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* Effect of different parameters using ] |
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==External links== |
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==External links== |
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{{Potassium compounds}} |
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{{Potassium compounds}} |
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{{DEFAULTSORT:Potassium Ferricyanide}} |
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