Potassium ferricyanide

Potassium ferricyanide is manufactured by passing chlorine through a solution of potassium ferrocyanide. Potassium ferricyanide separates from the solution:

:2 K₄[Fe(CN)₆] + Cl₂ → 2 K₃[Fe(CN)₆] + 2 KCl

Like other metal cyanides, solid potassium ferricyanide has a complicated polymeric structure. The polymer consists of octahedral [Fe(CN)₆]³⁻ centers crosslinked with K⁺ ions that are bound to the CN ligands.{{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 }} The K⁺---NCFe linkages break when the solid is dissolved in water.

The compound is also used to harden iron and steel, in electroplating, dyeing wool, as a laboratory reagent, and as a mild oxidizing agent in organic chemistry.

The compound has widespread use in blueprint drawing and in photography (Cyanotype process). Several photographic print toning 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.

Potassium ferricyanide was used as an oxidizing agent to remove silver 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 EDTA have been used in color processing since the 1972 introduction of the Kodak C-41 process. In color lithography, 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.

Ferricyanide is also used in black-and-white photography with sodium thiosulfate (hypo) to reduce the density of a negative or gelatin silver print where the mixture is known as Farmer's reducer; this can help offset problems from overexposure of the negative, or brighten the highlights in the print.{{ 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 }}

Potassium ferricyanide is a used as an oxidant in organic chemistry.{{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}}{{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}} It is an oxidant for catalyst regeneration in Sharpless dihydroxylations.{{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}}{{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}}

Potassium ferricyanide is also one of two compounds present in ferroxyl indicator solution (along with phenolphthalein) that turns blue (Prussian blue) in the presence of Fe²⁺ 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 Fe²⁺ ions by using a colorimeter, because of the very intense color of Prussian blue.

In physiology experiments potassium ferricyanide provides a means increasing a solution's redox potential (E°' ~ 436 mV at pH 7). As such, it can oxidize reduced cytochrome c (E°' ~ 247 mV at pH 7) in isolated mitochondria. Sodium dithionite is usually used as a reducing chemical in such experiments (E°' ~ −420 mV at pH 7).

Potassium ferricyanide is used to determine the ferric reducing power potential of a sample (extract, chemical compound, etc.).Nakajima, Y., Sato, Y., & Konishi, T. (2007). Antioxidant Small Phenolic Ingredients in

Inonotus obliquus (persoon) Pilat (Chaga). Chemical & Pharmaceutical Bulletin, 55(8), 1222–1276. Such a measurement is used to determine of the antioxidant property of a sample.

Potassium ferricyanide is a component of amperometric biosensors as an electron transfer agent replacing an enzyme's natural electron transfer agent such as oxygen as with the enzyme glucose oxidase. It is an ingredient in commercially available blood glucose meters for use by diabetics.

Potassium ferricyanide is combined with potassium hydroxide (or sodium hydroxide 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.

Prussian blue, the deep blue pigment in blue printing, is generated by the reaction of K₃[Fe(CN)₆] with ferrous (Fe²⁺) ions as well as K₄[Fe(CN)₆] with ferric salts.{{ 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 }}

In histology, 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 Prussian blue. To detect ferric (Fe³⁺) iron, potassium ferrocyanide is used instead in the Perls' Prussian blue staining method.{{ 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 }} The material formed in the Turnbull's blue reaction and the compound formed in the Prussian blue reaction are the same.{{ 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 }}{{ 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 }}

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 hydrogen cyanide gas is evolved, according to the equation:

:6 H⁺ + [Fe(CN)₆]³⁻ → 6 HCN + Fe³⁺{{ cite web | url = http://www.labchem.com/tools/msds/msds/LC19040.pdf | title = MSDS for potassium ferricyanide }}

For example, it will react with diluted sulfuric acid under heating forming potassium sulfate, ferric sulfate and hydrogen cyanide.

:2 K₃ [Fe(CN)₆] + 6 H₂SO₄ → 3 K₂ SO₄ + Fe₂ (SO₄)₃ + 12 HCN

This will not occur with concentrated sulfuric acid as hydrolysis to formic acid and dehydration to carbon monoxide will take place instead.{{ 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}}

:2 K₃ Fe(CN)₆ + 12 H₂ SO₄ + 12 H₂O → 3 K₂SO₄ + 6 (NH₄)₂ SO₄ + Fe₂ (SO₄)₃ + 12 CO

• Ferricyanide
• Ferrocyanide
• Potassium ferrocyanide

{{reflist}}

• [https://phadkeinstruments.com/study-of-ferricyanide-by-cyclic-voltammetry-using-phadkestat-20/ Studying redox reaction of Ferricyanide using Potentiostat] Effect of different parameters using Cyclic Voltammetry

• [http://www.inchem.org/documents/icsc/icsc/eics1132.htm International Chemical Safety Card 1132]
• [https://web.archive.org/web/20060517035532/http://www.npi.gov.au/database/substance-info/profiles/29.html National Pollutant Inventory – Cyanide compounds fact sheet]

{{Potassium compounds}}

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Category:Potassium compounds

Category:Iron(III) compounds

Category:Cyano complexes

Category:Iron complexes

Category:Photographic chemicals

Category:Oxidizing agents