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Potassium ferricyanide is the
chemical compound A chemical compound is a chemical substance composed of many identical molecules (or molecular entities) containing atoms from more than one chemical element held together by chemical bonds. A molecule consisting of atoms of only one element ...
with the formula K3 e(CN)6 This bright red salt contains the
octahedral In geometry, an octahedron (plural: octahedra, octahedrons) is a polyhedron with eight faces. The term is most commonly used to refer to the regular octahedron, a Platonic solid composed of eight equilateral triangles, four of which meet a ...
ly coordinated e(CN)6sup>3− ion. It is soluble in water and its solution shows some green-yellow
fluorescence Fluorescence is the emission of light by a substance that has absorbed light or other electromagnetic radiation. It is a form of luminescence. In most cases, the emitted light has a longer wavelength, and therefore a lower photon energy, tha ...
. It was discovered in 1822 by
Leopold Gmelin Leopold Gmelin (2 August 1788 – 13 April 1853) was a German chemist. Gmelin was a professor at the University of Heidelberg He worked on the red prussiate and created Gmelin's test, and wrote his ''Handbook of Chemistry'', which over successi ...
.


Preparation

Potassium ferricyanide is manufactured by passing
chlorine Chlorine is a chemical element with the symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between them. Chlorine i ...
through a solution of
potassium ferrocyanide Potassium ferrocyanide is the inorganic compound with formula K4 e(CN)6�3H2O. It is the potassium salt of the coordination complex e(CN)6sup>4−. This salt forms lemon-yellow monoclinic crystals. Synthesis In 1752, the French chemist Pie ...
. Potassium ferricyanide separates from the solution: :2 K4 e(CN)6+ Cl2 → 2 K3 e(CN)6+ 2 KCl


Structure

Like other metal cyanides, solid potassium ferricyanide has a complicated polymeric structure. The polymer consists of octahedral e(CN)6sup>3− centers crosslinked with K+ ions that are bound to the CN
ligand In coordination chemistry, a ligand is an ion or molecule ( functional group) that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's elec ...
s. The K+---NCFe linkages break when the solid is dissolved in water.


Applications

The compound is also used to harden
iron Iron () is a chemical element with Symbol (chemistry), symbol Fe (from la, Wikt:ferrum, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 element, group 8 of the periodic table. It is, Abundanc ...
and steel, in electroplating, dyeing
wool Wool is the textile fibre obtained from sheep and other mammals, especially goats, rabbits, and camelids. The term may also refer to inorganic materials, such as mineral wool and glass wool, that have properties similar to animal wool. ...
, as a
laboratory A laboratory (; ; colloquially lab) is a facility that provides controlled conditions in which scientific or technological research, experiments, and measurement may be performed. Laboratory services are provided in a variety of settings: physic ...
reagent, and as a mild
oxidizing agent An oxidizing agent (also known as an oxidant, oxidizer, electron recipient, or electron acceptor) is a substance in a redox chemical reaction that gains or " accepts"/"receives" an electron from a (called the , , or ). In other words, an oxi ...
in
organic chemistry Organic chemistry is a subdiscipline within chemistry involving the scientific study of the structure, properties, and reactions of organic compounds and organic materials, i.e., matter in its various forms that contain carbon atoms.Clayden, ...
.


Photography


Blueprint, cyanotype, toner

The compound has widespread use in
blueprint A blueprint is a reproduction of a technical drawing or engineering drawing using a contact print process on light-sensitive sheets. Introduced by Sir John Herschel in 1842, the process allowed rapid and accurate production of an unlimited number ...
drawing and in
photography Photography is the art, application, and practice of creating durable images by recording light, either electronically by means of an image sensor, or chemically by means of a light-sensitive material such as photographic film. It is employe ...
(
Cyanotype The cyanotype (from Ancient Greek κυάνεος - ''kuáneos'', “dark blue” + τύπος - ''túpos'', “mark, impression, type”) is a slow-reacting, economical photographic printing formulation sensitive to a limited near ultraviolet ...
process). Several photographic print toning processes involve the use of potassium ferricyanide.


Bleaching

Potassium ferricyanide was used as an
oxidizing agent An oxidizing agent (also known as an oxidant, oxidizer, electron recipient, or electron acceptor) is a substance in a redox chemical reaction that gains or " accepts"/"receives" an electron from a (called the , , or ). In other words, an oxi ...
to remove
silver Silver is a chemical element with the symbol Ag (from the Latin ', derived from the Proto-Indo-European ''h₂erǵ'': "shiny" or "white") and atomic number 47. A soft, white, lustrous transition metal, it exhibits the highest electrical ...
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 Ethylenediaminetetraacetic acid (EDTA) is an aminopolycarboxylic acid with the formula H2N(CH2CO2H)2sub>2. This white, water-soluble solid is widely used to bind to iron (Fe2+/Fe3+) and calcium ions (Ca2+), forming water-soluble complexes ev ...
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.


Farmers Reducer

Ferricyanide is also used in black-and-white photography with
sodium thiosulfate Sodium thiosulfate (sodium thiosulphate) is an inorganic compound with the formula . Typically it is available as the white or colorless pentahydrate, . The solid is an efflorescent (loses water readily) crystalline substance that dissolves well in ...
(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 In photography, exposure is the amount of light per unit area (the image plane's illuminance times the exposure time) reaching a frame of photographic film or the surface of an electronic image sensor, as determined by shutter speed, lens F- ...
of the negative, or brighten the highlights in the print.


Reagent in organic synthesis

Potassium ferricyanide is a used as an oxidant in organic chemistry. It is an oxidant for catalyst regeneration in
Sharpless dihydroxylation Sharpless asymmetric dihydroxylation (also called the Sharpless bishydroxylation) is the chemical reaction of an alkene with osmium tetroxide in the presence of a chiral quinine ligand to form a vicinal diol. The reaction has been applied to alk ...
s.


Sensors and indicators

Potassium ferricyanide is also one of two compounds present in
ferroxyl indicator solution Ferroxyl indicator is a solution containing potassium hexacyanoferrate(III) and phenolphthalein. It turns blue in the presence of Fe2+ ions, and pink in the presence of hydroxide ions. It can be used to detect metal oxidation, and is often used t ...
(along with
phenolphthalein Phenolphthalein ( ) is a chemical compound with the formula C20 H14 O4 and is often written as "HIn", "HPh", "phph" or simply "Ph" in shorthand notation. Phenolphthalein is often used as an indicator in acid–base titrations. For this applica ...
) that turns blue (
Prussian blue Prussian blue (also known as Berlin blue, Brandenburg blue or, in painting, Parisian or Paris blue) is a dark blue pigment produced by oxidation of ferrous ferrocyanide salts. It has the chemical formula Fe CN)">Cyanide.html" ;"title="e(Cyani ...
) 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 Prussian blue (also known as Berlin blue, Brandenburg blue or, in painting, Parisian or Paris blue) is a dark blue pigment produced by oxidation of ferrous ferrocyanide salts. It has the chemical formula Fe CN)">Cyanide.html" ;"title="e(Cyani ...
. In physiology experiments potassium ferricyanide provides a means increasing a solution's
redox potential Redox potential (also known as oxidation / reduction potential, ''ORP'', ''pe'', ''E_'', or E_) is a measure of the tendency of a chemical species to acquire electrons from or lose electrons to an electrode and thereby be reduced or oxidised respe ...
(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 Sodium dithionite (also known as sodium hydrosulfite) is a white crystalline powder with a sulfurous odor. Although it is stable in dry air, it decomposes in hot water and in acid solutions. Structure The structure has been examined by Raman s ...
is usually used as a reducing chemical in such experiments (E°' ~ −420 mV at pH 7). Potassum ferricyanide is used to determine the ferric reducing power potential of a sample (extract, chemical compound, etc.). Such a measurement is used to determine of the antioxidant property of a sample. Potassium ferricyanide is a component of amperometric
biosensor A biosensor is an analytical device, used for the detection of a chemical substance, that combines a biological component with a physicochemical detector. The ''sensitive biological element'', e.g. tissue, microorganisms, organelles, cell rece ...
s as an
electron transfer Electron transfer (ET) occurs when an electron relocates from an atom or molecule to another such chemical entity. ET is a mechanistic description of certain kinds of redox reactions involving transfer of electrons. Electrochemical processes ar ...
agent replacing an enzyme's natural electron transfer agent such as
oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as ...
as with the
enzyme Enzymes () are proteins that act as biological catalysts by accelerating chemical reactions. The molecules upon which enzymes may act are called substrates, and the enzyme converts the substrates into different molecules known as products ...
glucose oxidase The glucose oxidase enzyme (GOx or GOD) also known as notatin (EC number 1.1.3.4) is an oxidoreductase that catalyses the oxidation of glucose to hydrogen peroxide and D-glucono-δ-lactone. This enzyme is produced by certain species of fungi and ...
. It is an ingredient in commercially available blood glucose meters for use by
diabetics Diabetes, also known as diabetes mellitus, is a group of metabolic disorders characterized by a high blood sugar level (hyperglycemia) over a prolonged period of time. Symptoms often include frequent urination, increased thirst and increased a ...
.


Other

Potassium ferricyanide is combined with
potassium hydroxide Potassium hydroxide is an inorganic compound with the formula K OH, and is commonly called caustic potash. Along with sodium hydroxide (NaOH), KOH is a prototypical strong base. It has many industrial and niche applications, most of which exp ...
(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

Prussian blue Prussian blue (also known as Berlin blue, Brandenburg blue or, in painting, Parisian or Paris blue) is a dark blue pigment produced by oxidation of ferrous ferrocyanide salts. It has the chemical formula Fe CN)">Cyanide.html" ;"title="e(Cyani ...
, the deep blue pigment in blue printing, is generated by the reaction of K3 e(CN)6with ferrous (Fe2+) ions as well as K4 e(CN)6with ferric salts. In
histology Histology, also known as microscopic anatomy or microanatomy, is the branch of biology which studies the microscopic anatomy of biological tissues. Histology is the microscopic counterpart to gross anatomy, which looks at larger structures vi ...
, 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 Prussian blue (also known as Berlin blue, Brandenburg blue or, in painting, Parisian or Paris blue) is a dark blue pigment produced by oxidation of ferrous ferrocyanide salts. It has the chemical formula Fe CN)">Cyanide.html" ;"title="e(Cyani ...
. To detect ferric (Fe3+) iron, potassium ''ferrocyanide'' is used instead in the
Perls' Prussian blue In histology, histopathology, and clinical pathology, Perls Prussian blue is a commonly used method to detect the presence of iron in tissue or cell samples. Perls Prussian Blue derives its name from the German pathologist Max Perls (1843–188 ...
staining method. The material formed in the Turnbull's blue reaction and the compound formed in the Prussian blue reaction are the same.


Safety

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+ + e(CN)6sup>3− → 6 HCN + Fe3+


See also

*
Ferricyanide Ferricyanide is the anion e(CN)6sup>3−. It is also called hexacyanoferrate(III) and in rare, but systematic nomenclature, hexacyanidoferrate(III). The most common salt of this anion is potassium ferricyanide, a red crystalline material that ...
*
Ferrocyanide Ferrocyanide is the name of the anion CN)6">cyanide.html" ;"title="e(cyanide">CN)6sup>4−. Salts of this coordination complex give yellow solutions. It is usually available as the salt potassium ferrocyanide, which has the formula K4Fe(CN)6. e ...
*
Potassium ferrocyanide Potassium ferrocyanide is the inorganic compound with formula K4 e(CN)6�3H2O. It is the potassium salt of the coordination complex e(CN)6sup>4−. This salt forms lemon-yellow monoclinic crystals. Synthesis In 1752, the French chemist Pie ...


References


External links


International Chemical Safety Card 1132


{{DEFAULTSORT:Potassium Ferricyanide Potassium compounds Iron(III) compounds Cyano complexes Iron complexes Photographic chemicals Oxidizing agents