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Potassium ferrocyanide is the
inorganic compound In chemistry, an inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds, that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield of chemistry known as '' inorganic chemist ...
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
Pierre Joseph Macquer Pierre-Joseph Macquer (9 October 1718 – 15 February 1784) was an influential French people, French chemist. He is known for his ''Dictionnaire de chymie'' (1766). He was also involved in practical applications, to medicine and industry, such as ...
(1718–1784) first reported the preparation of potassium ferrocyanide, which he achieved by reacting
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(Cyanid ...
(iron(III) ferrocyanide) with potassium hydroxide.


Modern production

Potassium ferrocyanide is produced industrially from
hydrogen cyanide Hydrogen cyanide, sometimes called prussic acid, is a chemical compound with the formula HCN and structure . It is a colorless, extremely poisonous, and flammable liquid that boils slightly above room temperature, at . HCN is produced on an ...
, ferrous chloride, and
calcium hydroxide Calcium hydroxide (traditionally called slaked lime) is an inorganic compound with the chemical formula Ca( OH)2. It is a colorless crystal or white powder and is produced when quicklime (calcium oxide) is mixed or slaked with water. It has m ...
, the combination of which affords Ca2 e(CN)6·11H2O. This solution is then treated with potassium salts to precipitate the mixed calcium-potassium salt CaK2 e(CN)6 which in turn is treated with potassium carbonate to give the tetrapotassium salt.


Historical production

Historically, the compound was manufactured from organic compounds containing nitrogen, iron filings, and potassium carbonate. Common nitrogen and carbon sources were torrified horn, leather scrap, offal, or dried blood. It was also obtained commercially from gasworks spent oxide (purification of city gas from hydrogen cyanide).


Chemical reactions

Treatment of potassium ferrocyanide with nitric acid gives H2 e(NO)(CN)5 After neutralization of this intermediate with
sodium carbonate Sodium carbonate, , (also known as washing soda, soda ash and soda crystals) is the inorganic compound with the formula Na2CO3 and its various hydrates. All forms are white, odourless, water-soluble salts that yield moderately alkaline solutions ...
, red crystals of sodium nitroprusside can be selectively crystallized. Upon treatment with chlorine gas, potassium ferrocyanide converts to potassium ferricyanide: :2 K4 e(CN)6+ Cl2 → 2 K3 e(CN)6+ 2 KCl This reaction can be used to remove potassium ferrocyanide from a solution. A famous reaction involves treatment with ferric salts to give
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(Cyanid ...
. With the composition Fe CN)">Cyanide.html" ;"title="e(Cyanide">CN) this insoluble but deeply coloured material is the blue of blueprinting.


Applications

Potassium ferrocyanide finds many niche applications in industry. It and Sodium ferrocyanide, the related sodium salt are widely used as anticaking agents for both road salt and table salt. The potassium and sodium ferrocyanides are also used in the purification of tin and the separation of copper from molybdenum ores. Potassium ferrocyanide is used in the production of wine and citric acid. In the EU, ferrocyanides (E 535–538) were, as of 2017, solely authorised in two food categories as salt additives. The kidneys are the organ for ferrocyanide toxicity. It can also be used in animal feed. In the laboratory, potassium ferrocyanide is used to determine the concentration of potassium permanganate, a compound often used in titrations based on redox reactions. Potassium ferrocyanide is used in a mixture with potassium ferricyanide and phosphate buffered solution to provide a buffer for beta-galactosidase, which is used to cleave X-Gal, giving a bright blue visualization where an antibody (or other molecule), conjugated to Beta-gal, has bonded to its target. On reacting with Fe(3) it gives a Prussian blue colour. Thus it is used as an identifying reagent for iron in labs. Potassium ferrocyanide can be used as a fertilizer for plants. Prior to 1900, before the invention of the
Castner process The Castner process is a process for manufacturing sodium metal by electrolysis of molten sodium hydroxide at approximately 330 °C. Below that temperature, the melt would solidify; above that temperature, the molten sodium would start to dissolve ...
, potassium ferrocyanide was the most important source of
alkali metal The alkali metals consist of the chemical elements lithium (Li), sodium (Na), potassium (K),The symbols Na and K for sodium and potassium are derived from their Latin names, ''natrium'' and ''kalium''; these are still the origins of the names ...
cyanides. In this historical process,
potassium cyanide Potassium cyanide is a compound with the formula KCN. This colorless crystalline salt, similar in appearance to sugar, is highly soluble in water. Most KCN is used in gold mining, organic synthesis, and electroplating. Smaller applications includ ...
was produced by decomposing potassium ferrocyanide: K4 e(CN)6→ 4 KCN + FeC2 + N2


Structure

Like other metal cyanides, solid potassium ferrocyanide, both as the hydrate and anhydrous salts, has a complicated polymeric structure. The polymer consists of octahedral e(CN)6sup>4− centers crosslinked with K+ ions that are bound to the CN ligands.Willans, M.J.; Wasylishen, R.E.; McDonald, R. "Polymorphism of potassium ferrocyanide trihydrate as studied by solid-state multinuclear NMR spectroscopy and X-ray diffraction" Inorganic Chemistry 2009, volume 48, p4342-4353 The K+---NC linkages break when the solid is dissolved in water.


Toxicity

Potassium ferrocyanide is nontoxic, and is not decomposed to cyanide in the body. The toxicity in rats is low, with lethal dose (LD50) at 6400 mg/kg.


See also

*
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 ferricyanide * Ferricyanide


References


External links

* * {{DEFAULTSORT:Potassium Ferrocyanide Potassium compounds Iron(II) compounds Cyano complexes Coordination complexes E-number additives Nephrotoxins Iron complexes