Potassium ferrocyanide is the inorganic compound with formula K4[Fe(CN)6]·3H2O.

It is the
potassium salt of the coordination complex [Fe(CN)6]4−. This salt forms lemon-
yellow monoclinic crystals.

Synthesis[edit]
In 1752, the French chemist Pierre Joseph Macquer (1718–1784) first reported the preparation of
potassium ferrocyanide, which he achieved by reacting Prussian blue (iron(III) ferrocyanide)
with potassium carbonate.[4][5]

Modern production[edit]
Potassium ferrocyanide is produced industrially from hydrogen cyanide, ferrous chloride,
and calcium hydroxide, the combination of which affords Ca2[Fe(CN)6]·11H2O. This solution is
then treated with potassium salts to precipitate the mixed calcium-potassium salt CaK2[Fe(CN)6],
which in turn is treated with potassium carbonate to give the tetrapotassium salt.[6]

Historical production[edit]
Historically, the compound was manufactured from organic compounds containing nitrogen, iron
filings, and potassium carbonate.[7] Common nitrogen and carbon sources were torrified horn,
leather scrap, offal, or dried blood.

Chemical reactions[edit]
Treatment of potassium ferrocyanide with nitric acid gives H2[Fe(NO)(CN)5]. After neutralization
of this intermediate with sodium carbonate, red crystals of sodium nitroprusside can be
selectively crystallized.[8]
Upon treatment with chlorine gas, potassium ferrocyanide converts to potassium ferricyanide:
2 K4[Fe(CN)6] + Cl2 → 2 K3[Fe(CN)6] + 2 KCl
This reaction can be used to remove potassium ferrocyanide from a solution.[citation needed]
A famous reaction involves treatment with ferric salts to give Prussian blue. With the
approximate composition KFe2(CN)6, this insoluble but deeply coloured material is the blue
of blueprinting.

Applications[edit]
Potassium ferrocyanide finds many niche applications in industry. It and 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.[6]
In the EU, ferrocyanides (E 535–538) were, as of 2018, solely authorised in two food
categories as salt substitutes. Kidneys are the organ for ferrocyanide toxicity.[9]
It can also be used in animal feed.[10]
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.[citation needed]
Prior to 1900 AD, before the invention of the Castner process, potassium ferrocyanide was
the most important source of alkali metal cyanides.[6] In this historical process, potassium
cyanide was produced by decomposing potassium ferrocyanide:[7]
K4[Fe(CN)6] → 4 KCN + FeC2 + N2