Prussian blue (also known as Berlin blue, Brandenburg blue, Parisian and Paris blue) is a dark blue pigment produced by oxidation of ferrous ferrocyanide salts. It has the chemical formula Fe4[Fe(CN)6]3. It consists of Fe3+ cations, where iron is in the oxidation state of +3, and [Fe(CN)6]4− anions, where iron is in the oxidation state of +2, so, the other name of this salt is iron(III) hexacyanoferrate(II). Turnbull's blue is essentially identical chemically, excepting that it has different impurities and particle sizes—because it is made from different reagents—and thus it has a slightly different color. Prussian blue was created in the early 18th century and is the first modern synthetic pigment. It is prepared as a very fine colloidal dispersion, because the compound is not soluble in water. It contains variable amounts of other ions and its appearance depends sensitively on the size of the colloidal particles. The pigment is used in paints, it became prominent in 19th-century aizuri-e (藍摺り絵) Japanese woodblock prints, and it is the traditional "blue" in technical blueprints. In medicine, orally administered Prussian blue is used as an antidote for certain kinds of heavy metal poisoning, e.g., by thallium(I) and radioactive isotopes of caesium. The therapy exploits Prussian blue's ion-exchange properties and high affinity for certain "soft" metal cations. It is on the World Health Organization's List of Essential Medicines, the most important medications needed in a basic health system. Prussian blue lent its name to prussic acid (hydrogen cyanide) derived from it. In German, hydrogen cyanide is called Blausäure ('blue acid').
History
Prussian blue pigment is significant since it was the first stable and relatively lightfast blue pigment to be widely used since the loss of knowledge regarding the synthesis of Egyptian blue. European painters had previously used a number of pigments such as indigo dye, smalt, and Tyrian purple, and the extremely expensive ultramarine made from lapis lazuli. Japanese painters and woodblock print artists, likewise, did not have access to a long-lasting blue pigment until they began to import Prussian blue from Europe. Prussian blue Fe7(CN)18 (also (Fe4[Fe(CN)6]3·xH2O) was probably synthesized for the first time by the paint maker Johann Jacob Diesbach in Berlin around 1706. The pigment is believed to have been accidentally created when Diesbach used potash tainted with blood to create some red cochineal dye. The original dye required potash, ferric sulfate, and dried cochineal. Instead, the blood, potash, and iron sulfate reacted to create a compound known as iron ferrocyanide, which, unlike the desired red pigment, has a very distinct blue hue. It was named Preußisch blau and Berlinisch Blau in 1709 by its first trader. The pigment readily replaced the expensive lapis lazuli-derived ultramarine and was an important topic in the letters exchanged between Johann Leonhard Frisch and the president of the Prussian Academy of Sciences, Gottfried Wilhelm Leibniz, between 1708 and 1716. It is first mentioned in a letter written by Frisch to Leibniz, from March 31, 1708. Not later than 1708, Frisch began to promote and sell the pigment across Europe. By August 1709, the pigment had been termed Preussisch blau; by November 1709, the German name Berlinisch Blau had been used for the first time by Frisch. Frisch himself is the author of the first known publication of Prussian blue in the paper Notitia Coerulei Berolinensis nuper inventi in 1710, as can be deduced from his letters. Diesbach had been working for Frisch since about 1701.
The Entombment of Christ, dated 1709 by Pieter van der Werff (Picture Gallery, Sanssouci, Potsdam) is the oldest known painting where Prussian blue was used. Around 1710, painters at the Prussian court were already using the pigment. At around the same time, Prussian blue arrived in Paris, where Antoine Watteau and later his successors Nicolas Lancret and Jean-Baptiste Pater used it in their paintings. François Boucher used the pigment extensively for both blues and greens. The pigment was prominently used by the Japanese artist Katushika Hokusai in his woodblock print series Thirty-six Views of Mount Fuji, including the celebrated print The Great Wave off Kanagawa (c.1831). In 1731, Georg Ernst Stahl published an account of the first synthesis of Prussian blue. The story involves not only Diesbach, but also Johann Konrad Dippel. Diesbach was attempting to create a red lake pigment from cochineal, but obtained the blue instead as a result of the contaminated potash he was using. He borrowed the potash from Dippel, who had used it to produce his animal oil. No other known historical source mentions Dippel in this context. It is, therefore, difficult to judge the reliability of this story today. In 1724, the recipe was finally published by John Woodward. In 1752, French chemist Pierre J. Macquer made the important step of showing Prussian blue could be reduced to a salt of iron and a new acid, which could be used to reconstitute the dye. The new acid, hydrogen cyanide, first isolated from Prussian blue in pure form and characterized in 1782 by Swedish chemist Carl Wilhelm Scheele, was eventually given the name Blausäure (literally 'blue acid') because of its derivation from Prussian blue, and in English became known popularly as prussic acid. Cyanide, a colorless anion that forms in the process of making Prussian blue, derives its name from the Greek word for dark blue. In the late 1800s, Rabbi Gershon Henoch Leiner, the Hasidic Rebbe of Radzin, dyed tzitziyot with Prussian blue made with sepia, believing that this was the true techeiles dye. Even though some have questioned its identity as techeiles because of its artificial production, and claimed that had Rabbi Leiner been aware of this he would have retracted his position that his dye was techeiles, others have disputed this and claimed that Rabbi Leiner would not have retracted.
Military symbol
From the beginning of the 18th century, Prussian blue was the predominant uniform coat color worn by the infantry and artillery regiments of the Prussian Army. As Dunkelblau (dark blue), this shade achieved a symbolic importance and continued to be worn by most German soldiers for ceremonial and off-duty occasions until the outbreak of World War I, when it was superseded by greenish-gray field gray (Feldgrau).
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