Prussian blue

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Prussian blue
Sample of prussian blue
Identifiers
CAS number 14038-43-8 YesY
PubChem 2724251
ChemSpider 20074656 YesY
UNII TLE294X33A YesY
EC number 237-875-5
ChEBI CHEBI:30069 YesY
ChEMBL CHEMBL2096629 N
ATC code V03AB31
Gmelin Reference 1093743
Jmol-3D images Image 1
Properties
Molecular formula C18Fe7N18
Molar mass 859.23 g mol−1
Appearance Blue opaque crystals
Pharmacology
Routes of
administration
Oral
Hazards
MSDS MSDS prussian blue
Related compounds
Other cations Potassium ferrocyanide

Sodium ferrocyanide

Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
 N (verify) (what is: YesY/N?)
Infobox references

Prussian blue is a dark blue pigment with the idealized formula Fe7(CN)18. Another name for the color Prussian blue is Berlin blue or, in painting, Parisian blue. Turnbull's blue is the same substance but is made from different reagents, and its slightly different color stems from different impurities.

Prussian blue was one of the first synthetic pigments. It is employed as a very fine colloidal dispersion, as the compound itself is not soluble in water. It is famously complex,[1] owing to the presence of variable amounts of other ions and the sensitive dependence of its appearance on the size of the colloidal particles formed when it is made. The pigment is used in paints, and it is the traditional "blue" in blueprints.

In medicine, Prussian blue is used as an antidote for certain kinds of heavy metal poisoning, e.g., by caesium and thallium. In particular it was used to absorb 137Cs+ from those poisoned in the Goiânia accident.[1] Prussian Blue is orally administered. The therapy exploits Prussian Blue's ion exchange properties and high affinity for certain "soft" metal cations.

Prussian blue lent its name to prussic acid (hydrogen cyanide), which was derived from it. In Germany, hydrogen cyanide is called Blausäure ("blue acid"), and Joseph Louis Gay-Lussac gave cyanide its name, from the Greek word κυανός (kyanos, "blue"), because of the color of Prussian blue.

History[edit]

Prussian blue [Fe4[Fe(CN)6]3] was probably synthesized for the first time by the paint maker Diesbach in Berlin around the year 1706.[2] Most historical sources do not mention a first name of Diesbach. Only Berger refers to him as Johann Jacob Diesbach.[3] It was named "Preußisch blau" and "Berlinisch Blau" in 1709 by its first trader.[4] The pigment replaced the expensive Lapis lazuli and was an important topic in the letters exchanged between Johann Leonhard Frisch[5] and the president of the Royal Academy of Sciences, Gottfried Wilhelm Leibniz, between 1708 and 1716.[4] 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.

In 1731, Georg Ernst Stahl published an account of the first synthesis of Prussian blue.[6] 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.[7][8][9]

To date, 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.[10]

"The Great Wave off Kanagawa" by Hokusai, a famous artwork which makes extensive use of Prussian blue.

This Prussian blue pigment is significant since it was the first stable and relatively lightfast blue pigment to be widely used following 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, which tend to fade, 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.

In 1752 the French chemist Pierre J. Macquer made the important step of showing the Prussian blue could be reduced to a salt of iron and a new acid, which could be used to reconstitute the dye.[11] The new acid, hydrogen cyanide, first isolated from Prussian blue in pure form and characterized about 1783 by the 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.

Production[edit]

Prussian blue is produced by oxidation of ferrous ferrocyanide salts. These white solids have the formula M2Fe[Fe(CN)6] where M+ = Na+ or K+. The iron in this material is all ferrous, hence the absence of deep color associated with the mixed valency. Oxidation of this white solid with hydrogen peroxide or sodium chlorate produces ferricyanide and affords Prussian Blue.[12]

A "soluble" form of PB, K[FeIIIFeII(CN)6], which is really colloidal, can be made from potassium ferrocyanide and iron(III):

K+ + Fe3+ + [FeII(CN)6]4− → KFeIII[FeII(CN)6]

The similar reaction of potassium ferricyanide and iron(II) results in the same colloidal solution, because [FeIII(CN)6]3− is converted into ferrocyanide.

"Insoluble" Prussian blue is produced if in the reactions above an excess of Fe3+ or Fe2+, respectively, is added.  In the first case:

4Fe3+ + 3[FeII(CN)6]4− → FeIII[FeIIIFeII(CN)6]3 [13]

"Turnbull's blue"[edit]

Ferricyanide ion, used to make 'Turnbull's blue'.

In former times, it was thought that addition of Fe(II) salts to a solution of ferricyanide affords a material different from Prussian blue. The product was traditionally named "Turnbull's Blue" (TB). It has been shown, however, by means of X-ray diffraction and electron diffraction methods, that the structures of PB and TB are identical.[14][15] The differences in the colors for TB and PB reflect subtle differences in the method of precipitation, which strongly affects particle size and impurity content.

Properties[edit]

Prussian blue is a microcrystalline blue powder. It is insoluble, but the crystallites tend to form a colloid. Such colloids can pass through fine filters.[1] Despite being one of the oldest known synthetic compounds, the composition of Prussian blue remained uncertain for many years. The precise identification of Prussian blue was complicated by three factors:

  1. Prussian blue is extremely insoluble but also tends to form colloids;
  2. Traditional syntheses tend to afford impure compositions;
  3. Even pure Prussian blue is structurally complex, defying routine crystallographic analysis.

Crystal structure[edit]

The chemical formula of insoluble Prussian blue is Fe7(CN)18·xH2O, where x = 14–16. The structure was determined by using IR spectroscopy, Mössbauer spectroscopy, X-ray crystallography, and neutron crystallography. Since X-ray diffraction cannot distinguish carbon from nitrogen, the location of these lighter elements is deduced by spectroscopic means as well as by observing the distances from the iron atom centers.

PB has a cubic lattice structure. Soluble PB crystals contain interstitial K+ ions; insoluble PB has interstitial water instead.
In ideal insoluble PB crystals, the cubic framework is built from Fe(II)-C-N-Fe(III) sequences, with Fe(II)-carbon distances of 1.92 Å and Fe(III)-nitrogen distances of 2.03 Å. One-fourth of the sites of Fe(CN)6 subunits are vacant (empty), leaving three such groups. The empty nitrogen sites are filled with water molecules instead, which are coordinated to Fe(III).

The Fe(II) centers, which are low spin, are surrounded by six carbon ligands in an octahedral configuration. The Fe(III) centers, which are high spin, are octahedrally surrounded on average by 4.5 nitrogen atoms and 1.5 oxygen atoms (the oxygen from the six coordinated water molecules). Additional eight (interstitial) water molecules are present in the unit cell, either as isolated molecules or hydrogen bonded to the coordinated water.

The composition is notoriously variable due to the presence of lattice defects, allowing it to be hydrated to various degrees as water molecules are incorporated into the structure to occupy cation vacancies. The variability of Prussian blue's composition is attributable to its low solubility, which leads to its rapid precipitation without the time to achieve full equilibrium between solid and liquid.[16][17]

Color[edit]

Prussian blue pigment

Prussian blue is strongly colored and tends towards black and dark blue when mixed into oil paints. The exact hue depends on the method of preparation, which dictates the particle size. The intense blue color of Prussian blue is associated with the energy of the transfer of electrons from Fe(II) to Fe(III). Many such mixed-valence compounds absorb certain wavelengths of visible light resulting from intervalence charge transfer. In this case, orange-red light around 680 nanometers in wavelength is absorbed, and the reflected light appears blue as a result.

Like most high chroma pigments, Prussian blue cannot be accurately displayed on a computer display.

PB is electrochromic—changing from blue to colorless upon reduction. This change is caused by reduction of the Fe(III) to Fe(II) eliminating the intervalence charge transfer that causes Prussian blue's color.

Uses[edit]

Pigment[edit]

Vincent van Gogh's Starry Night uses Prussian and Cerulean blue pigments

Because it is easily made, cheap, non-toxic, and intensely colored, Prussian blue has attracted many applications. It was adopted as a pigment very soon after its invention and was almost immediately widely used in oil, watercolor and dyeing.[18] The dominant uses are for pigments: approximately 12,000 tonnes of Prussian blue are produced annually for use in black and bluish inks. A variety of other pigments also contain the material.[12] Engineer's blue and the pigment formed on cyanotypes—giving them their common name blueprints. Certain crayons were once colored with Prussian blue (later relabeled Midnight blue). It is also a popular pigment in paints. Similarly, Prussian blue is the basis for laundry bluing.

Medicine[edit]

Prussian blue's ability to incorporate monocations makes it useful as a sequestering agent for certain heavy metal poisons. Pharmaceutical-grade Prussian blue in particular is used for patients who have ingested thallium or radioactive caesium. According to the International Atomic Energy Agency, an adult male can eat at least 10 grams of Prussian blue per day without serious harm. The U.S. Food and Drug Administration (FDA) has determined that the "500 mg Prussian blue capsules, when manufactured under the conditions of an approved New Drug Application (NDA), can be found safe and effective therapy" in certain poisoning cases.[19] Radiogardase (Prussian blue in soluble capsules [20]) is a commercial product for the removal of caesium-137 from the intestine and so indirectly from the bloodstream by intervening in the enterohepatic circulation of caesium-137,[21] reducing the internal residency time (and exposure) by about two-thirds. It has been withdrawn from the US market because there are safer alternatives.

Laboratory histopathology stain for iron[edit]

Prussian blue stain

Prussian blue is a common histopathology stain used by pathologists to detect the presence of iron in biopsy specimens, such as in bone marrow samples. The original stain formula, known historically (1867) as "Perls' Prussian blue" after its inventor, German pathologist Max Perls (1843–1881), used separate solutions of potassium ferrocyanide and acid to stain tissue (these are now used combined, just before staining). Iron deposits in tissue then form the purple Prussian blue dye in place, and are visualized as blue or purple deposits.[22] The formula is also known as Perls Prussian blue and (incorrectly) as Perl's Prussian blue.

By machinists and toolmakers[edit]

Engineer's blue—Prussian blue in an oily base—is the traditional material used for spotting metal surfaces such as surface plates and bearings for hand scraping. A thin layer of non-drying paste is applied to a reference surface and transfers to the high spots of the workpiece. The toolmaker then scrapes, stones, or otherwise removes the marked high spots. Prussian blue is preferable because it will not abrade the extremely precise reference surfaces as many ground pigments may.

Analytical chemistry[edit]

Prussian blue is formed in the Prussian blue assay for total phenols. Samples and phenolic standards are given acidic ferric chloride and ferricyanide which is reduced to ferrocyanide by the phenols. The ferric chloride and ferrocyanide react to form Prussian blue. Comparing the absorbance at 700 nm of the samples to the standards allows for the determination of total phenols or polyphenols.[23][24]

Safety[edit]

Despite the fact that it is prepared from cyanide salts, Prussian blue is nontoxic because the cyanide groups are tightly bound to Fe. Other polymeric cyanometalates are similarly stable with low toxicity.[citation needed]

Military[edit]

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.[25] As Dunkelblau this shade achieved a symbolic importance and continued to be worn for ceremonial and off-duty occasions until the outbreak of World War I.[26]

See also[edit]

References[edit]

  1. ^ a b c Dunbar, K. R. and Heintz, R. A. (1997). "Chemistry of Transition Metal Cyanide Compounds: Modern Perspectives". Progress in Inorganic Chemistry 45: 283–391. 
  2. ^ Jens Bartoll. "The early use of prussian blue in paintings" (PDF). 9th International Conference on NDT of Art, Jerusalem Israel, 25–30 May 2008. Retrieved 2010-01-22. 
  3. ^ J. E. Berger: Kerrn aller Fridrichs=Städtschen Begebenheiten Manuskript, Berlin, ca.1730 (Berlin, Staatsbibliothek zu Berlin – Preußischer Kulturbesitz, Handschriftenabteilung, Ms. Boruss. quart. 124)
  4. ^ a b J. L. Frisch: Briefwechsel mit Gottfried Wilhelm Leibniz L. H. Fischer (ed.), Berlin, Stankiewicz Buchdruck, 1896, reprint Hildesheim/New York: Georg Olms Verlag, 1976
  5. ^ There is a Wikipedia article in German
  6. ^ G. E. Stahl: Experimenta, Observationes, Animadversiones CCC Numero, Chymicae et Physicae, (Berlin, 1731), pp. 281–283.
  7. ^ Woodward, J. (1724–1725). "Praeparatio coerulei Prussiaci es Germanica missa ad Johannem Woodward.." [Preparation of Prussian blue sent from Germany to John Woodward...]. Philosophical Transactions of the Royal Society of London 33 (381): 15–17. doi:10.1098/rstl.1724.0005. 
  8. ^ Brown, John (1724–1725). "Observations and Experiments upon the Foregoing Preparation". Philosophical Transactions 33 (381): 17–24. Bibcode:1724RSPT...33...17B. doi:10.1098/rstl.1724.0006. JSTOR 103734. . The recipe was subsequently published in [Étienne-François] Geoffroy, "Observations sur la Preparation de Bleu de Prusse ou Bleu de Berlin," Mémoires de l'Académie royale des Sciences année 1725 (Paris, 1727), pp. 153–172.
  9. ^ Sarah Lowengard, The Creation of Color in Eighteenth-Century Europe (New York, New York: Columbia University Press, 2008), Chapter 23: Prussian Blue.
  10. ^ J.Bartoll, B. Jackisch, M. Most, E. Wenders de Calisse, C. M. Vogtherr: Early Prussian Blue. Blue and green pigments in the paintings by Watteau, Lancret and Pater in the collection of Frederick II of Prussia In: TECHNE 25, 2007, pp. 39–46
  11. ^ Pierre-Joseph Macquer (1752) "Éxamen chymique de bleu de Prusse," Mémoires de l'Académie royale des Sciences année 1752 . . . (Paris, 1756), pp. 60–77. This article was reviewed in "Sur le bleu de Prusse," Histoire de l'Académie royale des Sciences... (1752), (Paris, 1756), pp. 79–85.
  12. ^ a b Völz, Hans G. et al. "Pigments, Inorganic" in Ullmann's Encyclopedia of Industrial Chemistry, 2006 Wiley-VCH, Weinheim. doi:10.1002/14356007.a20_243.pub2.
  13. ^ Egon Wiberg,Nils Wiberg,Arnold Frederick Holleman: Inorganic chemistry, p.1444. Academic Press, 2001; Google books
  14. ^ Ozeki, Toru.; Matsumoto, Koichi.; Hikime, Seiichiro. (1984). "Photoacoustic spectra of prussian blue and photochemical reaction of ferric ferricyanide". Analytical Chemistry 56 (14): 2819. doi:10.1021/ac00278a041. 
  15. ^ Izatt, Reed M.; Watt, Gerald D.; Bartholomew, Calvin H.; Christensen, James J. (1970). "Calorimetric study of Prussian blue and Turnbull's blue formation". Inorganic Chemistry 9 (9): 2019. doi:10.1021/ic50091a012. 
  16. ^ Herren, F.; Fischer, P.; Ludi, A.; Haelg, W. (1980). "Neutron diffraction study of Prussian Blue, Fe4[Fe(CN)6]3.xH2O. Location of water molecules and long-range magnetic order". Inorganic Chemistry 19 (4): 956. doi:10.1021/ic50206a032. 
  17. ^ Lundgren, C. A.; Murray, Royce W. (1988). "Observations on the composition of Prussian blue films and their electrochemistry". Inorganic Chemistry 27 (5): 933. doi:10.1021/ic00278a036. 
  18. ^ Berrie, Barbara H. 1997. Prussian Blue. In Artists' Pigments. A Handbook of their History and Characteristics, edited by E. W. FitzHugh. Washington, DC: National Gallery of Art.
  19. ^ "Questions and Answers on Prussian Blue". Retrieved 2009-06-06. 
  20. ^ Radiogardase: Package insert with formula
  21. ^ Heyltex Corporation – Toxicology
  22. ^ Formula for Perls' Prussian blue stain. Accessed April 2, 2009.
  23. ^ Tannin Chemistry PDF (1.41 MB)Accessed December 19, 2009
  24. ^ Stabilization of the Prussian blue color in the determination of polyphenols. Horace D. Graham, J. Agric. Food Chem., 1992, volume 40, issue 5, pages 801–805, doi:10.1021/jf00017a018
  25. ^ Philip Haythornthwaite, page 14 "Frederick the Great's Army – Infantry, ISBN 1855321602
  26. ^ Stephen Bull, pages 8–10 "World War One German Army", ISBN 1 85753 271

External links[edit]