Berlin blue

from Wikipedia, the free encyclopedia
Structural formula
Structure of Berlin blue
General
Surname Berlin blue
other names
  • Iron (III) hexacyanidoferrate (II / III)
  • Prussian blue
  • Turnbulls blue
  • blue acid iron
  • Ferric potassium cyanide
  • Further
Molecular formula Fe 4 [Fe (CN) 6 ] 3
Brief description

dark blue, odorless solid

External identifiers / databases
CAS number 14038-43-8
EC number 237-875-5
ECHA InfoCard 100.034.418
PubChem 2724251
ChemSpider 20074656
DrugBank DB06783
Wikidata Q421894
Drug information
ATC code

V03 AB31

properties
Molar mass 859.23 g · mol -1
Physical state

firmly

density

1.8 g cm −3

Melting point

Water release and partial decomposition from 250 ° C

solubility

practically insoluble in water

safety instructions
Please note the exemption from the labeling requirement for drugs, medical devices, cosmetics, food and animal feed
GHS labeling of hazardous substances
no GHS pictograms
H and P phrases H: no H-phrases
P: no P-phrases
Toxicological data

> 8000 mg kg −1 ( LD 50 ,  mouse ,  oral )

As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions .

Berlin blue is a lightfast , deep blue , inorganic pigment . It is an organometallic compound with the empirical formula Fe 4 [Fe (CN) 6 ] 3 • 15 H 2 O, which is known as insoluble Prussian blue . In addition, there are so-called soluble Prussian blue variants with the empirical formula M [Fe 3+ Fe 2+ (CN) 6 ], where M represents a potassium, sodium or ammonium ion. The soluble variants are in aqueous solution in the form of colloidal solutions; there is no real solubility with dissociation of the compound. Both Berlin blue variants are iron (III) salts of hexacyanoferrate (II).

Prussian blue contains iron in the +2 and +3 oxidation states , which are linked via the cyanide anion [C≡N] - . The essential structural element of the Berlin blue is the sequence Fe (II) - [C≡N] -Fe (III) in a three-dimensional, polymeric framework. It is a dark blue solid that is stable in air and water.

The Berlin paint manufacturer Johann Jacob Diesbach first produced Berlin blue around 1706. It immediately gained commercial importance as a pigment for oil painting and the dyeing of fabrics. With the publication of the recipe in 1724, several companies started producing Berlin blue under many other names.

Prussian blue is considered to be the first synthetic coordination compound . It owes its deep blue color to metal-metal-charge-transfer junctions , which absorb radiation in the yellow-red area and reflect the blue light as a complementary color .

The names hydrogen cyanide and cyanide (from Greek κυανός ( kyanos ) blue ) are derived from the color of Berlin blue. The term prussiate, in which a cyano ligand in the complex is replaced by another ligand , such as nitroprusside , is derived from the term Prussian blue. Berliner Blau is the namesake for the so-called Berliner Blau analogues , a class of microporous inorganic solids with a wide range of catalytic , electronic, optical and magnetic properties.

Due to its simple production from a solution of iron (III) salt and yellow blood liquor salt , it is mainly used as an inexpensive colorant . Prussian blue is practically non-toxic and is used as an antidote for poisoning with radioactive cesium or thallium . The therapy uses the ion exchange properties and the high affinity of the compound for certain metal cations. It's on the World Health Organization's list of Essential Medicines needed in a healthcare system.

nomenclature

Berlin blue was offered under a variety of names. The names refer to the names of the inventors or manufacturers, the places of manufacture, the color nuances, the applications or the chemical components and processes. The variants can differ in their color cast. All names refer to blue pigments based on the Fe (II) / Fe (III) cyano complex and differ only insignificantly in their composition. The type and amount of alkali metal or ammonium ions used influences the production of certain color nuances. Historically, the pigment was marketed as blue salt . In the Color Index , Berlin Blue is listed as CI Pigment Blue 27 according to color and structure as CI 77510 for potassium-doped iron blue and CI 77520 for ammonium-sodium-iron blue.

Diesbachblau is named after the name of the actual inventor. Turnbulls Blue was founded in 1828 by John Turnbull Jr. developed and distributed by the Scottish company Turnbull & Ramsay in Glasgow. Turnbulls Blue is a blue pigment formed from red blood lye salt with excess iron (II) ions. It is obtained by reacting iron (II) salts with potassium hexacyanidoferrate (III) in an aqueous solution. It was initially assumed that the dark blue precipitate that formed had a different composition than the Prussian blue obtained by reacting iron (III) salts with potassium hexacyanidoferrate (II) (yellow blood liquor salt). However, by means of EPR and Mössbauer spectroscopy it could be determined that the reaction products are largely identical, since the following equilibrium exists:

Milori blue refers to cooked types of the pigment that have a slightly warmer, red-tinged hue and were first produced by the Milori de France company. According to Diesbach, this had obtained a blue pigment in a different process, which compared to Prussian blue is somewhat weaker in its color strength. The name Milori blue has survived to this day. Vossenblau was named after L. Vossen & Co GmbH near Düsseldorf, which was exclusively responsible for sales from 1905.

French blue or Parisian blue refers to the headquarters of A. Milori. Prussian blue, also Prussian blue, and Zwickau blue also refer to production sites.

The name bronze blue refers to the bronzing red color cast that shows up with various binders. In particular, bronze blue refers to the reddish sheen of the unground, black-blue chunks.

Chinese Blue or China Blue takes its name from a decorative porcelain . This production variant of the pigment results in the purest and most brilliant colors with a green cast. It gives the best full tone and the highest opacity, but it has the hardest structure and the highest oil requirement. Saxon blue refers to the color of the uniforms of the Saxon army that have been dyed with Berlin blue. Toner blue or ink blue got this name because of its use to tint the reddish (brown) color cast of soot.

From the structure or composition of the pigment, the names are derived iron blue , Eisencyanblau , Eisenhexacyanidoferrat , steel blue , Eisencyanürcyanid, Ferrozyanblau and Ferriferrocyanidblau and steel blue from. Potash blue refers to the use of potash in its manufacture. Until the First World War, the cation of the complex salt was predominantly potassium. When the price of potash rose sharply at the beginning of the 20th century, the ammonium salt was produced with equally good properties. Iron blue also refers to an ancient pigment from the mineral vivianite .

Luisenblau, Modeblau, Wasserblau are product names for modified colorants in textile dyeing and may have originated as names for fashion colors. The red-tinged pigment is Milori blue, the green-tinged variant is Chinese blue.

In the French-speaking area , the terms Bleu de prusse or Bleu de Milori are common, in the English-speaking area the terms iron blue , toning blue or Prussian blue .

history

First syntheses

JK Dippel alias Christianus Democritus.

Johann Jacob Diesbach , a Berlin paint manufacturer, produced Berlin blue for the first time probably around 1706 . The earliest known written mention of the pigment is in a letter dated March 31, 1708, from Johann Leonhard Frisch to Gottfried Wilhelm Leibniz , President of the Prussian Academy of Sciences . In August 1709 he named the pigment Prussian blue , in November of the same year he changed the name to Berlinisch blue . Frisch was responsible for the early marketing of the pigment. He claimed to have improved the pigment through an acid treatment. Frisch is the author of the first publication on Berlin blue in Notitia Coerulei Berolinensis nuper inventi from 1710. Diesbach was in Frisch's service from around 1701.

In addition to Diesbach, Johann Konrad Dippel is associated with the invention. How reliable the corresponding information by Georg Ernst Stahl and the associated history of the first accidental production of the pigment is, is difficult to judge today. Accordingly Diesbach was busy producing a red dye when he ran out of potash (potassium carbonate) to precipitate the dye. He therefore had his colleague Johann Konrad Dippel give him a substitute (contaminated with “ Dippel's animal oil ”), which, contrary to his expectations, precipitated a blue pigment. The recipe could be kept secret for some time until the Englishman John Woodward published it in the Philosophical Transactions in 1724 . He got the information about this from the Berlin pharmacist Caspar Neumann .

Use in painting and textile dyeing

Berlin blue initially served as a pigment for painters, who used it to replace the relatively expensive ultramarine made from lapis lazuli . The painting "The Entombment of Christ" (Picture Gallery Sanssouci , Potsdam ) created by Pieter van der Werff in Rotterdam in 1709 represents the earliest known evidence of the use of the pigment in painting. Around 1710 it was widely used and achieved by painters at the Prussian court Paris, where it was used by Antoine Watteau and later by his successors Nicolas Lancret and Jean-Baptiste Pater .

A dyeing process developed by Pierre-Joseph Macquer , in which the Berlin blue was deposited directly onto the wool, cotton or silk fiber using yellow blood liquor, significantly improved the color fastness and led to an upswing in Berlin blue production from the 1760s. The invention gave Macquer the appointment of general inspector of the dye works. The increased demand led to the establishment of eleven Berlin blue factories in Germany between 1756 and 1799. The factories met their energy needs and the supply of potash largely by burning wood. The processing of animal waste was accompanied by an odor nuisance that required a certain distance from the residential buildings. As a result, these factories were often located near forests. Inorganic-chemical production in Germany began in the middle of the 18th century. Theodor Fontane described the industrial production of Berlin blue in his novel Frau Jenny Treibel , a Berlin family who owned large factories for the production of Berlin blue. The model for this literary figure is the Kunheim entrepreneurial family (Chemische Fabriken Kunheim u. Co. AG and from 1925 Rhenania-Kunheim Verein Chemischer Fabriken AG), with whom Fontane's sister Jenny Sommerfeld was friends.

Production was carried out with largely exclusion of air by pyrolysis of nitrogenous animal products such as blood, claws or wool in a potash melt at a temperature of around 900 to 1000 ° C in iron vessels. The target product potassium cyanide was formed , released ammonia could be further processed into salmia or stag's horn salt . The melt was dissolved in water, the potassium cyanide reacting with the iron (II) sulfide present as a by-product to form yellow blood liquor salt.

export

In 1759 the Swedish East India Company initially exported small quantities of Berlin blues to China and India. From 1775 larger quantities were exported to China and ten years later the export had already quadrupled.

Towards the end of the 18th century, Berlin blue was exported by the Dutch and Chinese to Japan, where it was called Bero, Bero-Ai or Beroin and was used in traditional Japanese color woodblock prints . The Japanese stopped imports from China in 1810. The Dutch resumed trading in 1818 and the Chinese in 1824. Berlin blue can be identified on two Japanese paintings from the Edo period , one from the 1760s and the other from 1817. Well-known works such as the series 36 Views of Mount Fuji created by Katsushika Hokusai from 1830 onwards often use Berlin blue.

Modern developments

In 1968, the German pharmacologist Horst Heydlauf investigated the effect of Berlin blue as an agent against thallium poisoning . Heydlauf showed that the thallium ions are stored in the lattice of Berlin blue and can thus be excreted from the body. The effectiveness has since been comprehensively confirmed. The same effect was shown for cesium ions. Berlin blue was used as an antidote in Brazil in 1987 when around 250 people were contaminated with radioactive cesium-137 in the Goiânia accident , which had been broken out of a stolen radiation therapy device from a disused hospital. The doctors treated 29 heavily contaminated people with Berlin blue, 25 of whom survived the cesium poisoning.

Of Holocaust deniers was claimed in the 1980s and 1990s that the lack of iron blue in the gas chambers of Auschwitz-Birkenau would be a proof that there are no people were killed with Zyklon B. The chemist Richard Green stated that the reports submitted for this did not consider essential influences on the formation of iron blue. In addition, a precisely calibrated method was used to detect soluble cyanides in the gas chambers. Comparative samples from non-fumigated buildings in the Auschwitz-Birkenau concentration camp did not contain these cyanides.

Modern research directions include, among other things, analogues of Prussian blue doped with other transition metals, their magnetic and electrochemical properties, their ability to act as gas stores, or their ion exchange properties. In addition, the use of other ligands such as dicyanamide or larger polycyano species such as tetracyanoquinodimethane is being investigated .

Occurrence

Berlin blue is considered to be the first modern pigment that does not occur naturally in this form. One of the main components, potassium hexacyanidoferrate (II), on the other hand, occurs as the rare mineral cafehydrocyanite .

Extraction and presentation

Prussian blue powder on a petri dish.

It is produced by adding a solution of potassium hexacyanidoferrate (II) with an iron (III) salt dissolved in water or a solution of potassium hexacyanidoferrate (III) with an iron (II) salt dissolved in water. In both cases, with a molar ratio of 1: 1, the same colloidally dissolved “soluble Berlin blue” (“soluble Turnbulls blue”) is created.

Only when excess iron (III) or iron (II) ions are added does a blue precipitate form , known as "insoluble Berlin blue" or "insoluble Turnbulls blue"

and can be used as a color pigment. The particle diameter is between 0.01 and 0.2 μm, depending on the manufacturing process. The intense blue color is caused by the charge transfer transition between the Fe 2+ and Fe 3+ ions.

industrial production

The direct reaction is used less often in pigment production. This reaction path is mostly used for the production of preparations. Iron and hexacyanidoferrate ions are mixed in water.

First, colloidal Prussian blue precipitates , with an excess of iron ions then Prussian blue forms.

Industrial production uses the indirect route via sales to the so-called Berliner Weiß . Ammonium salts are used more frequently instead of raw materials containing potassium.

The resulting Berlin white, the so-called white dough, is then extracted with sulfuric acid at 75-100 ° C and oxidized with sodium dichromate or sodium chlorate .

The product is washed and filtered or pressed, then dried at 15 to 30 ° C. The pigment is then rubbed out to the required grain size and packaged. The finished product still contains 4-7% absorbed and hydrated water. The very finely ground production result is the “soluble” Berlin blue, which is easily dispersed in water and persistent. Different post-treatments result in a wide range of products for the intended purposes. Further treatment with anionic, nonionic or cationic surfactants can lead to a drastic change in the oil requirement, structure and gloss.

For the Berlin blue pigment, other substances, such as potassium chloride, are added during formation . These substances physically influence the precipitation and form soluble salts in the filter cake . This means that no compact agglomerates are formed. For use as a color pigment, the inorganic product should be "soft"; this technical term means fine-grained. A “soft” pigment is easier to disperse in the binder.

In the mid-1980s, the annual production of Berlin blue in the western world peaked at around 50,000 tons per year. In 2012 the world annual production was only about 10,000 tons.

Historical proceedings

In the Diesbach method, cochineal scale insects are boiled in alum and iron sulfate . The pigment is then precipitated with " Dippels Animal Oil ". In the so-called English recipe , equal parts of potassium nitrate ( saltpeter ) and potassium tartrate ( leavening agent ) are heated in a melting pot. After adding dried animal blood, the mixture is heated further. The resulting mass is washed with water and mixed with alum and iron sulfate. A final treatment with hydrochloric acid changes the initially greenish color to deep blue.

properties

Physical Properties

Under an inert gas atmosphere to Prussian blue decomposes on heating above the steps of dehydration , followed by a change in the crystal structure , followed by decomposition. At 400 ° C a monoclinic Prussian blue phase forms, at higher temperatures various iron carbides are formed. At temperatures above 700 ° C, the iron carbides decompose to cementite (Fe 3 C), metallic iron and graphite.

By crystal structure analysis , the crystal structure was of Prussian blue are determined. It was found that the water is partly coordinated and partly stored in the cage structure of the Berlin blue. At a temperature of 5.6 K, a ferromagnetic phase transition takes place in Berlin blue .

Chemical properties

Prussian blue is stable to weak acids . The cyanoferrate complex is not destroyed because of the low solubility product and cyanide ions are not released, so that no free hydrocyanic acid is formed.

The pigment is attacked by alkalis , solid brown iron (III) oxide hydroxide and dissolved hexacyanidoferrate are formed. Therefore this blue pigment is not used for fresco paintings .

Prussian blue is said to be the first coordination compound. The essential structural element of the Prussian blue is the sequence Fe (III) -NC-Fe (II) in a three-dimensional polymer framework. The assignment of the oxidation states Fe (II) to a carbon octahedron and Fe (III) to a nitrogen-water environment has been clearly demonstrated by a large number of infrared , photoelectron and Mössbauer spectroscopic investigations as well as neutron scattering studies . The structure consists of the units 3 Fe (II) C 6 , Fe (III) N 6 and 3 Fe (III) N 4 O 2 . The mean distance for Fe (II) –C was determined by X-ray structure analysis to be 192 pm, the C – N distance to be 113 pm and the Fe (III) –N distance to be 203 pm.

Electronic properties

Energy level diagram of the splitting of the d orbitals of a complex center in the octahedral field.

The intense blue color of Berlin blue is due to so-called metal-metal- charge-transfer transitions . Cyanide is a ligand that creates a strong ligand field splitting and thus for the iron (II) ions in the lattice to form a low-spin configuration with Fe 2+ (t 2g ) 6 (e g ) 0 and a total spin of S = 0 leads.

The isycanide ligand of the iron (III) ions leads to a weaker ligand field splitting. The measurement of the magnetic susceptibility showed that the Fe (III) ions are in a high-spin configuration Fe 3+ (t 2g ) 3 (e g ) 2 with a total spin of S = 5/2.

The absorption of light results in a transition from the t 2g orbital of iron (II) to the t 2g and e g orbitals of iron (III). The required absorbed energy for this lies in the red-yellow range, the blue light is reflected as a complementary color.

use

Colorants

The largest quantities of Berlin blue are used for chemical coatings, for printing inks (as ISO blue), carbon paper and in the plastics industry. A smaller amount is used in papermaking. In its full shade, this pigment gives a very dark, almost black shade; In this form it is important for transparent finishes on metal foils, also for tin printing inks. The property is particularly suitable in connection with aluminum powder for glossy surface treatments. Prussian blue is used as a real colorant for fountain pen inks. For coloring plastics, Berlin blue has proven to be very useful for coloring ND and HD polyethylene. In papermaking, water-dispersible types known as soluble iron blue are commonly used.

The pigment has excellent color fastness . In addition to its brilliance, it has excellent hiding power and high color strength . The lightfastness of pure Berlin blue is good, with low pigmented pastel shades , for example when mixed with a white pigment such as white lead or zinc oxide , it fades a lot. Spectroscopic investigations attribute this fading to a reduction of the iron (III) ions on the surface of the pigment through exposure to light.

It does not bleed in water, ethanol or methyl ethyl ketone, nor in non-polar mineral oils, di-n-octyl phthalate or linseed oil varnish . However, it has only a low resistance to alkalis and is only moderately resistant to acids. The weather resistance is largely determined by the formulation .

Textile dyeing

The dyeing of wool, cotton, silk and linen was carried out in two steps. First the textiles were stained with an iron (III) salt. For this purpose, iron (III) sulfate was often dissolved in water with dilute nitric acid and the textiles boiled in the stain for several hours. During this process, iron (III) ions were drawn onto the fiber. In the second step, the textiles were dyed in a solution of yellow blood liquor. Silk was treated with an ammoniacal solution.

art

Due to its fine grain and the resulting glazing ability as well as its great color strength, Berlin blue is still used today for watercolor , oil and printing inks. In wall painting , however, it is of no use because it quickly turns brown due to the formation of iron oxides. Painters like Gainsborough and Canaletto but also impressionists like Monet or expressionists like Munch used it in oil painting. Painters at the Prussian court, in Rotterdam and Paris were already using Berlin blue on a large scale in 1710. The painting The Entombment of Christ by Pieter van der Werff from 1709 is considered to be the oldest painting to use Berlin blue.

The color became popular in Japanese color woodblock prints in the late Edo period. The work The Great Wave off Kanagawa, created by Katsushika Hokusai, is best known .

The pigment can be sufficiently dispersed and has good heat fastness . Depending on the application, the pigment's oil requirement is between 70 and 120 kg of oil for 100 kg of pigment. Since all of these blue pigments are made from the same raw materials, the process and manufacturing conditions are decisive for the properties and the intended use. Milori blue is often used in combination with chrome yellow (CI Pigment Yellow 34) to form what is known as chrome green . A very good green pigment is obtained due to the color strength and opacity of the Berlin blue.

medicine

In medicine, Berlin blue is used in some cases of poisoning - especially in the case of compounds with cesium and thallium - as a means of binding the poison, which is then excreted together with the pigment. It was used under the trade name Radiogardase, for example after the Chernobyl nuclear disaster , to decontaminate animals that had ingested radioactive cesium-137. The most extensive use of Berliner Blau in the history of nuclear accidents occurred in the context of the Goiânia accident . It has been used to decontaminate people as well as surfaces. Prussian blue deposited on graphene foam showed a 99.5% removal efficiency for cesium-137 from contaminated water.

The effectiveness of Prussian blue in thallium poisoning has been proven by several animal studies. Although there is little experience with this in humans, Berlin blue is the drug of choice for acute thallium poisoning.

Smart glass

Among the smart glass technologies include electrochromic lenses whose light transmission properties change when voltage is applied. In this application, Berlin blue allows a color change from transparent to intense blue. By applying a voltage to electrically conductive glass, Berlin blue can be reduced to Berlin white, K 2 [Fe (II) Fe (II) (CN) 6 ] and the glass loses its color. The process can be reversed by reversing the polarity.

Analytical chemistry

The so-called Berlin blue method is used to detect total phenols. Red blood lye salt is reduced by phenols to yellow blood lye salt, which reacts with the free iron (III) ions present to form Prussian blue. The comparison of the absorbance of the samples at a wavelength of 700 nm with a standard enables the determination of the total phenols.

The detection of nitrogen in organic substances takes place through a sodium digestion , whereby sodium cyanide is formed. Using the following Lassaigne sample , named after the French chemist Jean Louis Lassaigne , the cyanide formed is detected by the formation of Prussian blue.

The reaction to Berlin blue is a very sensitive method for detecting iron. In analytical chemistry, the Prussian blue reaction is therefore a widespread method as evidence of iron (or of cyanides). Due to the high sensitivity due to the high color strength, this is suitable in microchemistry and as a spot test . This evidence is used in pathology as a reaction to iron in order to diagnose heart defect cells or siderosis . Prussian blue is used to detect hemosiderin in urine to confirm the diagnosis of glucose-6-phosphate dehydrogenase deficiency .

Other uses

North Station in Boston (1912), example of a cyanotype

In the photographic printing technique of the cyanotype , the pigment under UV light consists of green ammonium iron (III) citrate and potassium hexacyanidoferrate (III) Berlin blue. The process was used well into the 20th century as a simple process to make copies of engineering drawings called blueprints . The blueprint technique was discovered in 1842. The technique was first used in the book Photographs of British Algae: Cyanotype Impressions by Anna Atkins . This is a botanical volume published in 1844 and contains images of algae.

  • Cystoseire granulata

  • Cystoseira foeniculacea

  • Fucus vesiculosus

In metal processing and mechanical engineering , Berlin blue is applied thinly as a paste to metal surfaces ( spotting ) in order to be able to assess the quality of scraped surfaces . The pigment is used today in the "Persian blue salt" of the same name, a table salt that is advertised as "absolutely natural", but actually contains Berlin blue, which, according to the testers at Stiftung Warentest, "has no place as a coloring agent in food."

Another application is the visualization of fingerprints. Here, cathodic Berlin blue can be deposited on the trace carrier on absorbent and electrically conductive substrates.

Prussian blue was used on a trial basis as a component of cherry fodder to reduce the cesium-137 exposure of wild boars. This averaged about 522  Becquerel per kilogram of muscle meat in a control group. The addition of Berliner Blau reduced the exposure by an average of 350 to 400 Becquerel per kilogram of muscle meat.

In winemaking, blue fining is used to remove metals such as iron, copper and zinc. To this end, potassium hexacyanidoferrate (II) is added to the wine, which initially reacts with the iron ions present to form soluble Prussian blue. This reacts further to the insoluble Berlin blue, which causes a so-called blue cloud to settle after a while .

Prussian blue analogues

The general chemical formula for Prussian blue analogues can be interpreted as A l M n [M * m (CN) 6 ] x H 2 O, where A corresponds to an alkali metal or ammonium ion, M and M * represent transition metal cations. Berliner Blue and Prussian blue analogues are porous coordination polymers that have transition metal ions bridged by cyano ligands as structural elements. The metal centers M and M * often have different oxidation states . The Berlin blue analogues are suitable for various applications, including gas storage, batteries, and targeted drug release in the body.

Super Berlin blue

By replacing iron (III) with an ion such as trimethyltin ion ((CH 3 ) 3 Sn + ), an organometallic polymer is obtained. The distance between the iron (II) ions is about one nanometer and is therefore twice as large as in the case of Berlin blue. The cage size is about one cubic nanometer. The iron cyanostructure can be replaced by other systems such as rhodium (III) thiocyanate ([Rh (SCN) 6 ] 3- ).

safety instructions

The absorbability of Prussian blue under physiological conditions is extremely low, as it is practically insoluble in water and dilute acids. It can be assumed that larger amounts are not absorbed through the skin, the respiratory tract or the digestive tract. Therefore it can be classified as practically non-toxic. If it is heated above 250 ° C, the complex loses cyanide ions, which are released as poisonous, gaseous dicyan .

literature

  • Alexander Kraft: Berlin blue. From early modern pigment to modern high-tech material GNT-Verlag 2019, ISBN 978-3-86225-118-6 .
  • Hans-Peter Schramm, Bernd Hering: Historical painting materials and their identification . o. V. Stuttgart, 1995. Reprint Ravensburg, 2000. ISBN 3-473-48067-3 .
  • Andreas Ludi: Prussian blue, an inorganic evergreen . In: Journal of Chemical Education , 58 (12), 1981, 1013.
  • Kurt Wehlte: Materials and techniques of painting . Otto Maier Verlag, Ravensburg 1967, ISBN 3-473-48359-1 (earlier: ISBN 3-473-61157-3 ).

Web links

Commons : Berliner Blau  - Collection of images, videos and audio files
Wiktionary: Berliner Blau  - explanations of meanings, word origins, synonyms, translations

Individual evidence

  1. ↑ a b c d Entry on iron (III) hexacyanoferrate (II) in the GESTIS substance database of the IFA , accessed on December 19, 2019 (JavaScript required)
  2. ↑ Franz v. Bruchhausen, Gerd Dannhardt, Siegfried Ebel, August W. Frahm, Eberhard Hackenthal, Ulrike Holzgrabe: Hagers Handbook of Pharmaceutical Practice Volume 8: Substances EO . Springer-Verlag, 2013, ISBN 978-3-642-57994-3 , pp. 15 ( limited preview in Google Book search).
  3. ↑ Entry on Berliner Blau in the ChemIDplus database of the United States National Library of Medicine (NLM)
  4. ↑ a b Joseph A. Sisteno: Feriferrocyanide Pigments . In: Temple C. Button: Pigment Handbook . Volume I, ICd.
  5. ↑ a b c d e Andreas Ludi: Berlin blue. In: Chemistry in Our Time . 22, 1988, pp. 123-127, doi: 10.1002 / ciuz.19880220403 .
  6. ↑ Martin Hoefflmayr: The manufacture of blue salt or crystallized potassium-iron-cyanur on a large scale. Verlag Grau, 1837, pp. 49/50 ( books.google.de ).
  7. ↑ Berlin blue. Entry in materialarchiv.ch.
  8. ^ Robert Warington: On the Preparation of Prussian Blue, generally known as "Turnbull's Blue. In: Journal of the Franklin Institute, of the State of Pennsylvania, for the Promotion of the Mechanic Arts; Devoted to Mechanical and Physical Science, Civil Engineering, the Arts and Manufactures, and the Recording of American and Other Patent Inventions. 1848; p. 200.
  9. ^ A b c A. F. Holleman , E. Wiberg , N. Wiberg : Textbook of Inorganic Chemistry . 102nd edition. Walter de Gruyter, Berlin 2007, ISBN 978-3-11-017770-1 , pp. 1649-1651.
  10. ↑ Jander, Blasius: Textbook of analytical and preparative inorganic chemistry . (13th edition)
  11. ↑ Eberhard Ehlers: Analytics I , (8th edition). (2012: ISBN 978-3-7692-7213-0 ).
  12. ↑ Kurt Wehlte: Materials and Techniques of Painting . Otto Maier Verlag, Ravensburg 1967, ISBN 3-473-48359-1 , p. 161 ff.
  13. ↑ a b J Bartoll, B. Jackisch, M. Most, E. Wenders de Calisse, CM 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.
  14. ^ A b Jens Bartoll: The Early Use of Prussian Blue in Paintings . Paper presented at the 9th International Conference on NDT of Art, Jerusalem Israel, May 25–30, 2008.
  15. ↑ a b JL Frisch: Correspondence with Gottfried Wilhelm Leibniz LH Fischer (editor), Berlin, Stankiewicz Buchdruck, 1896, reprint Hildesheim / New York: Georg Olms Verlag, 1976.
  16. ↑ Alexander Kraft: Notitia coerulei Berolinensis nuper inventi on the 300th anniversary of the first publication on Prussian blue. In: Bulletin for the history of chemistry . 36, 2011, pp. 3-9.
  17. ^ Georg Ernst Stahl: Experimenta, Observationes, Animadversiones, CCC Numero, Chymicae et Physicae . Berlin 1731, p. 281 ff.
  18. ↑ LJM Coleby: A history of Prussian blue , In: Annals of Science , 1939, pp. 206-211, doi: 10.1080 / 00033793900201211 .
  19. ^ John Woodward: IV. Præparatio cærulei prussiaci ex germaniâ missa ad Johannem Woodward, MD Prof. Med. Gresh. RS S. In: Philosophical Transactions of the Royal Society . 33, No. 381, doi: 10.1098 / rstl.1724.0005 1724, pp. 15-17 ( royalsocietypublishing.org PDF).
  20. ↑ Alexander Kraft On two letters from Caspar Neumann to John Woodward revealing the secret method for preparation of prussian blue. In: Bulletin History Chemistry. Volume 34, 2009, Issue 2, pp. 134-140 ( illinois.edu PDF).
  21. ↑ a b c d e Holger Andreas: "Cyan Industry" - beginnings of a chemical industry in Germany in the 18th century. In: Communications from the GDCh section on the history of chemistry , Frankfurt / Main, vol. 25, 2017, ISSN 0934-8506, pp. 47–56.
  22. ^ Hans Soost: Berliner Blau from the Kunheim company . In: Berlin monthly magazine ( Luisenstädtischer Bildungsverein ) . Issue 7, 2000, ISSN  0944-5560 , p. 24-29 ( luise-berlin.de ).
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