Scheele's Green

Last updated
Scheele's Green
Scheele's Green.png
Scheele's green.gif
Names
IUPAC name
copper hydrogen arsenite
Other names
Copper arsenite
Copper arsenate
Swedish Green
Cupric Green
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.030.573 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
  • InChI=1S/AsHO3.Cu/c2-1(3)4;/h2H;/q-2;+2 Yes check.svgY
    Key: BPQWCZKMOKHAJF-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/AsHO3.Cu/c2-1(3)4;/h2H;/q-2;+2
    Key: BPQWCZKMOKHAJF-UHFFFAOYAR
  • [Cu+2].[O-][As]([O-])O
Properties
AsCuHO3
Molar mass 187.474
Hazards
NIOSH (US health exposure limits):
PEL (Permissible)
[1910.1018] TWA 0.010 mg/m3 [1]
REL (Recommended)
Ca C 0.002 mg/m3 [15-minute] [1]
IDLH (Immediate danger)
Ca [5 mg/m3 (as As)] [1]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Scheele's Green, also called Schloss Green, is chemically a cupric hydrogen arsenite (also called copper arsenite or acidic copper arsenite), CuHAsO
3. It is chemically related to Paris Green. Scheele's Green was invented in 1775 by Carl Wilhelm Scheele. [2] [3] By the end of the 19th century, it had virtually replaced the older green pigments based on copper carbonate. It is a yellowish-green pigment commonly used during the early to mid-19th century in paints as well as being directly incorporated into a variety of products as a colorant. [4] It began to fall out of favor after the 1860s because of its toxicity and the instability of its color in the presence of sulfides and various chemical pollutants. [5] The acutely toxic nature of Scheele's green as well as other arsenic-containing green pigments such as Paris Green may have contributed to the sharp decline in the popularity of the color green in late Victorian society. [5] By the dawn of the 20th century, Scheele's green had completely fallen out of use as a pigment but was still in use as an insecticide into the 1930s. [6] [7] At least two modern reproductions of Scheele's green hue with modern non-toxic pigments have been made, with similar but non-identical color coordinates: one with hex#3c7a18 (RGB 60, 122, 24) and another with hex#478800 (RGB 71, 136, 0). [8] [9] The latter is the more typically reported color coordinate for Scheele's green. [10]

Contents

Preparation

Scheele's Green
 
Gtk-dialog-info.svg    Color coordinates
Hex triplet #478800
sRGB B (r, g, b)(71, 136, 0)
HSV (h, s, v)(89°, 100%, 53%)
CIELChuv (L, C, h)(51, 68, 118°)
Source[10]
B: Normalized to [0–255] (byte)

The pigment was originally prepared by making a solution of sodium carbonate at a temperature of around 90 °C (194 °F), then slowly adding arsenious oxide, while constantly stirring until everything had dissolved. This produced a sodium arsenite solution. Added to a copper sulfate solution, it produced a green precipitate of effectively insoluble copper arsenite. After filtration the product was dried at about 43 °C (109 °F). To enhance the color, the salt was subsequently heated to 60–70 °C (140–158 °F). The intensity of the color depends on the copper : arsenic ratio, which in turn was affected by the ratio of the starting materials, as well as the temperature.

It has been found that Scheele's green was composed of a variety of different compounds, including copper metaarsenite (CuO·As
2O
3), copper arsenite salt (CuHAsO
3 and Cu(AsO
3)
2·3H
2O)), neutral copper orthoarsenite (3CuO·As
2O
3·2H
2O), copper arsenate (CuAsO
2 and Cu(AsO
2)
2), and copper diarsenite (2CuO·As
2O
3·2H
2O). [11]

Uses

Scheele's Green was used to color wallpapers, paper furniture linings, and textiles used in clothing and bookbindings, along with paints, wax candles, and even some children's toys. [12] [13] [14] Scheele's Green is more brilliant and durable than the then-used copper carbonate pigments. However, because of its copper content it tends to fade and blacken when exposed to sulfides, whether in the form of atmospheric hydrogen sulfide or in pigment mixtures based on or containing sulfur. Emerald green, also known as Paris Green, was developed later in an attempt to improve Scheele's Green. It had the same tendency to blacken, but was more durable.

By the end of the 19th century, both greens were made obsolete by cobalt green, also known as zinc green, which is far less toxic.

Despite evidence of its high toxicity, Scheele's Green was also used as a food dye for sweets such as green blancmange, [15] a favorite of traders in 19th-century Greenock; this led to a long-standing Scottish prejudice against green sweets. [16]

Scheele's Green was used as an insecticide in the 1930s, together with Paris Green. [7] [17] [18]

Toxicity

In the 19th century, the toxicity of arsenic compounds was not readily known. Nineteenth-century journals contained reports of children wasting away in bright green rooms, of ladies in green dresses swooning, and of newspaper printers being overcome by arsenic vapors. There is one example of acute poisoning of children attending a Christmas party where dyed candles were burned. [19]

Although some European nations started banning arsenic-containing pigments in the 1830s and 1840s, Scheele's green did not completely fall out of favor until the 1860s. [20] Publicity associated the 1861 death of 19-year-old Matilda Scheueur as a result of her job dusting artificial foliage with the pigment increased public awareness of the toxicity of Scheele's green. An article "Pretty Poison-Wreaths" described her repeated illness from arsenic poisoning leading to her death, and detailed autopsy findings of eyes and fingernails turned green from the pigment. [5] By the 1890s the last brand of wallpaper using it ceased production. [6]

Illness associated with arsenic containing wallpaper

Woman Embroidering by Georg Friedrich Kersting (1812) Kersting - Die Stickerin - 3. Fassung.jpg
Woman Embroidering by Georg Friedrich Kersting (1812)

Two main theories on the cause of wallpaper poisoning events have been proposed: dust particles caused by pigment and paper flaking, and toxic gas production. Tiny particles of the pigment can flake off and become airborne, and then are absorbed by the lungs. Alternatively, toxic gas can be released from compounds containing arsenic following certain chemical processes, such as heating, or metabolism by an organism. When the wallpaper becomes damp and moldy, the pigment may be metabolised, causing the release of poisonous arsine gas (AsH
3). Fungi genera such as Scopulariopsis or Paecilomyces release arsine gas, when they are growing on a substance containing arsenic. [21] [22] The Italian physician Bartolomeo Gosio published in 1893 his results on "Gosio gas", that was subsequently shown to contain trimethylarsine. [23] Under wet conditions, the mold Scopulariopsis brevicaulis produced significant amounts of methyl arsines via methylation [24] of arsenic-containing inorganic pigments, especially Paris green and Scheele's Green.

In these compounds, the arsenic is either pentavalent or trivalent (arsenic is in group 15), depending on the compound. In humans, arsenic of these valences is readily absorbed by the gastrointestinal tract, which accounts for its high toxicity. Pentavalent arsenic tends to be reduced to trivalent arsenic and trivalent arsenic tends to proceed via oxidative methylation in which the trivalent arsenic is made into mono, di and trimethylated products by methyltransferases and an S-adenosyl-methionine methyl donating cofactor. [25] [26] However, newer studies indicate that trimethylarsine has a low toxicity, and could therefore not account for the death and the severe health problems observed in the 19th century. [27] [28]

Arsenic is not only toxic, but it also has carcinogenic effects. [26]

Role in Napoleon's death

During his exile on St. Helena, Napoleon resided in a house in which the rooms were painted bright green, his favorite color. The cause of his death is generally believed to have been stomach cancer, and arsenic exposure has been linked to an increased risk of gastric carcinoma. Analysis of samples of his hair revealed significant amounts of arsenic. [13] As St. Helena has a rather damp climate, it is likely that fungus grew on the walls. It has also been suggested that the presence of such abnormally high levels of arsenic might be due to attempts at preserving his body. [29] However, more recent research has proven this theory to be false, and Napoleon did indeed die of stomach cancer. [30] [31]

See also

Related Research Articles

<span class="mw-page-title-main">Arsenic</span> Chemical element, symbol As and atomic number 33

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<span class="mw-page-title-main">Arsenic poisoning</span> Illness from ingesting arsenic

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<span class="mw-page-title-main">Arsine</span> Chemical compound

Arsine (IUPAC name: arsane) is an inorganic compound with the formula AsH3. This flammable, pyrophoric, and highly toxic pnictogen hydride gas is one of the simplest compounds of arsenic. Despite its lethality, it finds some applications in the semiconductor industry and for the synthesis of organoarsenic compounds. The term arsine is commonly used to describe a class of organoarsenic compounds of the formula AsH3−xRx, where R = aryl or alkyl. For example, As(C6H5)3, called triphenylarsine, is referred to as "an arsine".

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Paris green is an arsenic-based organic pigment. As a green pigment it is also known as Mitis green, Schweinfurt green, Sattler green, emerald, or Vienna green, Emperor green or Mountain green. It is a highly toxic emerald-green crystalline powder that has been used as a rodenticide and insecticide, and also as a pigment. It was manufactured in 1814 to be a pigment to make a vibrant green paint, and was used by many notable painters in the 19th century. The color of Paris green is said to range from a pale blue green when very finely ground, to a deeper green when coarsely ground. Due to the presence of arsenic, the pigment is extremely toxic and in paintings, the color can degrade quickly.

<span class="mw-page-title-main">Cacodyl oxide</span> Chemical compound

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<span class="mw-page-title-main">Copper(II) arsenate</span> Chemical compound

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Trimethylarsine (abbreviated TMA or TMAs) is the chemical compound with the formula (CH3)3As, commonly abbreviated AsMe3 or TMAs. This organic derivative of arsine has been used as a source of arsenic in microelectronics industry, a building block to other organoarsenic compounds, and serves as a ligand in coordination chemistry. It has distinct "garlic"-like smell. Trimethylarsine had been discovered as early as 1854.

Potassium arsenite (KAsO2) is an inorganic compound that exists in two forms, potassium meta-arsenite (KAsO2) and potassium ortho-arsenite (K3AsO3). It is composed of arsenite ions (AsO33− or AsO2−) with arsenic always existing in the +3 oxidation state. Like many other arsenic containing compounds, potassium arsenite is highly toxic and carcinogenic to humans. Potassium arsenite forms the basis of Fowler’s solution, which was historically used as a medicinal tonic, but due to its toxic nature its use was discontinued. Potassium arsenite is still, however, used as a rodenticide.

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<span class="mw-page-title-main">Green pigments</span> Substances reflecting light between 475-590 nm

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References

  1. 1 2 3 NIOSH Pocket Guide to Chemical Hazards. "#0038". National Institute for Occupational Safety and Health (NIOSH).
  2. ↑ Scheele, Carl Wilhelm (1778). "Tilrednings-saettet af en ny groen Faerg" [Method of preparation of a new green color]. Kungliga Vetenskaps Akademiens Handlingar (in Swedish). 39: 327–328.
  3. ↑ "StudioMara – History of Pigments". www.lilinks.com.
  4. ↑ Ruiz, Ada (2018-08-01). "Poisonous Pigments: Scheele's Green". Los Angeles Art College | Fine Art | Concept Art | Degrees | Community Classes. Retrieved 2022-09-27.
  5. 1 2 3 "Scheele's Green - The Shunning of Green in the Victorian Era". DIEDFAMOUS. Retrieved 2022-09-27.
  6. 1 2 "Explore Meural's Permanent Art Collection | Digital Artwork". my.meural. Retrieved 2022-09-27.
  7. 1 2 "Early Insecticides Used Against Insects in the 1930s". www.livinghistoryfarm.org. Archived from the original on 2017-04-01. Retrieved 2016-01-29.
  8. ↑ "Samson Scheeles Green Precisely Matched For Paint and Spray Paint". MyPerfectColor.com. Retrieved 2022-09-27.
  9. ↑ Petherick, Andrew (2021-12-11). "Scheele's green as a home interior colour". Artichoke. Retrieved 2022-09-27.
  10. ↑ "Scheele's Green color hex code is #478800". www.color-name.com. Retrieved 2022-09-27.
  11. ↑ Nicholas Eastaugh; Valentine Walsh; Tracey Chaplin; Ruth Sidall. Pigment Compodium: A Dictionary of Historical Pigments. p. 122.
  12. ↑ Pye Henry Chavasse (1998). Advice to a Mother on the Management of her Children. Toronto: Willing & Williamson. ISBN   0-659-99653-7.
  13. 1 2 St. Clair, Kassia (2016). The Secret Lives of Colour. London: John Murray. pp. 224–226. ISBN   978-1-4736-3081-9. OCLC   936144129.
  14. ↑ University of Delaware. "Arsenic Bookbindings | Poison Book Project". Poison Book Project.
  15. ↑ Timbrell, John (2005). "Butter Yellow and Scheele's Green". The Poison Paradox: Chemicals as Friends and Foes . Oxford University Press. ISBN   978-0-19-280495-2.
  16. ↑ "Media Release". www.abdn.ac.uk. University of Aberdeen Web Team.
  17. ↑ "Dangers in the Manufacture of Paris Green and Scheele's Green". Monthly Review of the U.S. Bureau of Labor Statistics. 5 (2): 78–83. 4 February 2018. JSTOR   41829377.
  18. ↑ "Scheele's green". Cameo – cameo.mfa.org.
  19. ↑ "Acute Poisoning". Archived from the original on 2013-01-15.
  20. ↑ Moonlight, Under The (2018-03-17). "A Dark History of Arsenic Greens". Under The Moonlight. Retrieved 2022-09-27.
  21. ↑ "Fungal Glossary". www.dehs.umn.edu. University of Minnesota, Department of Environmental Health & Safety.
  22. ↑ "Mold Types and Mold Species". Archived from the original on 2008-03-06. Retrieved 2008-04-12.
  23. ↑ Frederick Challenger (1955). "Biological methylation". Q. Rev. Chem. Soc. 9 (3): 255–286. doi:10.1039/QR9550900255.
  24. ↑ Ronald Bentley & Thomas G. Chasteen (2002). "Microbial Methylation of Metalloids: Arsenic, Antimony, and Bismuth". Microbiology and Molecular Biology Reviews. 66 (2): 250–271. doi:10.1128/MMBR.66.2.250-271.2002. PMC   120786 . PMID   12040126.
  25. ↑ PL Goering; HV Aposhian; MJ Mass; M Cebrian; BD Beck; MP Waalkes (1999). "The enigma of arsenic carcinogenesis: role of metabolism". Toxicological Sciences . 49 (1): 5–14. doi: 10.1093/toxsci/49.1.5 . PMID   10367337.
  26. 1 2 "Was Napoleon Murdered?". 20 October 2012. Archived from the original on 20 October 2012.
  27. ↑ William R. Cullen; Ronald Bentley (2005). "The toxicity of trimethylarsine: an urban myth". J. Environ. Monit. 7 (1): 11–15. doi:10.1039/b413752n. PMID   15693178.
  28. ↑ Frederick Challenger; Constance Higginbottom; Louis Ellis (1933). "The formation of organo-metalloidal compounds by microorganisms. Part I. Trimethylarsine and dimethylethylarsine". J. Chem. Soc.: 95–101. doi:10.1039/JR9330000095.
  29. ↑ Jones, David (14 October 1982). "The Singular Case of Napoleon's Wallpaper". New Scientist. Reed Business Information: 101.[ permanent dead link ]
  30. ↑ "Debunking myths in history: The true death cause of Napoleon". Hyped For History. 2023-09-12. Retrieved 2023-09-16.
  31. ↑ HINDMARSH, J. T.; CORSO, P. F. (1998-07-01). "The Death of Napoleon Bonaparte: A Critical Review of the Cause". Journal of the History of Medicine and Allied Sciences. 53 (3): 201–218. doi:10.1093/jhmas/53.3.201. ISSN   0022-5045. PMID   9715589.
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