Wikipedia:WikiProject Chemicals/Chembox validation/VerifiedDataSandbox and Scheele's Green: Difference between pages

{{Short description|Highly toxic arsenic-based pigment}}

{{Redirect-distinguish|Copper arsenite|copper arsenate}}

| Verifiedfields = changed

| verifiedrevid = 464387783

| ImageFile = Scheele's Green.png

| ImageFile1 = Scheele's green.gif

| ImageSize = 180px

| IUPACName = copper hydrogen arsenite

| OtherNames = Copper arsenite<br />Copper arsenate<br />Swedish Green<br />Cupric Green

| Section1 = {{Chembox Identifiers

| CASNo_Ref = {{cascite|changed|??}}

| CASNo=1345-20-6

| Section2 = {{Chembox Properties

| Section3 = {{Chembox Hazards

| AutoignitionPt =

| IDLH = Ca [5 mg/m³ (as As)]<ref name=PGCH>{{PGCH|0038}}</ref>

| REL = Ca C 0.002 mg/m³ [15-minute]<ref name=PGCH/>

| PEL = [1910.1018] TWA 0.010 mg/m³<ref name=PGCH/>

'''Scheele's Green''', also called '''Schloss Green''', is chemically a [[copper|cupric]] hydrogen [[arsenite]] (also called '''copper arsenite''' or '''acidic copper arsenite'''), {{chem|CuHAsO|3}}. It is chemically related to [[Paris Green]]. Scheele's Green was invented in 1775 by [[Carl Wilhelm Scheele]].<ref>{{cite journal |last1=Scheele |first1=Carl Wilhelm |date=1778 |title=Tilrednings-saettet af en ny groen Faerg |trans-title=Method of preparation of a new green color |url=https://www.biodiversitylibrary.org/item/178460#page/355/mode/1up |journal=Kungliga Vetenskaps Akademiens Handlingar |language=Swedish |volume=39 |pages=327–328}}</ref><ref>{{cite web |title=StudioMara – History of Pigments |url=http://www.lilinks.com/mara/history.html |website=www.lilinks.com}}</ref> By the end of the 19th century, it had virtually replaced the older green pigments based on [[Basic copper carbonate|copper carbonate]]. It is a yellowish-green [[pigment]] commonly used during the early to mid-19th century in [[paint]]s as well as being directly incorporated into a variety of products as a colorant.<ref>{{Cite web |last=Ruiz |first=Ada |date=2018-08-01 |title=Poisonous Pigments: Scheele's Green |url=https://laafa.edu/poisonous-pigments-scheeles-green/ |access-date=2022-09-27 |website=Los Angeles Art College {{!}} Fine Art {{!}} Concept Art {{!}} Degrees {{!}} Community Classes |language=en-US}}</ref> It began to fall out of favor after the 1860s because of its [[toxicity]] and the instability of its color in the presence of [[sulfide]]s and various chemical pollutants.<ref name=":0">{{Cite web |title=Scheele's Green - The Shunning of Green in the Victorian Era |url=https://diedfamo.us/blog/2020/1/17/scheeles-green-the-shunning-of-green-in-the-victorian-era |access-date=2022-09-27 |website=DIEDFAMOUS |language=en-US}}</ref> The acutely toxic nature of Scheele's green as well as other arsenic-containing green pigments such as [[Paris green|Paris Green]] may have contributed to the sharp decline in the popularity of the color green in [[Victorian era|late Victorian]] society.<ref name=":0" /> 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.<ref name=":3">{{Cite web |title=Explore Meural's Permanent Art Collection {{!}} Digital Artwork |url=https://my.meural.netgear.com/ |access-date=2022-09-27 |website=my.meural |language=en}}</ref><ref name=":4" /> 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).<ref name=":1">{{Cite web |title=Samson Scheeles Green Precisely Matched For Paint and Spray Paint |url=https://www.myperfectcolor.com/paint/65431-samson-scheeles-green |access-date=2022-09-27 |website=MyPerfectColor.com |language=en}}</ref><ref name=":2">{{Cite web |last=Petherick |first=Andrew |date=2021-12-11 |title=Scheele's green as a home interior colour |url=https://www.artichoke-ltd.com/journal/home-interior-colour-scheeles-green/ |access-date=2022-09-27 |website=Artichoke |language=en-US}}</ref> The latter is the more typically reported color coordinate for Scheele's green.<ref>{{Cite web |title=Scheele's Green color hex code is #478800 |url=https://www.color-name.com/scheeles-green.color |access-date=2022-09-27 |website=www.color-name.com |language=en}}</ref>

==Preparation==

{{infobox color

|title=Scheele's Green

|hex=478800

|source=[10]

}}

The pigment was originally prepared by making a solution of [[sodium carbonate]] at a temperature of around {{convert|90|C}}, then slowly adding [[Arsenic trioxide|arsenious oxide]], while constantly stirring until everything had dissolved. This produced a [[sodium arsenite]] solution. Added to a [[Copper(II) sulfate|copper sulfate]] solution, it produced a green precipitate of effectively insoluble copper arsenite. After filtration the product was dried at about {{convert|43|C}}. To enhance the color, the salt was subsequently heated to {{convert|60|-|70|C}}. 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 ({{chem|CuO·As|2|O|3}}), copper arsenite salt ({{chem|CuHAsO|3}} and {{chem|Cu(AsO|3|)|2|·3H|2|O)}}), neutral copper orthoarsenite ({{chem|3CuO·As|2|O|3|·2H|2|O}}), copper arsenate ({{chem|CuAsO|2}} and {{chem|Cu(AsO|2|)|2}}), and copper diarsenite ({{chem|2CuO·As|2|O|3|·2H|2|O}}).<ref>{{cite book|title=Pigment Compodium: A Dictionary of Historical Pigments|author1=Nicholas Eastaugh |author2=Valentine Walsh |author3=Tracey Chaplin |author4=Ruth Sidall |page=122}}</ref>

==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.<ref>{{cite book|url=http://www.gutenberg.org/dirs/etext04/dvmth10.txt|title=Advice to a Mother on the Management of her Children|author=Pye Henry Chavasse|isbn=0-659-99653-7|year=1998|publisher=Willing & Williamson|location=Toronto}}</ref> <ref name="StClair">{{Cite book|title=The Secret Lives of Colour|last=St. Clair|first=Kassia|publisher=John Murray|year=2016|isbn=978-1-4736-3081-9|location=London|pages=224–226|oclc=936144129}}</ref> <ref>{{cite web |author=University of Delaware |title=Arsenic Bookbindings {{!}} Poison Book Project |url=https://sites.udel.edu/poisonbookproject/arsenic-bookbindings/ |website=Poison Book Project}}</ref> 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 [[sulfide]]s, whether in the form of atmospheric [[hydrogen sulfide]] or in pigment mixtures based on or containing [[sulfur]]. [[Paris green|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]],<ref>{{cite book|title = The Poison Paradox: Chemicals as Friends and Foes|chapter = Butter Yellow and Scheele's Green|first = John|last = Timbrell|publisher = Oxford University Press|year = 2005|isbn = 978-0-19-280495-2|url = https://archive.org/details/poisonparadoxche0000timb|url-access = registration}}</ref> a favorite of traders in 19th-century [[Greenock]]; this led to a long-standing Scottish prejudice against green sweets.<ref>{{cite web|url=http://www.abdn.ac.uk/mediareleases/release.php?id=104|title=Media Release|publisher=University of Aberdeen Web Team|website=www.abdn.ac.uk}}</ref>

Scheele's Green was used as an [[insecticide]] in the 1930s, together with Paris Green.<ref name=":4">{{cite web|url=http://www.livinghistoryfarm.org/farminginthe30s/pests_03.html|title=Early Insecticides Used Against Insects in the 1930s|website=www.livinghistoryfarm.org|access-date=2016-01-29|archive-date=2017-04-01|archive-url=https://web.archive.org/web/20170401135745/http://www.livinghistoryfarm.org/farminginthe30s/pests_03.html|url-status=dead}}</ref><ref>{{cite journal|title=Dangers in the Manufacture of Paris Green and Scheele's Green|date=4 February 2018|journal=Monthly Review of the U.S. Bureau of Labor Statistics|volume=5|issue=2|pages=78–83|jstor=41829377}}</ref><ref>{{cite web|url=http://cameo.mfa.org/wiki/Scheele's_green|title=Scheele's green |website=Cameo – cameo.mfa.org}}</ref>

==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.<ref>{{cite web|url=http://www.havaris.ca/01/047.htm|title=Acute Poisoning|archive-url=https://archive.today/20130115104827/http://www.havaris.ca/01/047.htm|archive-date=2013-01-15}}</ref>

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.<ref>{{Cite web |last=Moonlight |first=Under The |date=2018-03-17 |title=A Dark History of Arsenic Greens |url=https://underthemoonlight.ca/2018/03/17/a-dark-history-of-arsenic-greens/ |access-date=2022-09-27 |website=Under The Moonlight |language=en}}</ref> 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.<ref name=":0" /> By the 1890s the last brand of wallpaper using it ceased production.<ref name=":3" />

=== Illness associated with arsenic containing wallpaper ===

[[File:Kersting - Die Stickerin - 3. Fassung.jpg|alt=Woman doing embroidery in the light coming in through the window of a room with bright green wallpaper. A guitar lays on the couch in the background.|thumb|''Woman Embroidering'' by [[Georg Friedrich Kersting]] (1812)|388x388px]]

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 ({{chem|AsH|3}}). Fungi genera such as ''[[Scopulariopsis]]'' or ''[[Paecilomyces]]'' release arsine gas, when they are growing on a substance containing arsenic.<ref>{{cite web|url=http://www.dehs.umn.edu/iaq_fib_fg_gloss.htm|title=Fungal Glossary|publisher=University of Minnesota, Department of Environmental Health & Safety|website=www.dehs.umn.edu}}</ref><ref>{{cite web|url=http://www.alerchek.com/MoldTypesMoldSpecies.htm|title=Mold Types and Mold Species|access-date=2008-04-12|archive-date=2008-03-06|archive-url=https://web.archive.org/web/20080306030421/http://www.alerchek.com/MoldTypesMoldSpecies.htm|url-status=dead}}</ref>

The Italian physician [[Bartolomeo Gosio]] published in 1893 his results on "Gosio gas", that was subsequently shown to contain [[trimethylarsine]].<ref>{{cite journal

| author= Frederick Challenger

| title = Biological methylation

| journal = Q. Rev. Chem. Soc.

| year = 1955

| volume = 9

| pages = 255–286

| doi = 10.1039/QR9550900255

| issue= 3}}

</ref> Under wet conditions, the mold ''[[Scopulariopsis brevicaulis]]'' produced significant amounts of methyl arsines via methylation<ref>{{cite journal

|author1=Ronald Bentley |author2=Thomas G. Chasteen

|name-list-style=amp | title = Microbial Methylation of Metalloids: Arsenic, Antimony, and Bismuth

| journal = Microbiology and Molecular Biology Reviews

| year = 2002

| volume = 66

| issue = 2

| pages = 250–271

| doi = 10.1128/MMBR.66.2.250-271.2002

| pmid= 12040126

| pmc= 120786}}

</ref> of arsenic-containing inorganic [[pigment]]s, 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.<ref>{{cite journal|author=PL Goering |author2=HV Aposhian |author3=MJ Mass |author4=M Cebrian |author5=BD Beck |author6=MP Waalkes |volume= 49|issue=1|pages=5–14|journal=[[Toxicological Sciences]]|title=The enigma of arsenic carcinogenesis: role of metabolism|doi=10.1093/toxsci/49.1.5|pmid=10367337|year=1999|doi-access=free}}</ref><ref name=autogenerated1>{{cite web|url=http://www.btinternet.com/~ian.borthwick/LADAS/prog/01_napoleon.html|title=Was Napoleon Murdered?|date=20 October 2012|archive-url=https://web.archive.org/web/20121020213144/http://www.btinternet.com/~ian.borthwick/LADAS/prog/01_napoleon.html|archive-date=20 October 2012}}</ref>

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.<ref name=Cullen>{{cite journal

|author1=William R. Cullen |author2=Ronald Bentley | title = The toxicity of trimethylarsine: an urban myth

| journal = J. Environ. Monit.

| year = 2005

| volume = 7

| pages = 11–15

| doi = 10.1039/b413752n

| pmid= 15693178

| issue= 1}}</ref><ref>{{cite journal

|author1=Frederick Challenger |author2=Constance Higginbottom |author3=Louis Ellis | title = The formation of organo-metalloidal compounds by microorganisms. Part I. Trimethylarsine and dimethylethylarsine

| journal = J. Chem. Soc.

| year = 1933

| pages = 95–101

| doi = 10.1039/JR9330000095}}</ref>

Arsenic is not only toxic, but it also has carcinogenic effects.<ref name=autogenerated1 />

===Role in Napoleon's death===

During his exile on [[Napoleon#Exile on Saint Helena|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.<ref name="StClair" /> 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.<ref>{{cite journal|last1=Jones|first1=David|title=The Singular Case of Napoleon's Wallpaper|journal=New Scientist|date=14 October 1982|page=101|url=https://books.google.com/books?id=7bklpWKpfp0C&pg=PA101|publisher=Reed Business Information|language=en}}{{Dead link|date=March 2024 |bot=InternetArchiveBot |fix-attempted=yes }}</ref> However, more recent research has proven this theory to be false, and Napoleon did indeed die of stomach cancer.<ref>{{Cite web |date=2023-09-12 |title=Debunking myths in history: The true death cause of Napoleon |url=https://hypedforhistory.com/2023/09/12/debunking-myths-in-history-the-true-death-cause-of-napoleon/ |access-date=2023-09-16 |website=Hyped For History |language=en}}</ref><ref>{{Cite journal |last1=HINDMARSH |first1=J. T. |last2=CORSO |first2=P. F. |date=1998-07-01 |title=The Death of Napoleon Bonaparte: A Critical Review of the Cause |journal=Journal of the History of Medicine and Allied Sciences |volume=53 |issue=3 |pages=201–218 |doi=10.1093/jhmas/53.3.201 |pmid=9715589 |issn=0022-5045}}</ref>

==See also==

*Not to be confused with [[copper arsenate]]

*[[List of inorganic pigments]]

*''[[Shadows from the Walls of Death]]''

==References==

{{reflist|30em}}

==External links==

*[https://www.atsdr.cdc.gov/csem/csem.html Case Studies in Environmental Medicine – Arsenic Toxicity]

*[https://web.archive.org/web/20080302034606/http://www.npi.gov.au/database/substance-info/profiles/27.html National Pollutant Inventory – Copper and compounds fact sheet]

[[Category:Arsenites]]

[[Category:Copper(II) compounds]]

[[Category:Inorganic pigments]]

[[Category:Inorganic insecticides]]

[[Category:Carl Wilhelm Scheele]]