Paris green

Last updated

Paris green
Schweinfurter Grun.svg
Names
Other names
C.I. pigment green 21, emerald green, Schweinfurt green, imperial green, Vienna green, Mitis green, Veronese green [1]
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.125.242 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 601-658-7
PubChem CID
UNII
UN number 1585
  • InChI=1S/2C2H4O2.6AsHO2.4Cu/c2*1-2(3)4;6*2-1-3;;;;/h2*1H3,(H,3,4);6*(H,2,3);;;;/q;;;;;;;;4*+2/p-8
    Key: HTSABAUNNZLCMN-UHFFFAOYSA-F
  • CC(=O)[O-].CC(=O)[O-].[O-][As]=O.[O-][As]=O.[O-][As]=O.[O-][As]=O.[O-][As]=O.[O-][As]=O.[Cu+2].[Cu+2].[Cu+2].[Cu+2]
  • CC(=O)[O-].CC(=O)[O-].[O-][As]0O[As]([O-])O[As]([O-])O0.[O-][As]0O[As]([O-])O[As]([O-])O0.[Cu+2].[Cu+2].[Cu+2].[Cu+2]
Properties
Cu(C2H3O2)2·3Cu(AsO2)2
Molar mass 1013.79444 g/mol
AppearanceEmerald green crystalline powder
Density >1.1 g/cm3 (20 °C)
Melting point >345 °C (653 °F; 618 K)
Boiling point decomposes
insoluble
Solubility soluble but unstable in acids
insoluble in alcohol
Hazards
GHS labelling:
GHS-pictogram-skull.svg GHS-pictogram-pollu.svg
Danger
H302, H410
P260, P264, P273, P280, P301+P312, P301+P330+P331, P303+P361+P353, P304+P340, P305+P351+P338, P310, P362, P391, P405, P501
Lethal dose or concentration (LD, LC):
22 mg/kg
NIOSH (US health exposure limits):
PEL (Permissible)
[1910.1018] TWA 0.010 mg/m3 [2]
REL (Recommended)
Ca C 0.002 mg/m3 [15-minute] [2]
IDLH (Immediate danger)
Ca [5 mg/m3 (as As)] [2]
Safety data sheet (SDS) CAMEO MSDS
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 ?)
Paris green
 
Gtk-dialog-info.svg    Color coordinates
Hex triplet #50C878
sRGB B (r, g, b)(80, 200, 120)
HSV (h, s, v)(140°, 60%, 78%)
CIELChuv (L, C, h)(72, 71, 137°)
SourceMaerz and Paul [3]
ISCC–NBS descriptor Vivid yellowish green
B: Normalized to [0–255] (byte)

Paris green (copper(II) acetate triarsenite or copper(II) acetoarsenite) is an arsenic-based organic pigment. As a green pigment it is also known as Mitis green, Schweinfurt green, Sattler green, emerald , Vienna green, Emperor green or Mountain green. It is a highly toxic emerald-green crystalline powder [4] that has been used as a rodenticide and insecticide, [5] and also as a pigment.

Contents

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. In paintings, the color can degrade quickly.

Preparation and structure

Paris green may be prepared by combining copper(II) acetate and arsenic trioxide. [6] The structure was confirmed by X-ray crystallography. [7]

A subunit of the Cu2As3O6(OAc) framework, highlighting the [As3O6] ligand. Color code: Cu = blue, As = large gray, C = gray, O = red. Subunit of Cu2As3O3(OAc) (ASOCUA).png
A subunit of the Cu2As3O6(OAc) framework, highlighting the [As3O6] ligand. Color code: Cu = blue, As = large gray, C = gray, O = red.

History

In 1814, Paris green was invented by paint manufacturers Wilhelm Sattler and Friedrich Russ, in Schweinfurt, Germany for the Wilhelm Dye and White Lead Company. They were attempting to produce a more stable pigment than Scheele's green, seeking to make a green that was less susceptible to darkening around sulfides. [lower-roman 1] In 1822, the recipe for emerald green was published by Justus von Liebig and André Braconnot. [8]

In 1867, the pigment was named Paris green and was officially recognized as the first chemical insecticide in the world. Because of its arsenic content, the pigment was dangerous and toxic to manufacture, often resulting in factory poisonings. [9] [10] At the time, emerald green was praised as a more durable and vibrant substitute for Scheele's green, even though it would later prove to degrade quickly and react with other manufactured paints.[ citation needed ]

Pigment

In paintings, the pigment produces a rich, dark green with an undertone of blue. In comparison, Scheele's green is more yellow, and therefore, more lime-green. [11] :220 Paris green became popular in the 19th century because of its brilliant color. [11] :223 It was also called emerald green because of its resemblance to the gemstone's deep color.

Permanence

Can of Paris green pigment by Sherwin-Williams Co. Paris Green (Schweinfurter Grun).JPG
Can of Paris green pigment by Sherwin-Williams Co.

The pigment has a tendency to darken and turn brown. The issue was already apparent in the 19th century. In a 1888 study, watercolors with the pigment were shown to darken and turn brown when exposed to natural light and air. Experiments at the turn of the 20th century gave mixed results. Some found that the Paris green degraded slightly while other sources said the pigment was weatherproof. [11] :227 This discrepancy could be due to the fact that each experiment used a different brand of Paris green. [11] :228

Paris green in Descente des Vaches by Théodore Rousseau has changed significantly. [12]

Similar natural compounds are the minerals chalcophyllite Cu
18
Al
2
(AsO
4
)
3
(SO
4
)
3
(OH)
27
·36H
2
O
, conichalcite CaCu(AsO
4
)(OH)
, cornubite Cu
5
(AsO
4
)
2
(OH)
4
·H
2
O
, cornwallite Cu
5
(AsO
4
)
2
(OH)
4
·H
2
O
, and liroconite Cu
2
Al(AsO
4
)(OH)
4
·4H
2
O
. These minerals range in color from greenish blue to slightly yellowish green.[ citation needed ]

Scheele's green is a chemically simpler, less brilliant, and less permanent, copper-arsenic pigment used for a rather short time before Paris green was first prepared, which was approximately 1814. It was popular as a wallpaper pigment and would degrade, with moisture and molds, to arsine gas. Paris green was used in wallpaper to some extent and may have degraded similarly. [13] Both pigments were once used in printing ink formulations.[ citation needed ]

The ancient Romans used one of them, possibly conichalcite, as a green pigment. The Paris green paint used by the Impressionists is said to have been composed of relatively coarse particles. Later, the chemical was produced with increasingly small grinds and without carefully removing impurities. Its permanence suffered. It is likely that it was ground more finely for use in watercolors and inks.[ citation needed ]

Uses

Painting

Paris green was widely used by 19th-century artists. It is present in several paintings by Claude Monet and Paul Gauguin, who found its color difficult to replicate with natural materials. [11] :256 [14]

Vincent van Gogh, Self-Portrait (Dedicated to Paul Gauguin), September, 1888. Note the vivid background and undercoat of Paris green. Van Gogh self-portrait dedicated to Gauguin.jpg
Vincent van Gogh, Self-Portrait (Dedicated to Paul Gauguin), September, 1888. Note the vivid background and undercoat of Paris green.
Georges Seurat, A Sunday on la Grande Jatte: an example of a neo-Impressionist work using emerald green Georges Seurat - Un dimanche apres-midi a l'Ile de la Grande Jatte v2.jpeg
Georges Seurat, A Sunday on la Grande Jatte : an example of a neo-Impressionist work using emerald green

Insecticide

In 1867, farmers in Illinois and Indiana found that Paris green was effective against the Colorado potato beetle, an aggressive agricultural pest. Despite concerns regarding the safety of using arsenic compounds on food crops, Paris green became the preferred method for controlling the beetle. By the 1880s, Paris green had become the first widespread use of a chemical insecticide in the world. [16] It was also used widely in the Americas to control the tobacco budworm, Heliothis virescens. [17] To kill codling moth, it was mixed with lime and sprayed on fruit trees. [18]

Paris green was heavily sprayed by airplane in Italy, Sardinia, and Corsica during 1944 and in Italy in 1945 to control malaria. [19] It was once used to kill rats in Parisian sewers, which is how it acquired its common name. [20]

However, the manufacturing of the insecticide caused many health complications for factory workers, and in certain cases was lethal. [21]

Bookbindings

Throughout the 19th century, Paris green and similar arsenic pigments were used in books, particularly on bookcloth coverings, textblock edges, decorative labels and onlays, and in printed or manual illustrations. The colorant is particularly prevalent in bookbindings from the 1850s and 1860s published in Germany, England, France, and the United States. Use of arsenic-containing pigments waned in the later part of the 19th-century with heightened awareness of their toxicity and the availability of less toxic chromium- and cobalt-based alternatives. Since February 2024, several German libraries have started to block public access to their stock of 19th century books, to check for the degree of poisoning. [22] [23] [24] [25] [26] [27] The Poison Book Project has cataloged books with these bindings.

Wallpaper

Paris green became a popular paint in mass-produced wallpaper, which is believed to have shortened lifespans. [28] Wallpaper swatches from this era have been preserved in the book Shadows from the Walls of Death .

See also

Related Research Articles

<span class="mw-page-title-main">Arsenic</span> Chemical element with atomic number 33 (As)

Arsenic is a chemical element with the symbol As and the atomic number 33. It is a metalloid and one of the pnictogens, and therefore shares many properties with its group 15 neighbors phosphorus and antimony. Arsenic is a notoriously toxic heavy metal. It occurs naturally in many minerals, usually in combination with sulfur and metals, but also as a pure elemental crystal. It has various allotropes, but only the grey form, which has a metallic appearance, is important to industry.

<span class="mw-page-title-main">Pigment</span> Colored material

A pigment is a powder used to add color or change visual appearance. Pigments are completely or nearly insoluble and chemically unreactive in water or another medium; in contrast, dyes are colored substances which are soluble or go into solution at some stage in their use. Dyes are often organic compounds whereas pigments are often inorganic. Pigments of prehistoric and historic value include ochre, charcoal, and lapis lazuli.

<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".

<span class="mw-page-title-main">Copper phthalocyanine</span> Synthetic blue pigment from the group of phthalocyanine dyes

Copper phthalocyanine (CuPc), also called phthalocyanine blue, phthalo blue and many other names, is a bright, crystalline, synthetic blue pigment from the group of dyes based on phthalocyanines. Its brilliant blue is frequently used in paints and dyes. It is highly valued for its superior properties such as light fastness, tinting strength, covering power and resistance to the effects of alkalis and acids. It has the appearance of a blue powder, insoluble in most solvents including water.

<span class="mw-page-title-main">Dioptase</span> Cyclosilicate mineral

Dioptase is an intense emerald-green to bluish-green mineral that is cyclosilicate of copper. It is transparent to translucent. Its luster is vitreous to sub-adamantine. Its formula is Cu6Si6O18·6H2O, also reported as CuSiO2(OH)2. It has a Mohs hardness of 5, the same as tooth enamel. Its specific gravity is 3.28–3.35, and it has two perfect and one very good cleavage directions. Additionally, dioptase is very fragile, and specimens must be handled with great care. It is a trigonal mineral, forming six-sided crystals that are terminated by rhombohedra.

<span class="mw-page-title-main">Realgar</span> Arsenic sulfide mineral

Realgar, also known as ″arsenic blende″, ″ruby sulphur″ or ″ruby of arsenic″, is an arsenic sulfide mineral with the chemical formula α-As4S4. It is a soft, sectile mineral occurring in monoclinic crystals, or in granular, compact, or powdery form, often in association with the related mineral, orpiment. It is orange-red in color, melts at 320 °C, and burns with a bluish flame releasing fumes of arsenic and sulfur. Realgar is soft with a Mohs hardness of 1.5 to 2 and has a specific gravity of 3.5. Its streak is orange colored. It is trimorphous with pararealgar and bonazziite.

<span class="mw-page-title-main">Orpiment</span> Orange-yellow arsenic sulfide mineral

Orpiment, also known as ″yellow arsenic blende″ is a deep-colored, orange-yellow arsenic sulfide mineral with formula As
2
S
3
. It is found in volcanic fumaroles, low-temperature hydrothermal veins, and hot springs and may be formed through sublimation.

<span class="mw-page-title-main">Verdigris</span> Green copper-based pigment

Verdigris is a common name for any of a variety of somewhat poisonous copper salts of acetic acid, which range in colour from green to a bluish-green depending on their chemical composition. Once used as a medicine and pharmaceutical preparation, verdigris occurs naturally, creating a patina on copper, bronze, and brass, and is the main component of a historic green pigment used for artistic purposes from antiquity until the late 20th century, including in easel painting, polychromatic sculptures, and illumination of maps. However, due to its instability, its popularity declined as other green pigments became readily available. The instability of its appearance stems from its hydration level and basicity, which change as the pigment interacts with other materials over time.

<span class="mw-page-title-main">Arsenic trioxide</span> Chemical compound (industrial chemical and medication)

Arsenic trioxide is an inorganic compound with the formula As
2
O
3
. As an industrial chemical, its major uses include the manufacture of wood preservatives, pesticides, and glass. It is sold under the brand name Trisenox among others when used as a medication to treat a type of cancer known as acute promyelocytic leukemia. For this use it is given by injection into a vein.

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

Copper arsenate (Cu3(AsO4)2·4H2O, or Cu5H2(AsO4)4·2H2O), also called copper orthoarsenate, tricopper arsenate, cupric arsenate, or tricopper orthoarsenate, is a blue or bluish-green powder insoluble in water and alcohol and soluble in aqueous ammonium and dilute acids. Its CAS number is 7778-41-8 or 10103-61-4.

<span class="mw-page-title-main">Scheele's green</span> Highly toxic arsenic-based pigment

Scheele's green, also called Schloss green, is chemically a cupric hydrogen arsenite, CuHAsO
3
. It is chemically related to Paris green. Scheele's green was invented in 1775 by Carl Wilhelm Scheele. 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. 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. 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. 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. 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 and another with hex#478800. The latter is the more typically reported color coordinate for Scheele's green.

Chromated copper arsenate (CCA) is a wood preservative containing compounds of chromium, copper, and arsenic, in various proportions. It is used to impregnate timber and other wood products, especially those intended for outdoor use, in order to protect them from attack by microbes and insects. Like other copper-based wood preservatives, it imparts a greenish tint to treated timber.

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<span class="mw-page-title-main">Chalcophyllite</span>

Chalcophyllite is a rare secondary copper arsenate mineral occurring in the oxidized zones of some arsenic-bearing copper deposits. It was first described from material collected in Germany. At one time chalcophyllite from Wheal Tamar in Cornwall, England, was called tamarite, but this name is now discredited. At Wheal Gorland a specimen exhibiting partial replacement of liriconite, Cu
2
Al(AsO
4
)(OH)
4
·(4H
2
O)
, by chalcophyllite has been found. The mineral is named from the Greek, chalco "copper" and fyllon, "leaf", in allusion to its composition and platy structure. It is a classic Cornish mineral that can be confused with tabular spangolite.

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4
ions in the mineral skutterudite. In the +3 oxidation state, arsenic is typically pyramidal owing to the influence of the lone pair of electrons.

<span class="mw-page-title-main">Poison Book Project</span> University of Delaware cataloging project

The Poison Book Project is a project of the Winterthur Museum, Garden and Library and the University of Delaware to identify and catalog books known to contain poisonous substances, particularly arsenic in Paris green pigments. It was started in 2019 when Winterthur staff members Melissa Tedone and Rosie Grayburn identified a book containing Paris green in the institution's collection. The project has since confirmed at least 100 other books from libraries across the world that contain Paris green, allowing librarians to take measures to minimize the risk to those handling the books.

References

  1. Sulfur was commonly produced from burning coal fires.
  1. "Health & Safety in the Arts -- Painting & Drawing Pigments". Environmental Management Division, City of Tucson AZ. Archived from the original on 20 July 2011. Retrieved 7 February 2011.
  2. 1 2 3 NIOSH Pocket Guide to Chemical Hazards. "#0038". National Institute for Occupational Safety and Health (NIOSH).
  3. The color displayed in the color box above matches the color called emerald green in the 1930 book by Maerz and Paul A Dictionary of Color New York:1930 McGraw-Hill; the color emerald green is displayed on page 75, Plate 26, Color Sample J10.
  4. "Hazardous Substance Fact Sheet" (PDF). NJ Dept. of Health and Senior Services. Retrieved 7 February 2011.
  5. "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. 1917. JSTOR   41829377.
  6. "H.Wayne Richardson, "Copper Compounds" in Ullmann's Encyclopedia of Industrial Chemistry 2005, Wiley-VCH, Weinheim. doi : 10.1002/14356007.a07_567
  7. Pertlik, F. (1977). "Die Kristallstruktur von Cu2As3O6CH3COO". Zeitschrift für Kristallographie. 145 (1–2): 35–45. Bibcode:1977ZK....145...35P. doi:10.1524/zkri.1977.145.1-2.35.
  8. Zieske, Faith (1995). "An Investigation of Paul Cézanne's Watercolors With Emphasis on Emerald". The Book and Paper Group: Annual.
  9. Haynes, William (1954). American Chemical Industry: Background and Beginnings (Vol. 1 ed.). D. Van Nostrand Company, Inc. pp. 355–369.
  10. Emsley, John (2005). The Elements of Murder: A History of Poison . OUP. p.  118. ISBN   9780192805997.
  11. 1 2 3 4 5 Fiedler, Inge; Bayard, Michael A. (2012). "Emerald Green and Scheele's Green". Artists' Pigments: A Handbook of Their History and Characteristics. Vol. 3. Washington D.C.: National Gallery of Art. pp. 219–71.
  12. Keune, Katrien; Boon, Jaap J.; Boitelle, R.; Shimazdu, Y. (July 2013). "Degradation of Emerald Green in Oil Paint and Its Contribution to the Rapid Change in Colour of the Descente Des Vaches (1834-1835)". Studies in Conservation. 58 (3): 199–210. doi:10.1179/2047058412Y.0000000063. JSTOR   42751821 via JSTOR.
  13. Zawacki, Alexander J. (23 January 2018). "How a Library Handles a Rare and Deadly Book of Wallpaper Samples". Atlas Obscura.
  14. Mars, Ashley Grove (11 June 2020). "Chrysler Museum of Art |". Chrysler Museum of Art. Retrieved 3 August 2024.
  15. Lipscher, Juraj. ""Georges Seurat, A Sunday on La Grande Jatte"". Colorlex.
  16. Sorenson 1995
  17. Blanco, Carlos (2012). "Heliothis virescens and Bt cotton in the United States". GM Crops & Food: Biotechnology in Agriculture and the Food Chain. 3 (3): 201–212. doi: 10.4161/gmcr.21439 . PMID   22892654.
  18. https://www.newspapers.com/image/505098962/?match=1&terms=Lime Minister of Agriculture of the United States Gives Advice, Victoria Daily Times, March 27, 1895, p.2.
  19. Justin M. Andrews, Sc. D. (1963). "Preventive Medicine in World War II, Chapter V. North Africa, Italy, and the Islands of the Mediterranean". Washington, D.C. USA: Office of the Surgeon General, Department of the Army. p. 281. Retrieved 30 September 2008.
  20. The Natural Paint Book, by Lynn Edwards, Julia Lawless, Table of contents
  21. Whorton, James C. (2010). The Arsenic Century: How Victorian Britain was Poisoned at Home, Work, and Play. OUP. p. 162. ISBN   9780191623431.
  22. dbv-Kommission Bestandserhaltung (December 2023). "Information zum Umgang mit potentiell gesundheitsschädigenden Pigmentbestandteilen an historischen Bibliotheksbeständen (hier: arsenhaltige Pigmente)" (PDF). www.bibliotheksverband.de (in German). Archived (PDF) from the original on 17 March 2024. Retrieved 17 March 2024. (6 pages)
  23. "Arsenbelastete Bücher" [Arsen contaminated books]. www.uni-bielefeld.de (in German). Universität Bielefeld. 2024. Archived from the original on 11 March 2024. Retrieved 6 March 2024.
  24. "Werke aus dem 19. Jahrhundert: Arsenverdacht – Unibibliothek überprüft 15.000 Bücher". www.spiegel.de (in German). 6 March 2024. Archived from the original on 17 March 2024. Retrieved 6 March 2024.
  25. dbv-Kommission Bestandserhaltung (29 February 2024). "Aktuelles: Information zum Umgang mit potentiell gesundheitsschädigenden Pigmentbestandteilen, wie arsenhaltigen Pigmenten, an historischen Bibliotheksbeständen". www.bibliotheksverband.de (in German). Retrieved 6 March 2024.
  26. Pilz, Michael (4 March 2024). "Warum von grünen Büchern eine Gefahr ausgeht" [Why green books are dangerous]. Kultur > Arsen. Welt (in German). Archived from the original on 4 March 2024. Retrieved 17 March 2024.
  27. University of Delaware. "Arsenic Bookbindings | Poison Book Project". Poison Book Project.
  28. Bartrip, P. W. J. (1994). "How Green Was My Valance?: Environmental Arsenic Poisoning and the Victorian Domestic Ideal". The English Historical Review. 109 (433): 891–913. ISSN   0013-8266.

Further reading