Copper arsenite

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The copper (II) salts of arsenic acid and arsenic acid are referred to as copper arsenites . The term copper arsenate is incorrectly used in historical sources to refer to some compounds that are actually hydrates of copper arsenites. Today the terms are used synonymously. According to current sources, several dozen copper arsenites are known, including hydrates.

history

A mixture of normal and basic copper (II) arsenites was first produced by Carl Wilhelm Scheele in 1775 from copper sulfate , arsenic and sodium carbonate or potassium carbonate . The discovery was published in 1778, but its manufacture was kept a secret. This led to different variants with the approximate composition CuHAsO 3 or Cu 3 (AsO 3 ) 2 · 3H 2 O, of which an "improved" one was patented by Parker in England in 1812 as a Green patent. The substance was named Scheeles Green after its discoverer , but also as mineral green, Parisian green, Swedish green, Cuprum arsenicosum. This is a yellow-green solid that is practically insoluble in water and ethanol , but soluble in dilute acids and an aqueous ammonia solution . In addition to Schweinfurt green (copper (II) acetate arsenite), the substance was used as a green color pigment for a long time.

Occurrence

Copper arsenites occur naturally as various minerals . Among them are Lammerite Cu 3 (AsO 4 ) 2 , Trippkeit Cu [As 2 O 4 ], Babánekite Cu 3 (AsO 4 ) 2 · 8H 2 O and Rollandite Cu 3 (AsO 4 ) 2 · 4H 2 O. In addition, also those Kupferoxoarsenite Ericlaxmanit Cu 4 O (AsO 4 ) 2 , Kozyrevskit Cu 4 O (AsO 4 ) 2 , Popovit Cu 5 O 2 (AsO 4 ) 2 and other Kupferhydroxyarseniten such as Yvonit Cu (AsO 3 OH) · 2H 2 O and Geminit Cu (AsO 3 OH) · H 2 O.

presentation

Copper diarsenite can be obtained by reacting arsenic (III) oxide with copper (II) oxide in acetic acid at 200 ° C. Copper (II) arsenate (V) can be obtained by reacting sodium dihydrogen arsenate and copper (II) chloride in an aqueous solution. Copper (II) metal arsenite can be obtained by reacting copper (II) hydroxide or a mixture of copper (II) oxide and copper (II) chloride with arsenic (III) oxide.

properties

Copper arsenates (III) (also called copper (II) arsenites) are yellow-green powders that are insoluble in water and ethanol, but soluble in dilute acids. As a tetrahydrate, copper (II) arsenate (V) forms a bluish-green powder that is insoluble in water, but soluble in dilute acids and ammonia water. Copper diarsenite has a crystal structure with the space group P 4 (space group no. 75) . Copper (II) arsenate (V) has a monoclinic crystal structure with the space group P 2 1 / c (space group no. 14) . Template: room group / 75 Template: room group / 14

Copper arsenite
Surname Copper (II) hydrogen arsenite Copper diarsenite Copper (II) metaarsenite Copper (II) arsenate (V)
other names Copper arsenate (III)
Copper orthoarsenite
Scheeles green
Natural occurrence Trippiness Lammerite
Rollandite (tetrahydrate)
Babánekite (octahydrate)
Structural formula CuHAsO 3 Cu (AsO 2 ) 2 Cu 3 (AsO 3 ) 2 Cu 3 (AsO 4 ) 2
CAS number 10290-12-7 16509-22-1 73156-86-2 7778-41-8
10103-61-4 (tetrahydrate)
PubChem 25130 102601714 3055940 26065
Molar mass 187.46 g mol −1 277.39 g mol −1 436.48 g mol −1 341.38 g mol −1
Physical state firmly
Brief description yellow-green solids bluish-green solid
Melting point decomposition
density 4.49 g cm −3 4.8 g cm −3
Solubility in water practically insoluble practically insoluble
GHS
labeling 		from  Regulation (EC) No. 1272/2008 (CLP) , expanded if necessary
06 - Toxic or very toxic 09 - Dangerous for the environment
danger 		from  Regulation (EC) No. 1272/2008 (CLP) , expanded if necessary
06 - Toxic or very toxic 09 - Dangerous for the environment
danger 		from  Regulation (EC) No. 1272/2008 (CLP) , expanded if necessary
06 - Toxic or very toxic 08 - Dangerous to health 09 - Dangerous for the environment
danger
H and P phrases 331-301-410 331-301-410 301-331-350-410
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use

Copper (II) arsenate (V) was used as an insecticide , fungicide and wood preservative , but is allowed in various countries, e.g. B. in Germany, are no longer used in plant protection. The same also applies to the so-called copper arsenic broth (arsenic copper lime broth), an aqueous suspension of calcium arsenate and copper lime , which was previously used in viticulture.

Individual evidence

  1. ^ A b c Nicholas Eastaugh, Valentine Walsh, Tracey Chaplin, Ruth Siddall: Pigment Compendium: A Dictionary of Historical Pigments . Routledge, 2007, ISBN 978-1-136-37386-2 , pp. 122 ( limited preview in Google Book search).
  2. ↑ a b c d e f g h Entry on copper arsenates. In: Römpp Online . Georg Thieme Verlag, accessed on March 19, 2016.
  3. ↑ files.wordpress.com: A Tribute to the Memory of Carl Wilhelm Scheele (1742–1786) , by Professor Gunnar Svedberg, accessed on March 25, 2016
  4. ^ Hermann Hager, NA Frerichs, NA Arends, NA Zörnig, NA Rimbach, NA Mannheim, NA Hartwig, NA Bachem, NA Hilgers: Hager's Handbook of Pharmaceutical Practice For Pharmacists, Doctors, Druggists and Medical Officials . Springer-Verlag, 2013, ISBN 978-3-662-02106-4 , pp. 561 ( limited preview in Google Book search).
  5. ↑ egranth.ac.in: Chemistry of INSECTICIDES, FUNGICIDES AND HERBICIDES BY DONALD EH FREAR ( Memento of March 26, 2016 in the Internet Archive ), Second Edition, September 1948, accessed on March 26, 2016
  6. ↑ Ya-jie Zheng, Fa-xin Xiao, Yong Wang, Chun-hua Li, Wei Xu, Hong-sheng Jian, Yu-tian Ma: Industrial experiment of copper electrolyte purification by copper arsenite. In: Journal of Central South University of Technology. 15, 2008, p. 204, doi : 10.1007 / s11771-008-0039-2 .
  7. ^ PH List and L. Hörhammer in association with HJ Roth and W. Schmid: Hager's Handbook of Pharmaceutical Practice. Volume 4: Chemicals and Drugs (CI-G) . Springer-Verlag, 1973, ISBN 978-3-642-80620-9 , pp. 373 ( limited preview in Google Book search).
  8. ↑ a b c F. Pertlik: Refinement of the crystal structure of synthetic trippidity, CuAs2O4. In: TMPM Tschermaks Mineralogische und Petrographische Mitteilungen. 22, 1975, p. 211, doi : 10.1007 / BF01087840 .
  9. ↑ a b c Sandra J. Poulsen, C. Calvo: Crystal structure of Cu3 (AsO4) 2. In: Canadian Journal of Chemistry. 46, 1968, p. 917, doi : 10.1139 / v68-153 .
  10. Jump up ↑ Frost, Ray L. and Bahfenne, Silmarilly (2010) A Review of the Vibrational Spectroscopic Studies of Arsenite, Antimonite, and Antimonate Minerals. Applied Spectroscopy Reviews : an international journal of principles, methods, and applications, 45 (2). pp. 101-129.
  11. ↑ International Chemical Safety Card (ICSC) for COPPER (II) ARSENITE at the National Institute for Occupational Safety and Health (NIOSH), accessed on March 26, 2016.
  12. ^ A b Dale L. Perry: Handbook of Inorganic Compounds, Second Edition . CRC Press, 2011, ISBN 978-1-4398-1462-8 , pp. 143 ( limited preview in Google Book search).
  13. ↑ a b Entry on copper (II) arsenite in the GESTIS material database of the IFA , accessed on January 9, 2017 (JavaScript required)
  14. ↑ a b Not explicitly listed in Regulation (EC) No. 1272/2008 (CLP) , but with the specified labeling it falls under the group entry arsenic compounds, with the exception of those named in this annex in the Classification and Labeling Inventory of the European Chemicals Agency (ECHA) , accessed on January 9, 2017. Manufacturers or distributors can expand the harmonized classification and labeling .
  15. ↑ Not explicitly listed in Regulation (EC) No. 1272/2008 (CLP) , but with the specified labeling it falls under the group entry arsenic acid and its salts, unless specifically listed in this appendix in the Classification and Labeling Inventory of the European Chemicals Agency (ECHA) , accessed on January 9, 2017. Manufacturers or distributors can expand the harmonized classification and labeling .