Wikipedia

Calcium arsenate

Calcium arsenate is the inorganic compound with the formula Ca3(AsO4)2. A colourless salt, it was originally used as a pesticide and as a germicide. It is highly soluble in water, in contrast to lead arsenate, which makes it more toxic. Two minerals are hydrates of calcium arsenate: rauenthalite Ca3(AsO4)2·10H2O and phaunouxite Ca3(AsO4)2·11H2O.[4] A related mineral is ferrarisite (Ca5H2(AsO4)4·9H2O.[5]

Calcium arsenate
Calcium arsenate
Calcium arsenate
Names
IUPAC name
Calcium arsorate
Other names
Calcium orthoarsenate
Cucumber dust
Tricalcium arsenate
Tricalcium ortho-arsenate
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.029.003 Edit this at Wikidata
EC Number
  • 233-287-8
KEGG
RTECS number
  • CG0830000
UNII
  • InChI=1S/2AsH3O4.3Ca/c2*2-1(3,4)5;;;/h2*(H3,2,3,4,5);;;/q;;3*+2/p-6 ☒N
    Key: RMBBSOLAGVEUSI-UHFFFAOYSA-H ☒N
  • InChI=1/2AsH3O4.3Ca/c2*2-1(3,4)5;;;/h2*(H3,2,3,4,5);;;/q;;3*+2/p-6
    Key: RMBBSOLAGVEUSI-CYFPFDDLAC
  • [O-][As](=O)([O-])[O-].[O-][As](=O)([O-])[O-].[Ca+2].[Ca+2].[Ca+2]
Properties
Ca3(AsO4)2
Molar mass 398.072 g/mol
Appearance white powder
Odor odorless
Density 3.62 g/cm3, solid
Melting point 1,455 °C (2,651 °F; 1,728 K) (decomposes)
0.013 g/100 mL (25 °C)[1]
Solubility in Organic solvents insoluble
Solubility in acids soluble
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 carcinogen[2]
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 4: Very short exposure could cause death or major residual injury. E.g. VX gasFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
4
0
0
Flash point noncombustible[2]
Lethal dose or concentration (LD, LC):
20 mg/kg (rat, oral)
82 mg/kg (rat, oral)
74 mg/kg (mouse, oral)
50 mg/kg (rabbit, oral)
38 mg/kg (dog, oral)[3]
NIOSH (US health exposure limits):
PEL (Permissible)
 TWA 0.010 mg/m3[2]
REL (Recommended)
 Ca C 0.002 mg/m3 [15-minute][2]
IDLH (Immediate danger)
 5 mg/m3 (as As)[2]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is checkY☒N ?)

Preparation

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Calcium arsenate is commonly prepared from disodium hydrogen arsenate and calcium chloride:

2 Na2H[AsO4] + 3 CaCl2 → 4 NaCl + Ca3[AsO4]2 + 2 HCl

In the 1920s, it was made in large vats by mixing calcium oxide and arsenic oxide.[6] In the United States, 1360 metric tons were produced in 1919, 4540 in 1920, and 7270 in 1922.[1] The composition of commercially available calcium arsenate varies from manufacturer to manufacturer. A typical composition is 80-85% of Ca3(AsO4)2 a basic arsenate probably with a composition of 4CaO.As2O5 together with calcium hydroxide and calcium carbonate.[citation needed]

Use as a herbicide

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It was once a common herbicide and insecticide. 38,000,000 kilograms were reported to be produced in 1942 alone, mainly for protection of cotton crops. Its high toxicity led the development of DDT.[7]

Regulation

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Calcium arsenate use is now banned in the UK, and its use is strictly regulated in the United States. It is currently the active ingredient in TURF-Cal manufactured by Mallinckrodt, it is one of the few herbicides – used mainly for the control of Poa annua and crabgrass- that hinders earthworm activity. Its label states that it will "reduce and inhibit earthworm activity and survival" and is only recommended against serious earthworm infestations in places such as golf course greens.[8]

Toxicity and regulation

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Calcium arsenate is highly toxic, having both carcinogenic and systemic health effects.[9] The Occupational Safety and Health Administration has set a permissible exposure limit at 0.01 mg/m3 over an eight-hour time-weighted average, while the National Institute for Occupational Safety and Health recommends a limit five times less (0.002 mg/m3).[10]

It is classified as an extremely hazardous substance in the United States as defined in Section 302 of the U.S. Emergency Planning and Community Right-to-Know Act (42 U.S.C. 11002), and is subject to strict reporting requirements by facilities which produce, store, or use it in significant quantities.[11]

Other natural occurrences

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Weilite is the monohydrogenated counterpart, Ca(HAsO4),[12] while švenekite – the dihydrogenated one, Ca(H2AsO4)2.[13] Hydrated analogues of weilite are haidingerite (monohydrate) and pharmacolite (dihydrate), with the latter name reflecting arsenic-related toxicity. Examples of more complex, hydrated Ca arsenates with some anions hydrogenated, are ferrarisite,[14] guérinite,[15] sainfeldite,[16] vladimirite,[17] and jeankempite.[18][19]

References

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  1. ^ a b Tartar, H.V.; Wood, L; Hiner, E; A Basic Arsenate of Calcium. J. Am. Chem. Soc. 1924, vol. 46, 809-813.
  2. ^ a b c d e NIOSH Pocket Guide to Chemical Hazards. "#0089". National Institute for Occupational Safety and Health (NIOSH).
  3. ^ "Calcium arsenate (as As)". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  4. ^ Bari, Hubert; Catti, Michele; Ferraris, Giovanni; Ivaldi, Gabriella; Permingeat, François (1982). "Phaunouxite Ca3(AsO4)2•11H2O, a New Mineral Strictly Associated with Rauenthalite". Bulletin de Minéralogie. 105 (4): 327–332. doi:10.3406/bulmi.1982.7624.
  5. ^ Bari, Hubert; Permingeat, François; Pierrot, Roland; Walenta, Kurt (1980). "La ferrarisite Ca5H2(AsO4)4.9 H2O, une Nouvelle Espèce Minérale Dimorphe de la Guérinite". Bulletin de Minéralogie. 103 (5): 533–540. doi:10.3406/bulmi.1980.7417.
  6. ^ Smith, C.M.; Murray, C.W.; The Composition of Commercial Calcium Arsenate. Journal of Industrial and Engineering Chemistry; 1931, 23
  7. ^ Robert L. Metcalf "Insect Control" in Ullmann’s Encyclopedia of Industrial Chemistry Wiley-VCH, Weinheim, 2002. doi:10.1002/14356007.a14_263
  8. ^ Koval, C.F. "Turf insect pest control guide: Urban Phytonarian Series" (PDF). College of Agricultural and Life Sciences – University of Wisconsin-Madison. Retrieved 9 November 2018.
  9. ^ Tchounwou, P.B.; Patlolla, A.K.; Centeno, J.A.; Carcinogenic and Systematic Health Effects Associated with Arsenic – A Critical Review. Toxicologic Pathology; 2003, 31, 575-588
  10. ^ "Calcium Arsenate". NIOSH Pocket Guide to Chemical Hazards. Centers for Disease Control and Prevention. 4 April 2011. Retrieved 18 November 2013.
  11. ^ "40 C.F.R.: Appendix A to Part 355—The List of Extremely Hazardous Substances and Their Threshold Planning Quantities" (PDF) (1 July 2008 ed.). Government Printing Office. Archived from the original (PDF) on 25 February 2012. Retrieved 29 October 2011. {{cite journal}}: Cite journal requires |journal= (help)
  12. ^ "Weilite".
  13. ^ "Švenekite".
  14. ^ "Ferrarisite".
  15. ^ "Guérinite".
  16. ^ "Sainfeldite".
  17. ^ "Vladimirite".
  18. ^ "Jeankempite".
  19. ^ "List of Minerals". 21 March 2011.
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