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Arsenite

Chemical compounds containing arsenic at oxidation state +3

Chemical compounds containing arsenic at oxidation state +3

In chemistry, an arsenite is a chemical compound containing an arsenic oxyanion where arsenic has oxidation state +3. Note that in fields that commonly deal with groundwater chemistry, arsenite is used generically to identify soluble AsIII anions. IUPAC have recommended that arsenite compounds are to be named as arsenate(III), for example ortho-arsenite is called trioxidoarsenate(III). Ortho-arsenite contrasts to the corresponding anions of the lighter members of group 15, phosphite which has the structure and nitrite, which is bent.

A number of different arsenite anions are known:

  • ortho-arsenite, an ion of arsenous acid, with a pyramidal shape
  • meta-arsenite, a polymeric chain anion.
  • pyro-arsenite,
  • catena-triarsenite,
  • catena-tetraarsenite,
  • cyclo-tetraarsenite
  • , a polymeric anion

In all of these the geometry around the AsIII centers are approximately trigonal, the lone pair on the arsenic atom is stereochemically active. Well known examples of arsenites include sodium meta-arsenite which contains a polymeric linear anion, , and silver ortho-arsenite, , which contains the trigonal anion.

Preparation of arsenites

Some arsenite salts can be prepared from an aqueous solution of . Examples of these are the meta-arsenite salts and at low temperature, hydrogen arsenite salts can be prepared, such as , , and .

Arsenite minerals

A number of minerals contain arsenite anions: reinerite, ; finnemanite, ; paulmooreite, ; stenhuggarite, (contains a complex polymeric anion); schneiderhöhnite, FeFe; magnussonite, ; trippkeite, ; trigonite, ; tooeleite, .

Arsenites in the environment

Arsenic can enter groundwater due to naturally occurring arsenic at deeper levels or from mine workings. Arsenic(III) can be removed from water by a number of methods, oxidation of AsIII to AsV for example with chlorine followed by coagulation with for example iron(III) sulfate. Other methods include ion-exchange and filtration. Filtration is only effective if arsenic is present as particulates, if the arsenite is in solution it passes through the filtration membrane.

Uses

Sodium arsenite is used in the water gas shift reaction to remove carbon dioxide. Fowler's solution first introduced in the 18th century was made up from as a solution of potassium meta-arsenite, .

Arsenic in its trioxide, As2O3, (brand name Trisenox, ATO) is used as a chemotherapy drug against acute promyelocytic leukaemia (APL), a type of myeloid leukemia. The detailed mechanism of action is unknown, but it is suspected to speed up apoptosis of cancer cells. Arsenic trioxide triggers morphological changes and DNA fragmentations in NB4 in vitro model for APL. It also degrades retinoic acid receptor alpha (RARA). RARA gene is important regulator of premyelocytic immune cell development, differentiation, and apoptosis.

Bacteria using and generating arsenite

Some species of bacteria obtain their energy by oxidizing various fuels while reducing arsenates to form arsenites. The enzymes involved are known as arsenate reductases.

In 2008, bacteria were discovered that employ a version of photosynthesis with arsenites as electron donors, producing arsenates (just like ordinary photosynthesis uses water as electron donor, producing molecular oxygen). The researchers conjectured that historically these photosynthesizing organisms produced the arsenates that allowed the arsenate-reducing bacteria to thrive.

In humans, arsenite inhibits pyruvate dehydrogenase (PDH complex) in the pyruvate-acetyl CoA reaction, by binding to the –SH group of lipoamide, a participant coenzyme. It also inhibits the oxoglutarate dehydrogenase complex by the same mechanism. The inhibition of these enzymes disrupts energy production.

References

References

  1. {{Greenwood&Earnshaw
  2. (1998). "Chemistry of Arsenic, Antimony and Bismuth". Blackie Academic and Professional.
  3. (2006). "Die neuen Catena-Polyarsenite [As3O7]5− und [As4O9]6−". Zeitschrift für anorganische und allgemeine Chemie.
  4. (2006). "Sm2As4O9: Ein ungewöhnliches Samarium(III)-Oxoarsenat(III) gemäß Sm4[As2O5]2[As4O8]". Zeitschrift für anorganische und allgemeine Chemie.
  5. (1987). "Zur Kenntnis von Natriumarseniten im Dreistoffsystem Na2O–As2O3–H2O bei 6 °C". Zeitschrift für anorganische und allgemeine Chemie.
  6. Hawthorne, Frank C. "Schneiderhoehnite, {{chem. Fe. 2+. Fe. 3. 3+. As. 5. 3+. O. 13, a densely packed arsenite structure." ''The Canadian Mineralogist'' '''23.4''' (1985): 675–679.
  7. (2007). "Crystal structure of tooeleite, Fe6(AsO3)4SO4(OH)4•4H2O, a new iron arsenite oxyhydroxy-sulfate mineral relevant to acid mine drainage". American Mineralogist.
  8. EPA, United states Environmental Protection Agency, Report 815R00012, "Technologies and Costs for the Removal of Arsenic From Drinking Water", December 2000 [https://web.archive.org/web/20110212094243/http://water.epa.gov/drink/info/arsenic/upload/2005_11_10_arsenic_treatments_and_costs.pdf]
  9. ''Managing Arsenic in the Environment: From Soil to Human Health'', R. Naidu, Csiro Publishing, 2006, {{ISBN. 978-0643068681
  10. Jolliffe, D. M.. (1993). "A history of the use of arsenicals in man". Journal of the Royal Society of Medicine.
  11. "Arsenic trioxide (Trisenox, ATO)".
  12. EMA. (2018-09-17). "Trisenox".
  13. "RARA retinoic acid receptor alpha [Homo sapiens (human)] - Gene - NCBI".
  14. [https://www.chemistryworld.com/news/arsenic-loving-bacteria-rewrite-photosynthesis-rules/3000398.article "Arsenic-loving bacteria rewrite photosynthesis rules"], ''Chemistry World'', 15 August 2008
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arsenites pnictogen-oxyanions arsenic(iii)-compounds
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