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Arsenic acid

Arsenic acid
Structural formula
Ball-and-stick model
Names
IUPAC name
Arsoric acid[1]
Other names
  • Desiccant L-10
  • Orthoarsenic acid
  • Trihydrogen arsenate
  • Zotox
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.029.001 Edit this at Wikidata
EC Number
  • 231-901-9
KEGG
RTECS number
  • CG0700000
UNII
UN number 1553, 1554
  • InChI=1S/AsH3O4/c2-1(3,4)5/h(H3,2,3,4,5) checkY
    Key: DJHGAFSJWGLOIV-UHFFFAOYSA-N checkY
  • InChI=1/AsH3O4/c2-1(3,4)5/h(H3,2,3,4,5)
    Key: DJHGAFSJWGLOIV-UHFFFAOYAY
  • O[As+](O)([O-])O
Properties
H3AsO4
Molar mass 141.942 g·mol−1
Appearance White translucent or colorless crystals, hygroscopic
Density 2.5 g/cm3
Melting point 35.5 °C (95.9 °F; 308.6 K)
Boiling point 120 °C (248 °F; 393 K) decomposes
16.7 g/(100 mL)
Solubility soluble in ethanol
Vapor pressure 55 hPa (50 °C)
Acidity (pKa) pKa1 = 2.19
pKa2 = 6.94
pKa3 = 11.5[2]
Conjugate base Arsenate
Structure
Tetrahedral at arsenic atom
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 Extremely toxic, carcinogenic, corrosive
GHS labelling:
GHS05: CorrosiveGHS06: ToxicGHS07: Exclamation markGHS08: Health hazardGHS09: Environmental hazard
Danger
H301, H312, H314, H331, H350, H361, H410
P201, P202, P260, P261, P264, P270, P271, P273, P280, P281, P301+P310, P301+P330+P331, P302+P352, P303+P361+P353, P304+P340, P305+P351+P338, P308+P313, P310, P311, P312, P321, P322, P330, P363, P391, P403+P233, P405, P501
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 Non-flammable
Lethal dose or concentration (LD, LC):
48 mg/kg (rat, oral)

6 mg/kg (rabbit, oral)

Related compounds
Other cations
 Sodium arsenate
Related compounds
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
checkY verify (what is checkY☒N ?)
Three bottles of arsenic acid from the Great Exhibition: impure, pure and distilled.

Arsenic acid or arsoric acid is the chemical compound with the formula H3AsO4. More descriptively written as AsO(OH)3, this colorless acid is the arsenic analogue of phosphoric acid. Arsenate and phosphate salts behave very similarly. Arsenic acid as such has not been isolated, but is only found in solution, where it is largely ionized. Its hemihydrate form (2H3AsO4·H2O) does form stable crystals. Crystalline samples dehydrate with condensation at 100 °C.[3]

Properties

It is a tetrahedral species of idealized symmetry C3v with As–O bond lengths ranging from 1.66 to 1.71 Å.[4]

Being a triprotic acid, its acidity is described by three equilibria:

H3AsO4 + H2O ⇌ H2AsO−4 + [H3O]+, pKa1 = 2.19
H2AsO−4 + H2O ⇌ HAsO2−4 + [H3O]+, pKa2 = 6.94
HAsO2−4 + H2O ⇌ AsO3−4 + [H3O]+, pKa3 = 11.5

These pKa values are close to those for phosphoric acid. The highly basic arsenate ion (AsO3−
4) is the product of the third ionization. Unlike phosphoric acid, arsenic acid is an oxidizer, as illustrated by its ability to convert iodide to iodine.

Preparation

Arsenic acid is prepared by treating arsenic trioxide with concentrated nitric acid. Dinitrogen trioxide is produced as a by-product.[5]

As2O3 + 2 HNO3 + 2 H2O → 2 H3AsO4 + N2O3

The resulting solution is cooled to give colourless crystals of the hemihydrate H3AsO4·0.5H2O (or 2H3AsO4·H2O), although the dihydrate H3AsO4·2H2O is produced when crystallisation occurs at lower temperatures.[5]

Other methods

Arsenic acid is slowly formed when arsenic pentoxide is dissolved in water, and when meta- or pyroarsenic acid (H4As2O7) is treated with cold water. Arsenic acid can also be prepared directly from elemental arsenic by moistening it and treating with ozone.

2 As + 3 H2O + 5 O3 → 2 H3AsO4 + 5 O2

Applications

Commercial applications of arsenic acid are limited by its toxicity. It is a precursor to a variety of pesticides. It has found occasional use as a wood preservative, a broad-spectrum biocide, a finishing agent for glass and metal, and a reagent in the synthesis of some dyestuffs and organic arsenic compounds.[6]

Safety

Arsenic acid is extremely toxic and carcinogenic, like all arsenic compounds. It is also corrosive. The LD50 in rabbits is 6 mg/kg (0.006 g/kg).[7]

References

  1. ^ "Arsenic acid".
  2. ^ Perrin, D. D., ed. (1982) [1969]. Ionisation Constants of Inorganic Acids and Bases in Aqueous Solution. IUPAC Chemical Data (2nd ed.). Oxford: Pergamon (published 1984). Entry 11. ISBN 0-08-029214-3. LCCN 82-16524.
  3. ^ Holleman, A. F.; Wiberg, E. (2001). Inorganic Chemistry. San Diego: Academic Press. ISBN 0-12-352651-5.
  4. ^ Lee, C.; Harrison, W. T. A. (2007). "Tetraethylammonium dihydrogenarsenate bis(arsenic acid) and 1,4-diazoniabicyclo[2.2.2]octane bis(dihydrogenarsenate) arsenic acid: hydrogen-bonded networks containing dihydrogenarsenate anions and neutral arsenic acid molecules". Acta Crystallographica C. 63 (Pt 7): m308–m311. doi:10.1107/S0108270107023967. PMID 17609552.
  5. ^ a b G. Brauer, ed. (1963). "Arsenic Acid". Handbook of Preparative Inorganic Chemistry. Vol. 1 (2nd ed.). New York: Academic Press. p. 601.
  6. ^ Minerals Yearbook, 2008, V. 1, Metals and Minerals. Government Printing Office. 2010. pp. 6–. ISBN 978-1-4113-3015-3.
  7. ^ Grund, Sabina C.; Hanusch, Kunibert; Wolf, Hans Uwe (2008). "Arsenic and Arsenic Compounds". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a03_113.pub2. ISBN 978-3527306732.
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