Arsenic acid

Arsenic 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 (H3AsO4·12H2O) does form stable crystals. Crystalline samples dehydrate with condensation at 100 °C.[1]

Arsenic acid
Names
IUPAC name
Arsenic acid, arsoric acid
Other names
Arsenic acid
Orthoarsenic acid
Desiccant L-10
Zotox
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.029.001
EC Number
  • 231-901-9
KEGG
RTECS number
  • CG0700000
UNII
UN number 1553, 1554
Properties
H3AsO4
Molar mass 141.94 g/mol
Appearance White translucent 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 alcohol
Vapor pressure 55 hPa (50 °C)
Acidity (pKa) 2.19, 6.94, 11.5
Conjugate base Arsenate
Structure
Tetrahedral
Hazards
Main hazards Extremely toxic, carcinogenic, corrosive
GHS pictograms
GHS Signal word Danger
GHS hazard statements
H301, H312, H314, H318, H331, H350, H361, H400, H410
P201, P202, P260, P261, P264, P270, P271, P273, P280, P281, P301+310, P301+330+331, P302+352, P303+361+353, P304+340, P305+351+338, P308+313, P310, P311, P312, P321, P322, P330, P363, P391
NFPA 704 (fire diamond)
Flammability code 0: Will not burn. E.g. waterHealth code 4: Very short exposure could cause death or major residual injury. E.g. VX gasReactivity code 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
0
4
0
Flash point Non-flammable
Lethal dose or concentration (LD, LC):
48 mg/kg (rat, oral)

6 mg/kg (rabbit, oral)

Related compounds
Other anions
Phosphoric acid
Other cations
Sodium arsenate
Related compounds
Arsenous acid
Arsenic pentoxide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Properties

It is a tetrahedral species of idealized symmetry C3v with AsO bond lengths ranging from 1.66 to 1.71 Å.[2]

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

H3AsO4 + H2O H2AsO
4
+ H3O+ (K1 = 10−2.19)
H2AsO
4
+ H2O HAsO2−
4
+ H3O+ (K2 = 10−6.94)
HAsO2−
4
+ H2O AsO3−
4
+ H3O+ (K3 = 10−11.5)

These Ka 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.[3]

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

The resulting solution is cooled to give colourless crystals of the hemihydrate H3AsO4·12H2O, although the dihydrate H3AsO4·2H2O is produced when crystallisation occurs at lower temperatures.[3]

Other methods

Arsenic acid is slowly formed when arsenic pentoxide is dissolved in water, and when meta- or pyroarsenic acid 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.[4]

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).[5]

References

  1. Holleman, A. F.; Wiberg, E. (2001). Inorganic Chemistry. San Diego: Academic Press. ISBN 0-12-352651-5.
  2. 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.
  3. G. Brauer, ed. (1963). "Arsenic Acid". Handbook of Preparative Inorganic Chemistry. 1 (2nd ed.). New York: Academic Press. p. 601.
  4. Minerals Yearbook, 2008, V. 1, Metals and Minerals. Government Printing Office. 2010. pp. 6–. ISBN 978-1-4113-3015-3.
  5. 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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