Arsenic acid: Difference between revisions
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| verifiedrevid = 444189976 |
| verifiedrevid = 444189976 |
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| ImageFile = Arsenate.svg |
| ImageFile = Arsenate.svg |
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| ImageAlt = Structural formula |
| ImageAlt = Structural formula |
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| ImageFile1 = Arsenic-acid-3D-balls.png |
| ImageFile1 = Arsenic-acid-3D-balls.png |
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| ImageSize1 = 150px |
| ImageSize1 = 150px |
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| ImageAlt1 = Ball-and-stick model |
| ImageAlt1 = Ball-and-stick model |
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| IUPACName = Arsoric acid<ref>{{cite web | url=https://pubchem.ncbi.nlm.nih.gov/compound/234#section=IUPAC-Name&fullscreen=true | title=Arsenic acid }}</ref> |
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| IUPACName = Arsenic acid, arsoric acid |
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| OtherNames = |
| OtherNames = {{ubl|Desiccant L-10|Orthoarsenic acid|Trihydrogen arsenate|Zotox}} |
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|Section1={{Chembox Identifiers |
|Section1={{Chembox Identifiers |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| PubChem = 234 |
| PubChem = 234 |
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| UNNumber = 1553, 1554 |
| UNNumber = 1553, 1554 |
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}} |
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|Section2={{Chembox Properties |
|Section2={{Chembox Properties |
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| Formula = |
| Formula = {{chem2|H3AsO4}} |
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| H=3|As=1|O=4 |
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| MolarMass = 141.94 g/mol |
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| Appearance = White translucent crystals, |
| Appearance = White translucent or colorless crystals, [[hygroscopic]] |
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| Density = 2.5 g/cm<sup>3</sup> |
| Density = 2.5 g/cm<sup>3</sup> |
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| Solubility = 16.7 g/100 mL |
| Solubility = 16.7 g/(100 mL) |
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| SolubleOther = soluble in [[ |
| SolubleOther = soluble in [[ethanol]] |
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| MeltingPtC = 35.5 |
| MeltingPtC = 35.5 |
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| BoilingPtC = 120 |
| BoilingPtC = 120 |
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| BoilingPt_notes = decomposes |
| BoilingPt_notes = decomposes |
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| ConjugateBase = [[Arsenate]] |
| ConjugateBase = [[Arsenate]] |
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| pKa = p''K''<sub>a1</sub> = 2.19<br>p''K''<sub>a2</sub> = 6.94<br>p''K''<sub>a3</sub> = 11.5<ref name=P82db>{{cite book|title=Ionisation Constants of Inorganic Acids and Bases in Aqueous Solution|editor-first=D. D.|editor-last=Perrin|edition=2nd|series=[[IUPAC]] Chemical Data|issue=29|publisher=Pergamon|location=Oxford|year=1982|publication-date=1984|orig-date=1969|lccn=82-16524|isbn=0-08-029214-3|at=Entry 11}}</ref> |
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| pKa = 2.19, 6.94, 11.5 |
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| VaporPressure = 55 |
| VaporPressure = 55 hPa (50 °C) |
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}} |
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|Section3={{Chembox Structure |
|Section3={{Chembox Structure |
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| MolShape = Tetrahedral |
| MolShape = [[Tetrahedral molecular geometry|Tetrahedral]] at [[arsenic]] atom |
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| CrystalStruct = |
| CrystalStruct = |
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}} |
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|Section7={{Chembox Hazards |
|Section7={{Chembox Hazards |
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| MainHazards = Extremely toxic, carcinogenic, corrosive |
| MainHazards = Extremely toxic, carcinogenic, corrosive |
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| GHSPictograms = {{GHS05}}{{GHS06}}{{GHS07}}{{GHS08}}{{GHS09}} |
| GHSPictograms = {{GHS05}}{{GHS06}}{{GHS07}}{{GHS08}}{{GHS09}} |
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| GHSSignalWord = Danger |
| GHSSignalWord = Danger |
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| HPhrases = {{H-phrases|301|312|314 |
| HPhrases = {{H-phrases|301|312|314|331|350|361|410}} |
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| PPhrases = {{P-phrases|201|202|260|261|264|270|271|273|280|281|301+310|301+330+331|302+352|303+361+353|304+340|305+351+338|308+313|310|311|312|321|322|330|363|391|403+233|405|501}} |
| PPhrases = {{P-phrases|201|202|260|261|264|270|271|273|280|281|301+310|301+330+331|302+352|303+361+353|304+340|305+351+338|308+313|310|311|312|321|322|330|363|391|403+233|405|501}} |
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| NFPA-H = 4 |
| NFPA-H = 4 |
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| LD50 = 48 mg/kg (rat, oral) |
| LD50 = 48 mg/kg (rat, oral) |
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6 mg/kg (rabbit, oral) |
6 mg/kg (rabbit, oral) |
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}} |
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|Section8={{Chembox Related |
|Section8={{Chembox Related |
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| OtherAnions = [[Phosphoric acid]] |
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| OtherCations = [[Sodium arsenate]] |
| OtherCations = [[Sodium arsenate]] |
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| OtherCompounds = [[Arsenous acid]] |
| OtherCompounds = {{ubl|[[Arsenous acid]]|[[Arsenic pentoxide]]|[[Phosphoric acid]]}} |
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}} |
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}} |
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[[File:Arseniksyrlighet, prov.jpg|thumb|Three bottles of arsenic acid from the [[Great Exhibition]]: impure, pure and distilled.]] |
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'''Arsenic acid''' is the [[chemical compound]] with the [[chemical formula|formula]] |
'''Arsenic acid''' or '''arsoric acid''' is the [[chemical compound]] with the [[chemical formula|formula]] {{chem2|H3AsO4}}. More descriptively written as {{chem2|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 ({{chem2|2H3AsO4*H2O}}) does form stable crystals. Crystalline samples dehydrate with condensation at 100 °C.<ref>{{ cite book |author1=Holleman, A. F. |author2=Wiberg, E. | title = Inorganic Chemistry | publisher = Academic Press | location = San Diego | year = 2001 | isbn = 0-12-352651-5 }}</ref> |
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==Properties== |
==Properties== |
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It is a tetrahedral species of idealized [[symmetry group|symmetry]] ''C<sub>3v</sub> |
It is a tetrahedral species of idealized [[symmetry group|symmetry]] ''C''<sub>3v</sub> with As–O bond lengths ranging from 1.66 to 1.71 Å.<!--the terminal As=O is not so clear due to H-bonding--><ref>{{cite journal |author1=Lee, C. |author2=Harrison, W. T. A. | title = 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 | journal = [[Acta Crystallographica C]] | year = 2007 | volume = 63 | issue = Pt 7 | pages = m308–m311 | doi = 10.1107/S0108270107023967 | pmid = 17609552 }}</ref> |
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Being a [[triprotic]] acid, its acidity is described by three equilibria: |
Being a [[triprotic]] acid, its acidity is described by three equilibria: |
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:{{chem2|H3AsO4 + H2O ⇌ H2AsO4- + [H3O]+}}, p''K''<sub>a1</sub> = 2.19 |
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:H<sub>3</sub>AsO<sub>4</sub> + H<sub>2</sub>O {{eqm}} H<sub>2</sub>AsO{{su|b=4|p=−}} + H<sub>3</sub>O<sup>+</sup> (''K''<sub>1</sub> = 10<sup>−2.19</sup>) |
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:{{chem2|H2AsO4- + H2O ⇌ HAsO4(2-) + [H3O]+}}, p''K''<sub>a2</sub> = 6.94 |
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: |
:{{chem2|HAsO4(2-) + H2O ⇌ AsO4(3-) + [H3O]+}}, p''K''<sub>a3</sub> = 11.5 |
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These ''K''<sub>a</sub> values are close to those for phosphoric acid. The highly basic [[arsenate|arsenate ion]] ( |
These [[acid dissociation constant|p''K''<sub>a</sub>]] values are close to those for [[phosphoric acid]]. The highly basic [[arsenate|arsenate ion]] ({{chem|AsO|4|3-}}) 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]]. |
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==Preparation== |
==Preparation== |
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Arsenic acid is prepared by treating arsenic trioxide with concentrated [[nitric acid]]. [[Dinitrogen trioxide]] is produced as a by-product.<ref name=Brauer>{{ cite book | chapter = Arsenic Acid | title = Handbook of Preparative Inorganic Chemistry | edition = 2nd | editor = G. Brauer | publisher = Academic Press | year = 1963 | location = New York | volume = 1 | page = 601 }}</ref> |
Arsenic acid is prepared by treating arsenic trioxide with concentrated [[nitric acid]]. [[Dinitrogen trioxide]] is produced as a by-product.<ref name=Brauer>{{ cite book | chapter = Arsenic Acid | title = Handbook of Preparative Inorganic Chemistry | edition = 2nd | editor = G. Brauer | publisher = Academic Press | year = 1963 | location = New York | volume = 1 | page = 601 }}</ref> |
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:{{chem2|As2O3 + 2 HNO3 + 2 H2O → 2 H3AsO4 + N2O3}} |
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:As<sub>2</sub>O<sub>3</sub> + 2 HNO<sub>3</sub> + 2 H<sub>2</sub>O → 2 H<sub>3</sub>AsO<sub>4</sub> + N<sub>2</sub>O<sub>3</sub> |
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The resulting solution is cooled to give colourless crystals of the [[hemihydrate]] |
The resulting solution is cooled to give colourless crystals of the [[hemihydrate]] {{chem2|H3AsO4*0.5H2O}} (or {{chem2|2H3AsO4*H2O}}), although the dihydrate {{chem2|H3AsO4*2H2O}} is produced when crystallisation occurs at lower temperatures.<ref name=Brauer/> |
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===Other methods=== |
===Other methods=== |
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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 is slowly formed when [[arsenic pentoxide]] is dissolved in water, and when ''meta''- or [[pyroarsenic acid]] ({{chem2|H4As2O7}}) is treated with cold water. Arsenic acid can also be prepared directly from elemental arsenic by moistening it and treating with [[ozone]]. |
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:2 As |
:{{chem2|2 As + 3 H2O + 5 O3 → 2 H3AsO4 + 5 O2}} |
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==Applications== |
==Applications== |
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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 [[dyestuff]]s and organic arsenic compounds.<ref name="MY2008">{{cite book|title=Minerals Yearbook, 2008, V. 1, Metals and Minerals|url=https://books.google.com/books?id=tL4hau707bwC&pg=SA6-PA10|year=2010|publisher=Government Printing Office|isbn=978-1-4113-3015-3|pages=6–}}</ref> |
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 [[dyestuff]]s and organic arsenic compounds.<ref name="MY2008">{{cite book|title=Minerals Yearbook, 2008, V. 1, Metals and Minerals|url=https://books.google.com/books?id=tL4hau707bwC&pg=SA6-PA10|year=2010|publisher=Government Printing Office|isbn=978-1-4113-3015-3|pages=6–}}</ref> |
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==Safety== |
==Safety== |
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Arsenic acid is extremely toxic and carcinogenic, like all arsenic compounds. |
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).<ref name="GrundHanusch2008">{{cite book|last1=Grund|first1=Sabina C.|title=Ullmann's Encyclopedia of Industrial Chemistry|last2=Hanusch|first2=Kunibert|last3=Wolf|first3=Hans Uwe|chapter=Arsenic and Arsenic Compounds|year=2008|doi=10.1002/14356007.a03_113.pub2|isbn=978-3527306732}}</ref> |
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==References== |
==References== |
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[[Category:Arsenates]] |
[[Category:Arsenates]] |
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[[Category: |
[[Category:Arsenic(V) compounds]] |
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⚫ | |||
[[Category:Oxidizing acids]] |
[[Category:Oxidizing acids]] |
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⚫ |
Latest revision as of 03:30, 10 June 2024
Names | |
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IUPAC name
Arsoric acid[1]
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Other names
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Identifiers | |
3D model (JSmol)
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ChEBI | |
ChEMBL | |
ChemSpider | |
ECHA InfoCard | 100.029.001 |
EC Number |
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KEGG | |
PubChem CID
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RTECS number |
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UNII | |
UN number | 1553, 1554 |
CompTox Dashboard (EPA)
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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
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Extremely toxic, carcinogenic, corrosive |
GHS labelling: | |
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) | |
Flash point | Non-flammable |
Lethal dose or concentration (LD, LC): | |
LD50 (median dose)
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48 mg/kg (rat, oral)
6 mg/kg (rabbit, oral) |
Related compounds | |
Other cations
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Sodium arsenate |
Related compounds
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Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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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
[edit]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
[edit]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
[edit]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
[edit]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
[edit]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
[edit]- ^ "Arsenic acid".
- ^ 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.
- ^ Holleman, A. F.; Wiberg, E. (2001). Inorganic Chemistry. San Diego: Academic Press. ISBN 0-12-352651-5.
- ^ 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.
- ^ a b G. Brauer, ed. (1963). "Arsenic Acid". Handbook of Preparative Inorganic Chemistry. Vol. 1 (2nd ed.). New York: Academic Press. p. 601.
- ^ Minerals Yearbook, 2008, V. 1, Metals and Minerals. Government Printing Office. 2010. pp. 6–. ISBN 978-1-4113-3015-3.
- ^ 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.