Arsenic acid: Difference between revisions

Arsenic acid
Names
	IUPAC name Arsoric acid
	Other names Desiccant L-10; Orthoarsenic acid; Trihydrogen arsenate; Zotox;
Identifiers
CAS Number	7778-39-4 ;
3D model (JSmol)	Interactive image;
ChEBI	CHEBI:18231 ;
ChEMBL	ChEMBL2374288;
ChemSpider	229 ;
ECHA InfoCard	100.029.001
EC Number	231-901-9;
KEGG	C01478 ;
PubChem CID	234;
RTECS number	CG0700000;
UNII	N7CIZ75ZPN ;
UN number	1553, 1554
CompTox Dashboard (EPA)	DTXSID1034341 ;
	InChI InChI=1S/AsH3O4/c2-1(3,4)5/h(H3,2,3,4,5) Key: DJHGAFSJWGLOIV-UHFFFAOYSA-N ; InChI=1/AsH3O4/c2-1(3,4)5/h(H3,2,3,4,5) Key: DJHGAFSJWGLOIV-UHFFFAOYAY;
	SMILES O[As+](O)([O-])O;
Properties
Chemical formula	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
Solubility in water	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
Conjugate base	Arsenate
Structure
Molecular shape	Tetrahedral at arsenic atom
Hazards
	Occupational safety and health (OHS/OSH):
Main hazards	Extremely toxic, carcinogenic, corrosive
	GHS labelling:
Pictograms
Signal word	Danger
Hazard statements	H301, H312, H314, H331, H350, H361, H410
Precautionary statements	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)	4 0 0
Flash point	Non-flammable
	Lethal dose or concentration (LD, LC):
LD50 (median dose)	48 mg/kg (rat, oral) 6 mg/kg (rabbit, oral)
Related compounds
Other cations	Sodium arsenate
Related compounds	Arsenous acid; Arsenic pentoxide; Phosphoric acid;
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). verify (what is ?) Infobox references

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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

It is a tetrahedral species of idealized symmetry C_3v 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]⁺, pK_a1 = 2.19

H₂AsO−4 + H₂O ⇌ HAsO2−4 + [H₃O]⁺, pK_a2 = 6.94

HAsO2−4 + H₂O ⇌ AsO3−4 + [H₃O]⁺, pK_a3 = 11.5

These pK_a 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

^ "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.

[1] "Arsenic acid".

[P82db-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.

[Brauer-5] G. Brauer, ed. (1963). "Arsenic Acid". Handbook of Preparative Inorganic Chemistry. Vol. 1 (2nd ed.). New York: Academic Press. p. 601.

[MY2008-6] Minerals Yearbook, 2008, V. 1, Metals and Minerals. Government Printing Office. 2010. pp. 6–. ISBN 978-1-4113-3015-3.

[GrundHanusch2008-7] 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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[2]

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@@ Line 1: / Line 1: @@
-{{chembox
+{{Chembox
 | Watchedfields = changed
 | verifiedrevid = 444189976
@@ Line 8: / Line 8: @@
 | ImageSize1 = 150px
 | ImageAlt1 = Ball-and-stick model
+| IUPACName = Arsoric acid<ref>{{cite web | url=https://pubchem.ncbi.nlm.nih.gov/compound/234#section=IUPAC-Name&fullscreen=true | title=Arsenic acid }}</ref>
-| IUPACName = Arsenic acid, arsoric acid
-| OtherNames = {{ubl|Arsenic acid|Orthoarsenic acid|Desiccant L-10|Zotox}}
+| OtherNames = {{ubl|Desiccant L-10|Orthoarsenic acid|Trihydrogen arsenate|Zotox}}
 |Section1={{Chembox Identifiers
 | ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
@@ Line 33: / Line 33: @@
 | PubChem = 234
 | UNNumber = 1553, 1554
-  }}
+ }}
 |Section2={{Chembox Properties
 | Formula = {{chem2|H3AsO4}}
+| H=3|As=1|O=4
-| MolarMass = 141.94 g/mol
-| Appearance = White translucent crystals, [[hygroscopic]]
+| Appearance = White translucent or colorless crystals, [[hygroscopic]]
 | Density = 2.5 g/cm<sup>3</sup>
-| Solubility = 16.7 g/100 mL
+| Solubility = 16.7 g/(100 mL)
-| SolubleOther = soluble in [[ethanol|alcohol]]
+| SolubleOther = soluble in [[ethanol]]
 | MeltingPtC = 35.5
 | BoilingPtC = 120
 | BoilingPt_notes = decomposes
 | ConjugateBase = [[Arsenate]]
+| 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.&nbsp;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&nbsp;11}}</ref>
-| pKa = 2.19, 6.94, 11.5
 | VaporPressure = 55&nbsp;hPa (50&nbsp;°C)
-  }}
+ }}
 |Section3={{Chembox Structure
-| MolShape = Tetrahedral
+| MolShape = [[Tetrahedral molecular geometry|Tetrahedral]] at [[arsenic]] atom
 | CrystalStruct =
-  }}
+ }}
 |Section7={{Chembox Hazards
 | MainHazards = Extremely toxic, carcinogenic, corrosive
@@ Line 58: / Line 58: @@
 | GHSPictograms = {{GHS05}}{{GHS06}}{{GHS07}}{{GHS08}}{{GHS09}}
 | GHSSignalWord = Danger
-| HPhrases = {{H-phrases|301|312|314|318|331|350|361|400|410}}
+| HPhrases = {{H-phrases|301|312|314|331|350|361|410}}
 | 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}}
 | NFPA-H = 4
@@ Line 65: / Line 65: @@
 | LD50 = 48 mg/kg (rat, oral)
 mg/kg (rabbit, oral)
-  }}
+ }}
 |Section8={{Chembox Related
-| OtherAnions = [[Phosphoric acid]]
 | OtherCations = [[Sodium arsenate]]
-| OtherCompounds = [[Arsenous acid]]<br />[[Arsenic pentoxide]]
+| OtherCompounds = {{ubl|[[Arsenous acid]]|[[Arsenic pentoxide]]|[[Phosphoric acid]]}}
-  }}
+ }}
 }}
 [[File:Arseniksyrlighet, prov.jpg|thumb|Three bottles of arsenic acid from the [[Great Exhibition]]: impure, pure and distilled.]]
-'''Arsenic 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&nbsp;°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>
+'''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&nbsp;°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>
 ==Properties==
@@ Line 80: / Line 79: @@
 Being a [[triprotic]] acid, its acidity is described by three equilibria:
-:H<sub>3</sub>AsO<sub>4</sub> + H<sub>2</sub>O {{eqm}} {{chem|H|2|AsO|4|-}} + H<sub>3</sub>O<sup>+</sup> {{pad|2em}}(p''K''<sub>a1</sub> = 2.19)
+:{{chem2|H3AsO4 + H2O ⇌ H2AsO4- + [H3O]+}}, p''K''<sub>a1</sub> = 2.19
-:{{chem|H|2|AsO|4|-}} + H<sub>2</sub>O {{eqm}} {{chem|HAsO|4|2-}} + H<sub>3</sub>O<sup>+</sup> {{pad|2em}}(p''K''<sub>a2</sub> = 6.94)
+:{{chem2|H2AsO4- + H2O ⇌ HAsO4(2-) + [H3O]+}}, p''K''<sub>a2</sub> = 6.94
-:{{chem|HAsO|4|2-}} + H<sub>2</sub>O {{eqm}} {{chem|AsO|4|3-}} + H<sub>3</sub>O<sup>+</sup> {{pad|2em}}(p''K''<sub>a3</sub> = 11.5)
+:{{chem2|HAsO4(2-) + H2O ⇌ AsO4(3-) + [H3O]+}}, p''K''<sub>a3</sub> = 11.5
 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]].
@@ Line 88: / Line 87: @@
 ==Preparation==
 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>
+:{{chem2|As2O3 + 2 HNO3 + 2 H2O → 2 H3AsO4 + N2O3}}
-: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>
-The resulting solution is cooled to give colourless crystals of the [[hemihydrate]] H<sub>3</sub>AsO<sub>4</sub>·{{sfrac|1|2}}H<sub>2</sub>O, although the dihydrate H<sub>3</sub>AsO<sub>4</sub>·2H<sub>2</sub>O is produced when crystallisation occurs at lower temperatures.<ref name=Brauer/>
+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/>
 ===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]].
+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]].
+:{{chem2|2 As + 3 H2O + 5 O3 → 2 H3AsO4 + 5 O2}}
-:2&nbsp;As + 3&nbsp;H<sub>2</sub>O + 5&nbsp;O<sub>3</sub> → 2&nbsp;H<sub>3</sub>AsO<sub>4</sub> + 5&nbsp;O<sub>2</sub>
 ==Applications==