Peroxymonosulfuric acid: Difference between revisions

Peroxymonosulfuric acid
Names
	IUPAC names Peroxysulfuric acid; Sulfuroperoxoic acid
	Systematic IUPAC name (Dioxidanido)hydroxidodioxidosulfur
	Other names Peroxosulfuric acid; Peroxomonosulfuric acid[citation needed]; Persulfuric acid[citation needed]; Caro's acid
Identifiers
CAS Number	7722-86-3 ;
3D model (JSmol)	Interactive image; Interactive image;
ChEBI	CHEBI:29286 ;
ChemSpider	2035480 ;
ECHA InfoCard	100.028.879
EC Number	231-766-6;
Gmelin Reference	101039
PubChem CID	2754594;
UNII	JC6U8R2UJ9 ;
UN number	1483
CompTox Dashboard (EPA)	DTXSID90884417 ;
	InChI InChI=1S/H2O5S/c1-5-6(2,3)4/h1H,(H,2,3,4) Key: FHHJDRFHHWUPDG-UHFFFAOYSA-N ;
	SMILES OOS(O)(=O)=O; [O].[O].OOSO;
Properties
Chemical formula	H; 2SO; 5
Molar mass	114.078 g mol−1
Appearance	White crystals
Density	2.239 g cm−3
Melting point	45 °C
Acidity (pKa)	1, 9.3
Conjugate base	Peroxomonosulfate
Structure
Coordination geometry	Tetrahedral at S
Hazards
	Occupational safety and health (OHS/OSH):
Main hazards	strong oxidizer
	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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Peroxymonosulfuric acid, also known as persulfuric acid, peroxysulfuric acid is the inorganic compound with the formula H₂SO₅. It is a white solid. It is a component of Caro's acid, which is a solution of peroxymonosulfuric acid in sulfuric acid containing small amounts of water.^[4] Peroxymonosulfuric acid is a very strong oxidant (E⁰ = +2.51 V).

Structure

In peroxymonosulfuric acid, the S(VI) center adopts its characteristic tetrahedral geometry; the connectivity is indicated by the formula HO–O–S(O)₂–OH. The S-O-H proton is more acidic.^[4]

History

The German chemist Heinrich Caro first reported investigations of mixtures of hydrogen peroxide and sulfuric acid.^[5]

Synthesis and production

One laboratory scale preparation of Caro's acid involves the combination of chlorosulfuric acid and hydrogen peroxide:^[6]

H₂O₂ + ClSO₂OH ⇌ H₂SO₅ + HCl

Patents include more than one reaction for preparation of Caro's acid, usually as an intermediate for the production of potassium monopersulfate (PMPS), a bleaching and oxidizing agent. One route employs the following reaction:^[7]

H₂O₂ + H₂SO₄ ⇌ H₂SO₅ + H₂O

This reaction is related to "piranha solution".

Uses in industry

H
₂SO
₅ and Caro's acid have been used for a variety of disinfectant and cleaning applications, e.g., swimming pool treatment and denture cleaning. It is used in gold mining to destroy the cyanide in the waste stream ("Tailings").

Alkali metal salts of H
₂SO
₅, especially oxone, are widely investigated.

Hazards

These peroxy acids can be explosive. Explosions have been reported at Brown University^[8] and Sun Oil. As with all strong oxidizing agents, peroxysulfuric acid is incompatible with organic compounds.

References

^ ^a ^b ^c International Union of Pure and Applied Chemistry (2005). Nomenclature of Inorganic Chemistry (IUPAC Recommendations 2005). Cambridge (UK): RSC–IUPAC. ISBN 0-85404-438-8. p. 139. Electronic version.
^ "Peroxysulfuric acid (CHEBI:29286)". Chemical Entities of Biological Interest. UK: European Bioinformatics Institute. 20 November 2007. Retrieved 17 November 2011.
^ 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 176. ISBN 0-08-029214-3. LCCN 82-16524.
^ ^a ^b Jakob, Harald; Leininger, Stefan; Lehmann, Thomas; Jacobi, Sylvia; Gutewort, Sven (2007). "Peroxo Compounds, Inorganic". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a19_177.pub2. ISBN 978-3-527-30673-2.
^ Caro, H. (1898). "Zur Kenntniss der Oxydation aromatischer Amine" [[Contribution] to [our] knowledge of the oxidation of aromatic amines]. Zeitschrift für angewandte Chemie. 11 (36): 845–846. doi:10.1002/ange.18980113602.
^ "Synthesis of Caro's acid". PrepChem.com. 2017-02-13. Retrieved 2018-10-12.
^ A method and apparatus for producing a peroxyacid solution, retrieved 2018-10-12
^ Edwards, J.O. (1955). "Safety". Chem. Eng. News. 33 (32): 3336. doi:10.1021/cen-v033n032.p3336.

[redbookname-1] International Union of Pure and Applied Chemistry (2005). Nomenclature of Inorganic Chemistry (IUPAC Recommendations 2005). Cambridge (UK): RSC–IUPAC. ISBN 0-85404-438-8. p. 139. Electronic version.

[2] "Peroxysulfuric acid (CHEBI:29286)". Chemical Entities of Biological Interest. UK: European Bioinformatics Institute. 20 November 2007. Retrieved 17 November 2011.

[P82db-3] 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 176. ISBN 0-08-029214-3. LCCN 82-16524.

[Ullmann-4] Jakob, Harald; Leininger, Stefan; Lehmann, Thomas; Jacobi, Sylvia; Gutewort, Sven (2007). "Peroxo Compounds, Inorganic". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a19_177.pub2. ISBN 978-3-527-30673-2.

[5] Caro, H. (1898). "Zur Kenntniss der Oxydation aromatischer Amine" [[Contribution] to [our] knowledge of the oxidation of aromatic amines]. Zeitschrift für angewandte Chemie. 11 (36): 845–846. doi:10.1002/ange.18980113602.

[PrepChem-6] "Synthesis of Caro's acid". PrepChem.com. 2017-02-13. Retrieved 2018-10-12.

[Martin_patent-7] A method and apparatus for producing a peroxyacid solution, retrieved 2018-10-12

[8] Edwards, J.O. (1955). "Safety". Chem. Eng. News. 33 (32): 3336. doi:10.1021/cen-v033n032.p3336.

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@@ Line 1: / Line 1: @@
+{{Short description|Powerful oxidizing agent}}
 {{Chembox
 | Verifiedfields = changed
@@ Line 11: / Line 12: @@
 | ImageName1 = Ball and stick model of peroxymonosulfuric acid
 | IUPACNames = Peroxysulfuric acid<br />Sulfuroperoxoic acid<ref name="redbookname">{{RedBookRef|page=139}}</ref>
-| SystematicName = (Dioxidanido)hydroxidodioxidosulfur<ref name="redbookname"/><ref>{{Cite web|title = peroxysulfuric acid (CHEBI:29286)|url = http://www.ebi.ac.uk/chebi/searchId.do?chebiId=CHEBI:29286|work = Chemical Entities of Biological Interest|publisher = European Bioinformatics Institute|accessdate = 17 November 2011|location = UK|date = 20 November 2007}}</ref>
+| SystematicName = (Dioxidanido)hydroxidodioxidosulfur<ref name="redbookname"/><ref>{{Cite web|title = Peroxysulfuric acid (CHEBI:29286)|url = http://www.ebi.ac.uk/chebi/searchId.do?chebiId=CHEBI:29286|work = Chemical Entities of Biological Interest|publisher = European Bioinformatics Institute|access-date = 17 November 2011|location = UK|date = 20 November 2007}}</ref>
 | OtherNames = Peroxosulfuric acid<ref name="redbookname"/><br />Peroxomonosulfuric acid{{Citation needed|date = November 2011}}<br />
-Persulfuric acid{{Citation needed|date = November 2011}}
+Persulfuric acid{{Citation needed|date = November 2011}}<br />Caro's acid
 |Section1={{Chembox Identifiers
-| CASNo = 10361-76-9
+| CASNo = 7722-86-3
-| CASNo_Ref = {{cascite|changed|??}}
+| CASNo_Ref = {{cascite|changed|CAS}}
+| UNII_Ref = {{fdacite|correct|FDA}}
+| UNII = JC6U8R2UJ9
 | PubChem = 2754594
 | ChemSpiderID = 2035480
@@ Line 38: / Line 41: @@
 | Density = 2.239 g cm<sup>−3</sup>
 | ConjugateBase = [[Peroxomonosulfate]]
+| pKa = 1, 9.3<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;176}}</ref>
 | MeltingPt = 45 °C
 }}
@@ Line 47: / Line 51: @@
 }}
 }}
-'''Peroxymonosulfuric acid''', (H<sub>2</sub>SO<sub>5</sub>), also known as '''persulfuric acid''', '''peroxysulfuric acid''', or '''Caro's acid'''.  In this [[acid]], the S(VI) center adopts its characteristic tetrahedral geometry; the connectivity is indicated by the formula HO–O–S(O)<sub>2</sub>–OH. It is one of the strongest oxidants known ([[Electrode potential|''E''<sup>0</sup>]]&nbsp;= +2.51&nbsp;V) and is highly explosive.
+'''Peroxymonosulfuric acid''', also known as '''persulfuric acid''', '''peroxysulfuric acid''' is the [[inorganic compound]] with the formula {{chem2|H2SO5}}.  It is a white solid.  It is a component of '''Caro's acid''', which is a solution of peroxymonosulfuric acid in [[sulfuric acid]] containing small amounts of water.<ref name=Ullmann/>  Peroxymonosulfuric acid is a very strong oxidant ([[Electrode potential|''E''<sup>0</sup>]]&nbsp;= +2.51&nbsp;V).
+==Structure==
-H<sub>2</sub>SO<sub>5</sub> is sometimes confused with H<sub>2</sub>S<sub>2</sub>O<sub>8</sub>, known as [[peroxydisulfuric acid]].  The disulfuric acid, which appears to be more widely used as its alkali metal salts, has the structure HO–S(O)<sub>2</sub>–O–O–S(O)<sub>2</sub>–OH.
+In peroxymonosulfuric acid, the S(VI) center adopts its characteristic tetrahedral geometry; the connectivity is indicated by the formula HO–O–S(O)<sub>2</sub>–OH. The S-O-''H'' proton is more acidic.<ref name=Ullmann>{{cite book |doi=10.1002/14356007.a19_177.pub2 |chapter=Peroxo Compounds, Inorganic |title=Ullmann's Encyclopedia of Industrial Chemistry |date=2007 |last1=Jakob |first1=Harald |last2=Leininger |first2=Stefan |last3=Lehmann |first3=Thomas |last4=Jacobi |first4=Sylvia |last5=Gutewort |first5=Sven |isbn=978-3-527-30673-2 }}</ref>
-<!--what about (HOO)2SO2?, e.g. SO2Cl2 + 2 H2O2 to give the diperoxide?-->
 ==History==
-H<sub>2</sub>SO<sub>5</sub> was first described in 1898 by [[Heinrich Caro]], after whom it is named.<ref>{{cite journal |first=H. |last=Caro |year=1898 |title=Zur Kenntniss der Oxydation aromatischer Amine |trans-title=[Contribution] to [our] knowledge of the oxidation of aromatic amines |journal=[[Angewandte Chemie|Zeitschrift für angewandte Chemie]] |volume=11 |issue=36 |pages=845–846 |url=http://babel.hathitrust.org/cgi/pt?id=mdp.39015073166319;view=1up;seq=855 |doi=10.1002/ange.18980113602 }}</ref>
+The German chemist [[Heinrich Caro]] first reported investigations of mixtures of hydrogen peroxide and sulfuric acid.<ref>{{cite journal |first=H. |last=Caro |year=1898 |title=Zur Kenntniss der Oxydation aromatischer Amine |trans-title=[Contribution] to [our] knowledge of the oxidation of aromatic amines |journal=[[Angewandte Chemie|Zeitschrift für angewandte Chemie]] |volume=11 |issue=36 |pages=845–846 |url=http://babel.hathitrust.org/cgi/pt?id=mdp.39015073166319;view=1up;seq=855 |doi=10.1002/ange.18980113602 }}</ref>
 ==Synthesis and production==
-The laboratory scale preparation of Caro's acid involves the combination of [[chlorosulfuric acid]] and [[hydrogen peroxide]].
+One laboratory scale preparation of Caro's acid involves the combination of [[chlorosulfuric acid]] and [[hydrogen peroxide]]:<ref name="PrepChem">{{Cite web |url=http://www.prepchem.com/synthesis-caros-acid/ |title=Synthesis of Caro's acid |date=2017-02-13 |website=PrepChem.com |language=en-US |access-date=2018-10-12}}</ref>
+:{{chem2 | H2O2 + ClSO2OH <-> H2SO5 + HCl }}
-::H<sub>2</sub>O<sub>2</sub> + ClSO<sub>2</sub>OH   ⇌  H<sub>2</sub>SO<sub>5</sub>  + HCl <ref name="PrepChem">{{Cite web |url=http://www.prepchem.com/synthesis-caros-acid/ |title=Synthesis of Caro's acid |date=2017-02-13 |website=PrepChem.com |language=en-US |access-date=2018-10-12}}</ref>
-Published patents include more than one reaction for preparation of Caro's acid, usually as an intermediate for the production of [[Potassium peroxymonosulfate|potassium monopersulfate (PMPS)]], a bleaching and oxidizing agent.  One patent for production of Caro's acid for this purpose gives the following reaction:
+Patents include more than one reaction for preparation of Caro's acid, usually as an intermediate for the production of [[Potassium peroxymonosulfate|potassium monopersulfate (PMPS)]], a bleaching and oxidizing agent.  One route employs the following reaction:<ref name="Martin patent">{{Citation |title=A method and apparatus for producing a peroxyacid solution |url=https://patents.google.com/patent/WO2005016511A1/da |access-date=2018-10-12}}</ref>
+:{{chem2 | H2O2 + H2SO4 <-> H2SO5 + H2O }}
-::H<sub>2</sub>O<sub>2</sub> + H<sub>2</sub>SO<sub>4</sub> ⇌  H<sub>2</sub>SO<sub>5</sub> + H<sub>2</sub>O<!--probably also made electrochemically-->  <ref name="Martin patent">{{Citation |title=A method and apparatus for producing a peroxyacid solution |url=https://patents.google.com/patent/WO2005016511A1/da |access-date=2018-10-12}}</ref>
+This reaction is related to "[[piranha solution]]".
 ==Uses in industry==
+{{Chem|H|2|S|O|5}} and Caro's acid have been used for a variety of disinfectant and cleaning applications, e.g., swimming pool treatment and denture cleaning.  It is used in [[gold mining]]  to destroy the [[cyanide]] in the waste stream ("[[Tailings]]").
-H<sub>2</sub>SO<sub>5</sub> has been used for a variety of disinfectant and cleaning applications, e.g., swimming pool treatment and denture cleaning.  Alkali metal salts of H<sub>2</sub>SO<sub>5</sub> show promise for the [[lignin|delignification]] of wood.<ref>{{cite journal |title=Treatment of softwood kraft pulps with peroxymonosulfate before oxygen delignification |last=Springer |first=E. L. |last2=McSweeny |first2=J. D. |journal=TAPPI Journal |year=1993 |volume=76 |issue=8 |pages=194–199 |doi= |url=http://www.tappi.org/Bookstore/Technical-Papers/Journal-Articles/TAPPI-JOURNAL/Archives/1993/August/Treatment-of-softwood-kraft-pulps-with-peroxymonosulfate-before-oxygen-delignification-TAPPI-JOURNA.aspx |issn=0734-1415 |access-date=2011-05-14 |archive-url=https://web.archive.org/web/20110929012348/http://www.tappi.org/Bookstore/Technical-Papers/Journal-Articles/TAPPI-JOURNAL/Archives/1993/August/Treatment-of-softwood-kraft-pulps-with-peroxymonosulfate-before-oxygen-delignification-TAPPI-JOURNA.aspx |archive-date=2011-09-29 |url-status=dead }}</ref>
+Alkali metal salts of {{Chem|H|2|S|O|5}}, especially [[oxone]], are widely investigated.
-[[Ammonium]], [[sodium]], and [[potassium]] salts of H<sub>2</sub>SO<sub>5</sub> are used in the [[plastics industry|plastic industry]] as [[polymerization]] initiators, etchants, desizing agents, [[soil conditioner]], and for decolorizing and deodorizing oils.
-[[Potassium peroxymonosulfate]], KHSO<sub>5</sub>, is the [[potassium]] [[acid salt]] of peroxymonosulfuric acid. It is widely used as an [[oxidizing agent]].
 ==Hazards==
-Pure Caro's acid is highly explosive. Explosions have been reported at Brown University<ref>{{cite journal | author = J.O. Edwards | journal = [[Chem. Eng. News]] | volume = 33 | pages = 3336 | year = 1955 | doi = 10.1021/cen-v033n032.p3336 | title = SAFETY | issue = 32}}</ref> and Sun Oil. As with all strong oxidizing agents, peroxysulfuric acid should be kept away from organic compounds such as ethers and ketones because of its ability to peroxidize these compounds, creating highly unstable molecules such as [[acetone peroxide]].
+These peroxy acids can be explosive. Explosions have been reported at [[Brown University]]<ref>{{cite journal | last1 = Edwards | first1 = J.O. | journal = [[Chem. Eng. News]] | volume = 33 | pages = 3336 | year = 1955 | doi = 10.1021/cen-v033n032.p3336 | title = Safety | issue = 32}}</ref> and [[Sun Oil]]. As with all strong oxidizing agents, peroxysulfuric acid is incompatible with [[organic compound]]s.
 ==See also==
-* [[Peroxydisulfuric acid]]
+* [[Peroxydisulfuric acid]] {{Chem|H|2|S|2|O|8}},
 * [[Peroxomonosulfate]]
@@ Line 82: / Line 85: @@
 {{Hydrogen compounds}}
+{{Persulfates}}
-{{sulfur compounds}}
 {{DEFAULTSORT:Peroxymonosulfuric Acid}}
 [[Category:Hydrogen compounds]]
 [[Category:Sulfur oxoacids]]
+[[Category:Liquid explosives]]
 [[Category:Persulfates]]
 [[Category:Peroxy acids]]
-[[Category:Oxidizing agents]]
 [[Category:Explosive chemicals]]