Potassium peroxymonosulfate

"Oxone" redirects here. Not to be confused with the gas ozone.

Not to be confused with Potassium persulfate.

Potassium peroxymonosulfate is widely used as an oxidizing agent, for example, in pools and spas (usually referred to as monopersulfate or "MPS"). It is the potassium salt of peroxymonosulfuric acid. Usually potassium peroxymonosulfate is available as the triple salt 2KHSO₅·KHSO₄·K₂SO₄, known as Oxone.

Potassium peroxymonosulfate

Names
IUPAC name Potassium peroxysulfate
Other names Caroat Oxone potassium monopersulfate MPS KMPS potassium caroate non-chlorine shock^[1]^[2]
Identifiers
CAS Number	10058-23-8^Y 37222-66-5 (triple salt)^Y 70693-62-8^Y
3D model (JSmol)	Interactive image
ChemSpider	8053100^N
ECHA InfoCard	100.030.158
PubChem CID	11804954
UNII	040ZB27861^Y HL6A2XXU5D (triple salt)^Y
CompTox Dashboard (EPA)	DTXSID1034840
InChI InChI=1S/K.H2O5S/c;1-5-6(2,3)4/h;1H,(H,2,3,4)/q+1;/p-1^N Key: OKBMCNHOEMXPTM-UHFFFAOYSA-M^N InChI=1S/K.H2O4S/c;1-4-5(2)3/h;1H,(H,2,3)/q+1;/p-1 Key: GZHFEBOLZPYNER-UHFFFAOYSA-M InChI=1/K.H2O5S/c;1-5-6(2,3)4/h;1H,(H,2,3,4)/q+1;/p-1 Key: OKBMCNHOEMXPTM-REWHXWOFAJ
SMILES [K+].[O-]S(=O)(=O)OO
Properties
Chemical formula	KHSO5
Molar mass	152.2 g/mol (614.76 g/mol as triple salt)
Appearance	Off-white powder
Solubility in water	Decomposes
Hazards
Occupational safety and health (OHS/OSH):
Main hazards	Oxidant, corrosive
NFPA 704 (fire diamond)	^[3] 3 0 1
Safety data sheet (SDS)	Degussa Caroat MSDS
Related compounds
Related compounds	Potassium persulfate
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). N verify (what is ^YN ?) Infobox references

The standard electrode potential for potassium peroxymonosulfate is +1.81 V with a half reaction generating the hydrogen sulfate (pH = 0):^[4]

HSO−5 + 2H⁺ + 2e⁻ → HSO−4 + H₂O

Oxone

Potassium peroxymonosulfate per se is a relatively obscure salt, but its derivative called Oxone is of commercial value. Oxone refers to the triple salt 2KHSO₅·KHSO₄·K₂SO₄. Oxone has a longer shelf life than does potassium peroxymonosulfate. A white, water-soluble solid, Oxone loses <1% of its oxidizing power per month.^[5]

Production

Oxone is produced from peroxysulfuric acid, which is generated in situ by combining oleum and hydrogen peroxide. Careful neutralization of this solution with potassium hydroxide allows the crystallization of the triple salt.

Uses

Cleaning

Oxone is used widely for cleaning. It whitens dentures,^[6] oxidizes organic contaminants in swimming pools,^{[citation needed]} and cleans chips for the manufacture of microelectronics.^[6][7][8]

Organic chemistry

Oxone is a versatile oxidant in organic synthesis. It oxidizes aldehydes to carboxylic acids; in the presence of alcoholic solvents, the esters may be obtained.^[9] Internal alkenes may be cleaved to two carboxylic acids (see below), while terminal alkenes may be epoxidized. Sulfides give sulfones, tertiary amines give amine oxides, and phosphines give phosphine oxides.

Further illustrative of the oxidative power of this salt is the conversion of an acridine derivative to the corresponding acridine-N-oxide.^[10]

 

Oxone oxidizes sulfides to sulfoxides and then to sulfones.^[11]

 

Oxone converts ketones to dioxiranes. The synthesis of dimethyldioxirane (DMDO) from acetone is representative. Dioxiranes are versatile oxidising agents and may be used for the epoxidation of olefins. In particular, if the starting ketone is chiral then the epoxide may be generated enantioselectively, which forms the basis of the Shi epoxidation.^[12]

 

The Shi epoxidation

References

1. Wu, Mingsong; Xu, Xinyang; Xu, Xun (November 2014). "Algicidal and Bactericidal Effect of Potassium Monopersulfate Compound on Eutrophic Water". Applied Mechanics and Materials. 707: 259. doi:10.4028/www.scientific.net/AMM.707.259. S2CID 98000605.
2. Pool School. Trouble Free Pool. p. PT4. Retrieved November 30, 2018.
3. (PDF). Archived from the original (PDF) on 2014-08-15. Retrieved 2012-01-26.
4. Spiro, M. (1979). "The standard potential of the peroxosulphate/sulphate couple". Electrochimica Acta. 24 (3): 313–314. doi:10.1016/0013-4686(79)85051-3. ISSN 0013-4686.
5. Crandall, Jack K.; Shi, Yian; Burke, Christopher P.; Buckley, Benjamin R. (2001). Encyclopedia of Reagents for Organic Synthesis. John Wiley & Sons, Ltd. doi:10.1002/047084289x.rp246.pub3. ISBN 978-0-470-84289-8.
6. Harald Jakob; Stefan Leininger; Thomas Lehmann; Sylvia Jacobi; Sven Gutewort. "Peroxo Compounds, Inorganic". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a19_177.pub2. ISBN 978-3527306732.
7. Peroxy Compounds Human Health and Ecological Draft Risk Assessment DP 455445, 455446 (Report). United States Environmental Protection Agency. 2020-03-11. p. 9-10. Retrieved 2021-09-24.
8. Wacławek, Stanisław; Lutze, Holger V.; Grübel, Klaudiusz; Padil, Vinod V.T.; Černík, Miroslav; Dionysiou, Dionysios. D. (2017-12-15). "Peroxy Compounds Human Health and Ecological Draft Risk Assessment DP 455445, 455446". Chemical Engineering Journal. 330: 44–62. doi:10.1016/j.cej.2017.07.132.
9. Benjamin R. Travis; Meenakshi Sivakumar; G. Olatunji Hollist & Babak Borhan (2003). "Facile Oxidation of Aldehydes to Acids and Esters with Oxone". Organic Letters. 5 (7): 1031–4. doi:10.1021/ol0340078. PMID 12659566.
10. Bell, Thomas W.; Cho, Young-Moon; Firestone, Albert; Healy, Karin; Liu, Jia; Ludwig, Richard; Rothenberger, Scott D. (1990). "9-n-Butyl-1,2,3,4,5,6,7,8-Octahydroacridin-4-ol". Organic Syntheses. 69: 226. doi:10.15227/orgsyn.069.0226.
11. McCarthy, James R.; Matthews, Donald P.; P. Paolini, John (1995). "Reaction of Sulfoxides with Diethylaminosulfur Trifluoride". Organic Syntheses. 72: 209. doi:10.15227/orgsyn.072.0209.
12. Frohn, Michael; Shi, Yian (2000). "Chiral Ketone-Catalyzed Asymmetric Epoxidation of Olefins". Synthesis. 2000 (14): 1979–2000. doi:10.1055/s-2000-8715.