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A peroxy acid (often spelled as one word, peroxyacid, and sometimes called peracid) is an acid which contains an acidic –OOH group. The two main classes are those derived from conventional mineral acids, especially sulfuric acid, and the peroxy derivatives of organic carboxylic acids. They are generally strong oxidizers.

Inorganic peroxy acids

Peroxymonosulfuric acid (Caro's acid) is probably the most important inorganic peracid, at least in terms of its production scale.^[1] It is used for the bleaching of pulp and for the detoxification of cyanide in the mining industry. It is produced by treating sulfuric acid with hydrogen peroxide. Peroxymonophosphoric acid (H₃PO₅) is prepared similarly.^[2]

Some peroxy acids are only hypothetical, but their anions are known. This is the case for peroxycarbonate^[3] and perborate (see sodium perborate).^[4]

Organic peracids

Several organic peroxyacids are commercially useful.^[5] They can be prepared in several ways. Most commonly, peracids are generated by treating the corresponding carboxylic acid with hydrogen peroxide:^[6]

RCO₂H + H₂O₂ ⇌ RCO₃H + H₂O

A related reaction involves treatment of the carboxylic anhydride:

(RCO)₂O + H₂O₂ → RCO₃H + RCO₂H

This method is popular for converting cyclic anhydrides to the corresponding monoperoxyacids, for example monoperoxyphthalic acid.
The third method involves treatment of acid chlorides:

RC(O)Cl + H₂O₂ → RCO₃H + HCl

meta-Chloroperoxybenzoic acid (mCPBA) is prepared in this way.^[7]

A related method starts with the peroxyanhydride.^[8]

Aromatic aldehydes can be autoxidized to give peroxycarboxylic acids:

Ar-CHO + O₂ → Ar-COOOH (Ar = aryl group)

The products, however, react with the initial aldehyde forming the carboxylic acid:

Ar-COOOH + Ar-CHO → 2 Ar-COOH

Properties and uses

In terms of acidity, peroxycarboxylic acids are about 1000 times weaker than the parent carboxylic acid, due to the absence of resonance stabilization of the anion. For similar reasons, their pK_a values tend also to be relatively insensitive to substituents.

The most common use of organic peroxy acids is for the conversion of alkenes to epoxides, the Prilezhaev reaction. Another common reaction is conversion of cyclic ketones to the ring-expanded esters using peracids in a Baeyer-Villiger oxidation. They are also used for the oxidation of amines and thioethers to amine oxides and sulfoxides. The laboratory applications of the valued reagent mCPBA illustrate these reactions.

Reaction of peroxycarboxylic acids with acid chlorides affords diacyl peroxides:

RC(O)Cl + RC(O)O₂H → (RC(O))₂O₂ + HCl

The oxidizing tendency of peroxides is related to the electronegativity of the substituents. Electrophilic peroxides are stronger oxygen-atom transfer agents. The oxygen-atom donor tendency correlates with the acidity of the O−H bond. Thus, the order of oxidizing power is CF₃CO₃H > CH₃CO₃H > H₂O₂.

Usage

Peroxycarboxylic acids are available in both solid and liquid forms. Due to their oxidizing and disinfecting properties, they can be used in both professional and domestic settings.^[9]

Bleaching Agents

Peroxycarboxylic acids are bleaching agents and are used globally, particularly for tooth whitening. They are employed in various concentrations in dentistry to effectively bleach teeth. Lower concentrations are common for home use. Compared to hydrogen peroxide, peroxycarboxylic acids are approved as cosmetics in Europe under Regulation (EC) No. 1223/2009 of the European Parliament.^[10]

Bleaching Agents

In healthcare, peroxycarboxylic acids are primarily used for wound disinfection and cleaning contact lenses.

Peroxycarboxylic acids are also found in cleaning agents, disinfectants, and detergents, as they reliably kill germs and bacteria.

References

^ Harald Jakob; et al. "Peroxy Compounds, Inorganic". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a19_177.pub2. ISBN 978-3527306732.
^ Creaser, I.I.; Edwards, J.O. (1972). "?". Topics in Phosphorus Chemistry. 7: 379–435.
^ Chen, Li-Jiang; Lin, Chang-Jian; Zuo, Juan; Song, Ling-Chun; Huang, Chao-Ming (2004). "First Spectroscopic Observation of Peroxocarbonate/ Peroxodicarbonate in Molten Carbonate". The Journal of Physical Chemistry B. 108 (23): 7553–7556. doi:10.1021/jp035749l.
^ "perborate(2-) (CHEBI:30175)". www.ebi.ac.uk.
^ Herbert Klenk; Peter H. Götz; Rainer Siegmeier; Wilfried Mayr. "Peroxy Compounds, Organic". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a19_199. ISBN 978-3527306732.
^ Silbert, L. S.; Siegel, E.; Swern, D. (1964). "Peroxybenzoic Acid". Org. Synth. 44: 81. doi:10.15227/orgsyn.044.0081.
^ Richard N. McDonald; Richard N. Steppel; James E. Dorsey (1970). "m-Chloroperbenzoic Acid". Org. Synth. 50: 15. doi:10.15227/orgsyn.050.0015.
^ Géza Braun (1928). "Perbenzoic Acid". Org. Synth. 8: 30. doi:10.15227/orgsyn.008.0030.
^ "Peroxygens". Solvay.
^ "Verordnung - 1223/2009 - EN - EUR-Lex".

[1] Harald Jakob; et al. "Peroxy Compounds, Inorganic". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a19_177.pub2. ISBN 978-3527306732.

[2] Creaser, I.I.; Edwards, J.O. (1972). "?". Topics in Phosphorus Chemistry. 7: 379–435.

[chen-3] Chen, Li-Jiang; Lin, Chang-Jian; Zuo, Juan; Song, Ling-Chun; Huang, Chao-Ming (2004). "First Spectroscopic Observation of Peroxocarbonate/ Peroxodicarbonate in Molten Carbonate". The Journal of Physical Chemistry B. 108 (23): 7553–7556. doi:10.1021/jp035749l.

[4] "perborate(2-) (CHEBI:30175)". www.ebi.ac.uk.

[5] Herbert Klenk; Peter H. Götz; Rainer Siegmeier; Wilfried Mayr. "Peroxy Compounds, Organic". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a19_199. ISBN 978-3527306732.

[6] Silbert, L. S.; Siegel, E.; Swern, D. (1964). "Peroxybenzoic Acid". Org. Synth. 44: 81. doi:10.15227/orgsyn.044.0081.

[7] Richard N. McDonald; Richard N. Steppel; James E. Dorsey (1970). "m-Chloroperbenzoic Acid". Org. Synth. 50: 15. doi:10.15227/orgsyn.050.0015.

[8] Géza Braun (1928). "Perbenzoic Acid". Org. Synth. 8: 30. doi:10.15227/orgsyn.008.0030.

[9] "Peroxygens". Solvay.

[10] "Verordnung - 1223/2009 - EN - EUR-Lex".

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@@ Line 1: / Line 1: @@
+{{Short description|Organic acid having a peroxide bond}}
-[[File:Peracid Acid General Formulae V.1.png|right|thumb|160px|General formulae of an organic peroxy acid (top) compared with a carboxylic acid (bottom).]]
+[[File:Peracid Acid General Formulae V.1.png|right|thumb|160px|General formulas of an organic peroxy acid (top) compared with a carboxylic acid (bottom).]]
-A '''peroxy acid''' (often spelled as one word, '''peroxyacid''', and sometimes called '''peracid''') is an [[acid]] which contains an acidic -OOH group.  The two main classes are those derived from conventional mineral acids, especially sulfuric acid, and the organic derivatives of carboxylic acids.  They are generally strong [[oxidizer]]s.
+A '''peroxy acid''' (often spelled as one word, '''peroxyacid''', and sometimes called '''peracid''') is an [[acid]] which contains an acidic –OOH group.  The two main classes are those derived from conventional [[mineral acid]]s, especially [[sulfuric acid]], and the peroxy derivatives of organic [[carboxylic acid]]s.  They are generally strong [[oxidizer]]s.
 ==Inorganic peroxy acids==
-{{main|Peroxymonosulfuric acid}}
+{{See also|Peroxymonosulfuric acid|Peroxynitric acid|Peroxymonophosphoric acid}}
-[[Peroxysulfuric acid]] (Caro's acid) is probably the most important inorganic peracid, at least in terms of the scale.<ref>{{Ullmann | author = Harald Jakob et al. | title = Peroxy Compounds, Inorganic | doi = 10.1002/14356007.a19_177.pub2}}</ref> It is used for the bleaching of [[pulp (paper)|pulp]] and for the detoxification of cyanide in the mining industry. It is produced by treating sulfuric acid with [[hydrogen peroxide]]. Peroxyphosphoric acid (H<sub>3</sub>PO<sub>5</sub>) is prepared similarly.
+[[Peroxymonosulfuric acid]] (Caro's acid) is probably the most important inorganic peracid, at least in terms of its production scale.<ref>{{Ullmann | author = Harald Jakob |display-authors=etal | title = Peroxy Compounds, Inorganic | doi = 10.1002/14356007.a19_177.pub2}}</ref> It is used for the bleaching of [[pulp (paper)|pulp]] and for the detoxification of cyanide in the mining industry. It is produced by treating sulfuric acid with [[hydrogen peroxide]]. [[Peroxymonophosphoric acid]] (H<sub>3</sub>PO<sub>5</sub>) is prepared similarly.<ref>{{cite journal |last1=Creaser |first1=I.I. |last2=Edwards |first2=J.O. |journal=Topics in Phosphorus Chemistry |date=1972 |volume=7|title=? |pages=379–435 }}</ref>
+Some peroxy acids are only hypothetical, but their anions are known. This is the case for [[peroxycarbonate]]<ref name="chen">{{cite journal | doi = 10.1021/jp035749l | title = First Spectroscopic Observation of Peroxocarbonate/ Peroxodicarbonate in Molten Carbonate | year = 2004 | last1 = Chen | first1 = Li-Jiang | last2 = Lin | first2 = Chang-Jian | last3 = Zuo | first3 = Juan | last4 = Song | first4 = Ling-Chun | last5 = Huang | first5 = Chao-Ming | journal = The Journal of Physical Chemistry B | volume = 108 | issue = 23 | pages = 7553–7556 }}</ref> and [[perborate]] (see [[sodium perborate]]).<ref>{{cite web |title=perborate(2-) (CHEBI:30175) |url=https://www.ebi.ac.uk/chebi/searchId.do?chebiId=CHEBI:30175 |website=www.ebi.ac.uk}}</ref>
-==Organic peracids==
-Several organic peroxyacids are commercially useful.<ref>{{Ullmann | author = Herbert Klenk, Peter H. Götz, Rainer Siegmeier, Wilfried Mayr | title = Peroxy Compounds, Organic | doi = 10.1002/14356007.a19_199}}</ref> They can be prepared in several ways.  Most commonly, peracids are generated by treating the corresponding [[carboxylic acid]] with hydrogen peroxide:
+=={{anchor|Peroxycarboxylic acid}}Organic peracids==
-:RCO<sub>2</sub>H  +  H<sub>2</sub>O<sub>2</sub>   <math>\overrightarrow{\leftarrow}</math>   RCO<sub>3</sub>H  +  H<sub>2</sub>O
+Several organic peroxyacids are commercially useful.<ref>{{Ullmann |author=Herbert Klenk |author2=Peter H. Götz |author3=Rainer Siegmeier |author4=Wilfried Mayr | title = Peroxy Compounds, Organic | doi = 10.1002/14356007.a19_199}}</ref> They can be prepared in several ways.  Most commonly, peracids are generated by treating the corresponding [[carboxylic acid]] with hydrogen peroxide:<ref>{{cite journal |author=Silbert, L. S. |author2=Siegel, E. |author3=[[Swern oxidation|Swern]], D. |journal=Org. Synth.| title = Peroxybenzoic Acid | volume = 44 | pages = 81 | year = 1964 | doi = 10.15227/orgsyn.044.0081}}</ref>
+:RCO<sub>2</sub>H  +  H<sub>2</sub>O<sub>2</sub>   {{eqm}}   RCO<sub>3</sub>H  +  H<sub>2</sub>O
 A related reaction involves treatment of the carboxylic anhydride:
 :(RCO)<sub>2</sub>O  +  H<sub>2</sub>O<sub>2</sub>   →   RCO<sub>3</sub>H  +  RCO<sub>2</sub>H
-This method is popular for converting cyclic anhydrides to the corresponding monoperoxyacids, for example monoperoxyphthalic acid.</br>
+This method is popular for converting cyclic anhydrides to the corresponding monoperoxyacids, for example monoperoxyphthalic acid.<br />
 The third method involves treatment of [[acid chloride]]s:
 :RC(O)Cl  +  H<sub>2</sub>O<sub>2</sub>   →   RCO<sub>3</sub>H  +  HCl
-[[Meta-Chloroperoxybenzoic acid|''meta''-chloroperoxybenzoic acid]] (mCPBA) is prepared in this way.
+[[Meta-Chloroperoxybenzoic acid|''meta''-Chloroperoxybenzoic acid]] (''m''CPBA) is prepared in this way.<ref>{{cite journal |author=Richard N. McDonald |author2=Richard N. Steppel |author3=James E. Dorsey |journal=Org. Synth.| title = m-Chloroperbenzoic Acid | volume = 50 | pages = 15 | year = 1970 | doi = 10.15227/orgsyn.050.0015}}</ref>
+A related method starts with the peroxyanhydride.<ref>{{cite journal | title = Perbenzoic Acid |journal=Org. Synth. |author=Géza Braun | volume = 8 | pages = 30 | year = 1928 | doi = 10.15227/orgsyn.008.0030}}</ref>
+Aromatic [[aldehydes]] can be [[autoxidation|autoxidized]] to give peroxycarboxylic acids:
+:Ar-CHO + O<sub>2</sub> → Ar-COOOH (Ar = [[aryl]] group)
+The products, however, react with the initial aldehyde forming the carboxylic acid:
+:Ar-COOOH + Ar-CHO → 2 Ar-COOH
 ===Properties and uses===
-Peroxycarboxylic acids are about 1000x weaker than the parent carboxylic acid, owing the absence of resonance stabilization of the anion.  For similar reasons, their pK<sub>a</sub>s tend also to be relatively insensitive to the substituent R.
+In terms of acidity, peroxycarboxylic acids are about 1000 times weaker than the parent carboxylic acid, due to the absence of [[Resonance (chemistry)|resonance]] stabilization of the anion.  For similar reasons, their p''K''<sub>a</sub> values tend also to be relatively insensitive to substituents.
-The largest use of organic peroxy acids is for the conversion of alkenes to epoxides.  Certain cyclic ketones are converted to the ring-expanded esters using peracids in a [[Baeyer-Villiger oxidation]].  They are also used for the oxidation of [[amine]]s and [[thioether]]s to [[amine oxide]]s and [[sulfoxide]]s.  The laboratory applications of the valued reagent [[mCPBA]] illustrate these reactions.  It is used as a [[reagent]] in the Baeyer-Villiger oxidation and in oxidation of [[carbon]]-carbon [[double bond]]s in [[alkene]]s to generate [[epoxide]]s (oxiranes).  Reaction of peroxycarboxylic acids with acid chlorides affords diacyl peroxides:
+The most common use of organic peroxy acids is for the conversion of alkenes to epoxides, the [[Prilezhaev reaction]].  Another common reaction is conversion of cyclic ketones to the ring-expanded esters using peracids in a [[Baeyer-Villiger oxidation]].  They are also used for the oxidation of [[amine]]s and [[thioether]]s to [[amine oxide]]s and [[sulfoxide]]s.  The laboratory applications of the valued reagent ''m''CPBA illustrate these reactions.
+Reaction of peroxycarboxylic acids with acid chlorides affords diacyl peroxides:
-:RC(O)Cl  +  RC<sub>2</sub>O<sub>2</sub>H   →   (RCO)<sub>2</sub>O<sub>2</sub>  +  HCl
+:RC(O)Cl  +  RC(O)O<sub>2</sub>H   →   (RC(O))<sub>2</sub>O<sub>2</sub>  +  HCl
+The oxidizing tendency of peroxides is related to the [[electronegativity]] of the substituents. [[Electrophilic]] peroxides are stronger oxygen-atom transfer agents. The oxygen-atom donor tendency correlates with the [[acidity]] of the O−H bond. Thus, the order of oxidizing power is CF<sub>3</sub>CO<sub>3</sub>H > CH<sub>3</sub>CO<sub>3</sub>H > H<sub>2</sub>O<sub>2</sub>.
+==Usage==
+Peroxycarboxylic acids are available in both solid and liquid forms. Due to their oxidizing and disinfecting properties, they can be used in both professional and domestic settings.<ref>{{cite web |url=https://www.solvay.com/en/chemical-categories/peroxygens |publisher=Solvay |title=Peroxygens}}</ref>
+===Bleaching Agents===
+Peroxycarboxylic acids are bleaching agents and are used globally, particularly for tooth whitening. They are employed in various concentrations in dentistry to effectively bleach teeth. Lower concentrations are common for home use. Compared to hydrogen peroxide, peroxycarboxylic acids are approved as cosmetics in Europe under Regulation (EC) No. 1223/2009 of the European Parliament.<ref>{{cite web |url=https://eur-lex.europa.eu/eli/reg/2009/1223/oj/deu |title=Verordnung - 1223/2009 - EN - EUR-Lex }}</ref>
+===Bleaching Agents===
+In healthcare, peroxycarboxylic acids are primarily used for wound disinfection and cleaning contact lenses.
+Peroxycarboxylic acids are also found in cleaning agents, disinfectants, and detergents, as they reliably kill germs and bacteria.
 ==See also==
 * [[Organic peroxide]]
-* [[Meta-Chloroperoxybenzoic acid]]
 * [[Peracetic acid]]
 * [[Peroxyacyl nitrates]]
@@ Line 31: / Line 58: @@
 <references/>
+{{Authority control}}
 {{DEFAULTSORT:Peroxy Acid}}
-[[Category:Oxidizing agents]]
+[[Category:Organic peroxy acids]]
-[[Category:Peroxy acids]]
+[[Category:Peroxy acids| ]]
-[[Category:Functional groups]]
-[[cs:Peroxidová kyselina]]
-[[de:Peroxycarbonsäuren]]
-[[es:Ácido peroxi]]
-[[fr:Peracide]]
-[[it:Perossiacido]]
-[[nl:Peroxycarbonzuur]]
-[[ja:過酸]]
-[[ru:Надкислоты]]
-[[sk:Peroxokyselina]]
-[[uk:Надкислоти]]
-[[zh:过氧酸]]