Hypochlorous acid
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IUPAC name
Hypochlorous acid
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Other names
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Identifiers | |
3D model (
JSmol ) |
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ChEBI | |
ChemSpider | |
ECHA InfoCard
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100.029.302 |
EC Number |
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PubChem CID
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UNII | |
CompTox Dashboard (EPA)
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Properties | |
HOCl | |
Molar mass | 52.46 g·mol−1 |
Appearance | Colorless aqueous solution |
Density | Variable |
Soluble | |
Acidity (pKa) | 7.53[1] |
Conjugate base
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Hypochlorite |
Hazards | |
Occupational safety and health (OHS/OSH): | |
Main hazards
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corrosive, oxidizing agent |
GHS labelling: | |
H320, H335 | |
P301+P330+P331, P302+P352, P304+P340, P305+P351+P338 | |
NFPA 704 (fire diamond) | |
Safety data sheet (SDS) | chemfresh.com |
Related compounds | |
Other anions
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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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Hypochlorous acid is an
Because of its strong antimicrobial properties, the related compounds
Like many other disinfectants, hypochlorous acid solutions will destroy
History
Hypochlorous acid was discovered in 1834 by the French chemist Antoine Jérôme Balard (1802–1876) by adding, to a flask of chlorine gas, a dilute suspension of mercury(II) oxide in water.[10] He also named the acid and its compounds.[11]
Despite being relatively easy to make, it is difficult to maintain a stable hypochlorous acid solution. It is not until recent years that scientists have been able to cost-effectively produce and maintain hypochlorous acid water for stable commercial use.
Uses
- In chlorohydrins.[12]
- In biology, hypochlorous acid is generated in activated neutrophils by myeloperoxidase-mediated peroxidation of chloride ions, and contributes to the destruction of bacteria.[13][14][15]
- In medicine, hypochlorous acid water has been used as a disinfectant and sanitiser.[6][9][5]
- In wound care,[16][17][18] and as of early 2016 the U.S. Food and Drug Administration has approved products whose main active ingredient is hypochlorous acid for use in treating wounds and various infections in humans and pets. It is also FDA-approved as a preservative for saline solutions.
- In disinfection, it has been used in the form of liquid spray, wet wipes and aerosolised application. Recent studies have shown hypochlorous acid water to be suitable for fog and aerosolised application for disinfection chambers and suitable for disinfecting indoor settings such as offices, hospitals and healthcare clinics.[19]
- In food service and water distribution, specialized equipment to generate weak solutions of HClO from water and salt is sometimes used to generate adequate quantities of safe (unstable) disinfectant to treat food preparation surfaces and water supplies.[20][21] It is also commonly used in restaurants due to its non-flammable and nontoxic characteristics.
- In water treatment, hypochlorous acid is the active sanitizer in hypochlorite-based products (e.g. used in swimming pools).[22]
- Similarly, in ships and yachts, marine sanitation devices[23] use electricity to convert seawater into hypochlorous acid to disinfect macerated faecal waste before discharge into the sea.
- In deodorization, hypochlorous acid has been tested to remove up to 99% of foul odours including garbage, rotten meat, toilet, stool, and urine odours.[citation needed]
Formation, stability and reactions
Addition of chlorine to water gives both hydrochloric acid (HCl) and hypochlorous acid (HClO):[24]
- Cl2 + H2O ⇌ HClO + HCl
- Cl2 + 4 OH− ⇌ 2 ClO− + 2 H2O + 2 e−
- Cl2 + 2 e− ⇌ 2 Cl−
When acids are added to aqueous salts of hypochlorous acid (such as sodium hypochlorite in commercial bleach solution), the resultant reaction is driven to the left, and chlorine gas is formed. Thus, the formation of stable hypochlorite bleaches is facilitated by dissolving chlorine gas into basic water solutions, such as sodium hydroxide.
The acid can also be prepared by dissolving dichlorine monoxide in water; under standard aqueous conditions, anhydrous hypochlorous acid is currently impossible to prepare due to the readily reversible equilibrium between it and its anhydride:[25]
- 2 HClO ⇌ Cl2O + H2O, K = 3.55 × 10−3 dm3/mol (at 0 °C)
The presence of light or transition metal oxides of copper, nickel, or cobalt accelerates the exothermic[dubious ] decomposition into hydrochloric acid and oxygen:[25]
- 2 Cl2 + 2 H2O → 4 HCl + O2
Fundamental reactions
In aqueous solution, hypochlorous acid partially dissociates into the anion hypochlorite ClO−:
- HClO ⇌ ClO− + H+
Salts of hypochlorous acid are called hypochlorites. One of the best-known hypochlorites is NaClO, the active ingredient in bleach.
HClO is a stronger oxidant than chlorine under standard conditions.
- 2 HClO(aq) + 2 H+ + 2 e− ⇌ Cl2(g) + 2 H2O, E = +1.63 V
HClO reacts with HCl to form chlorine:
- HClO + HCl → H2O + Cl2
HClO reacts with ammonia to form monochloramine:
- NH3 + HClO → NH2Cl + H2O
HClO can also react with organic
Hypochlorous acid exists in equilibrium with its
- 2 HClO ⇌ Cl2O + H2O, K = 3.55 × 10−3 dm3/mol (at 0 °C)
Reactivity of HClO with biomolecules
Hypochlorous acid reacts with a wide variety of biomolecules, including DNA, RNA,[15][26][27][28] fatty acid groups, cholesterol[29][30][31][32][33][34][35][36] and proteins.[32][37][38][39][40][41][42]
Reaction with protein sulfhydryl groups
Knox et al.
Reaction with protein amino groups
Hypochlorous acid reacts readily with amino acids that have
Reaction with DNA and nucleotides
Hypochlorous acid reacts slowly with DNA and RNA as well as all nucleotides in vitro.[26][47] GMP is the most reactive because HClO reacts with both the heterocyclic NH group and the amino group. In similar manner, TMP with only a heterocyclic NH group that is reactive with HClO is the second-most reactive. AMP and CMP, which have only a slowly reactive amino group, are less reactive with HClO.[47] UMP has been reported to be reactive only at a very slow rate.[15][26] The heterocyclic NH groups are more reactive than amino groups, and their secondary chloramines are able to donate the chlorine.[28] These reactions likely interfere with DNA base pairing, and, consistent with this, Prütz[47] has reported a decrease in viscosity of DNA exposed to HClO similar to that seen with heat denaturation. The sugar moieties are nonreactive and the DNA backbone is not broken.[47] NADH can react with chlorinated TMP and UMP as well as HClO. This reaction can regenerate UMP and TMP and results in the 5-hydroxy derivative of NADH. The reaction with TMP or UMP is slowly reversible to regenerate HClO. A second slower reaction that results in cleavage of the pyridine ring occurs when excess HClO is present. NAD+ is inert to HClO.[28][47]
Reaction with lipids
Hypochlorous acid reacts with
Mode of disinfectant action
E. coli exposed to hypochlorous acid lose viability in less than 0.1 seconds due to inactivation of many vital systems.[24][51][52][53][54] Hypochlorous acid has a reported LD50 of 0.0104–0.156 ppm[55] and 2.6 ppm caused 100% growth inhibition in 5 minutes.[45] However, the concentration required for bactericidal activity is also highly dependent on bacterial concentration.[40]
Inhibition of glucose oxidation
In 1948, Knox et al.
Depletion of adenine nucleotides
Having eliminated loss of respiration, Albrich et al.
Inhibition of DNA replication
Recently it has been proposed that bacterial inactivation by HClO is the result of inhibition of DNA replication. When bacteria are exposed to HClO, there is a precipitous decline in DNA synthesis that precedes inhibition of protein synthesis, and closely parallels loss of viability.[45][63] During bacterial genome replication, the origin of replication (oriC in E. coli) binds to proteins that are associated with the cell membrane, and it was observed that HClO treatment decreases the affinity of extracted membranes for oriC, and this decreased affinity also parallels loss of viability. A study by Rosen et al.[64] compared the rate of HClO inhibition of DNA replication of plasmids with different replication origins and found that certain plasmids exhibited a delay in the inhibition of replication when compared to plasmids containing oriC. Rosen's group proposed that inactivation of membrane proteins involved in DNA replication are the mechanism of action of HClO.
Protein unfolding and aggregation
HClO is known to cause post-translational modifications to
Hypochlorites
Hypochlorites are the salts of hypochlorous acid; commercially important hypochlorites are calcium hypochlorite and sodium hypochlorite.
Production of hypochlorites using electrolysis
Solutions of hypochlorites can be produced in-situ by electrolysis of an aqueous sodium chloride solution in both batch and flow processes.[66] The composition of the resulting solution depends on the pH at the anode. In acid conditions the solution produced will have a high hypochlorous acid concentration, but will also contain dissolved gaseous chlorine, which can be corrosive, at a neutral pH the solution will be around 75% hypochlorous acid and 25% hypochlorite. Some of the chlorine gas produced will dissolve forming hypochlorite ions. Hypochlorites are also produced by the disproportionation of chlorine gas in alkaline solutions.
Safety
HClO is classified as Non-Hazardous by the Environmental Protection Agency in the US. As any oxidising agent it can be corrosive or irritant depending on its concentration and pH.
In a clinical test, hypochlorous acid water was tested for eye irritation, skin irritation, and toxicity. The test concluded that it was non-toxic and nonirritating to the eye and skin.[67]
In a 2017 study, a saline hygiene solution preserved with pure hypochlorous acid was shown to reduce the bacterial load significantly without altering the diversity of bacterial species on the eyelids. After 20 minutes of treatment, there was >99% reduction of the Staphylococci bacteria.[68]
Commercialisation
For disinfection, despite being discovered a long time ago, the stability of hypochlorous acid water is difficult to maintain. In solution, the active compounds quickly deteriorate back into salt water, losing its disinfecting capability, which makes it difficult to transport for wide use. Despite its stronger disinfecting capabilities, it is less commonly used as a disinfectant compared to bleach and alcohol due to cost.
Technological developments have reduced manufacturing costs and allow for manufacturing and bottling of hypochlorous acid water for home and commercial use. However, most hypochlorous acid water has a short shelf life. Storing away from heat and direct sunlight can help slow the deterioration. The further development of continuous flow electrochemical cells has been implemented in new products, allowing the commercialisation of domestic and industrial continuous flow devices for the in-situ generation of hypochlorous acid for disinfection purposes.[69]
See also
- Dichlorine monoxide: the corresponding acidic oxide
- Hypofluorous acid
- Perchloric acid
References
- ^ Harris, Daniel C. (2009). Exploring Chemical Analysis (Fourth ed.). p. 538.
- ^ "Hypochlorous acid". CAS Common Chemistry. CAS, a division of the American Chemical Society, n.d. CAS RN: 7790-92-3. Retrieved 2022-04-12.
- ^ "hypochlorous acid". Chemical Entities of Biological Interest. European Bioinformatics Institute. CHEBI:24757. Retrieved 2022-04-12.
- ^ Sansebastiano, G. et al. Page 262 in Food Safety: A Practical and Case Study Approach (Ed: R. J. Marshall) 2006, Springer Science & Business Media, Berlin.
- ^ PMID 32653307.
- ^ a b "Treating Chronic Wounds With Hypochlorous Acid Disrupts Biofilm". Today's Wound Clinic. Retrieved 2021-02-08.
- PMID 27178483.
- ^ US EPA, OCSPP (2020-03-13). "List N: Disinfectants for Coronavirus (COVID-19)". US EPA. Retrieved 2021-02-08.
- ^ a b "Pure Hypochlorous Acid: A Primer on pH and Wound Solutions". WoundSource. 2020-11-05. Retrieved 2021-02-08..
- ^ See:
- Balard, A. J. (1834). "Recherches sur la nature des combinaisons décolorantes du chlore" [Investigations into the nature of bleaching compounds of chlorine]. Annales de Chimie et de Physique. 2nd series (in French). 57: 225–304. From p. 246: " … il est beaucoup plus commode … environ d'eau distillée." ( … it is much easier to pour, into flasks full of chlorine, red mercury oxide [that has been] reduced to a fine powder by grinding and diluted in about twelve times its weight of distilled water.)
- Graham, Thomas (1840). Elements of Chemistry. Vol. 4. London, England: H. Baillière. p. 367.
- ^ (Balard, 1834), p. 293. From p. 293: "Quelle dénomination … appelées hypochlorites." (What name should one assign to this compound? It's obvious that that of "chlorous acid" can hardly be retained for it, and that it is more appropriate to call it hypochlorous acid, a name that recalls its similarity of composition with hyposulfurous acid, hypophosphorous acid, etc., [which are] formed, like it, from 1 equivalent of their radical and 1 equivalent of oxygen. Its compounds will be called hypochlorites.)
- PMID 176150.
- ^ PMID 217834.
- ^ PMID 6264434.)
{{cite journal}}
: CS1 maint: multiple names: authors list (link - ^ Wang L et al. "Hypochlorous acid as a potential wound care agent. Part I Stabilized hypochlorous acid: a component of the inorganic armamentarium of innate immunity". J Burns and Wounds 2007; April: 65–79.
- ^ Robson MC et al. "Hypochlorous acid as a potential wound care agent. Part II Stabilized hypochlorous acid: its role in decreasing tissue bacterial bioburden and overcoming the inhibition of infection on wound healing". Journal of Burns and Wounds 2007; April: 80–90.
- PMID 16669304.
- PMID 33519249.
- ^ "Disinfection of Facility H2O" Archived 2019-01-22 at the Wayback Machine.
- ^ "Water Works: Hyatt's New Disinfectant/Cleaner Comes from the Tap", Bloomberg Businessweek.
- ISBN 9780060936778.
Similarly, we add HOCl to swimming pools to kill bacteria.
- ^ e.g. Raritan Electro Scan device
- ^ PMID 18145494.)
{{cite journal}}
: CS1 maint: multiple names: authors list (link - ^ a b c Inorganic chemistry, Egon Wiberg, Nils Wiberg, Arnold Frederick Holleman, "Hypochlorous acid", p. 442, section 4.3.1
- ^ doi:10.1016/0043-1354(79)90023-X.)
{{cite journal}}
: CS1 maint: multiple names: authors list (link - ^ Jacangelo, J. G., and V. P. Olivieri. 1984. Aspects of the mode of action of monochloramine. In R. L. Jolley, R. J. Bull, W. P. Davis, S. Katz, M. H. Roberts, Jr., and V. A. Jacobs (ed.), Water Chlorination, vol. 5. Lewis Publishers, Inc., Williamsburg.
- ^ PMID 9439597.
- ^ PMID 8521532.
- ^ PMID 8806710.
- ^ PMID 9754324.
- ^ PMID 8068018.)
{{cite journal}}
: CS1 maint: multiple names: authors list (link - ^ PMID 8798498.
- PMID 9461501.
- ^ PMID 8070673.
- PMID 1321589.
- ^ S2CID 40223719.
- ^ PMID 2557918.
- ^ .
- ^ PMID 16561477.
- PMID 1846732.
- ^ PMID 2986713.
- ^ PMID 4745674.
- ISBN 0-683-30740-1
- ^ PMID 2848494.
- PMID 9478947.
- ^ PMID 8806715.
- PMID 11301330.
- PMID 29394241.
- PMID 29739865.
- PMID 1692736.
- ^ PMID 2545243.
- PMID 2982737.
- ^ doi:10.1016/S0021-9258(18)48129-X.)
{{cite journal}}
: CS1 maint: multiple names: authors list (link - PMID 8606194.
- ^ .
- ^ )
- ^ PMID 2820883.
- PMID 378130.
- .
- PMID 1662610.
- PMID 6292201.
- PMID 2175901.
- PMID 9596730.
- PMID 19013278.
- PMID 27429291.
- PMID 17492050.
- PMID 28458509.
- ^ "In situ generation: Active substances vs biocidal products". www.hse.gov.uk. Retrieved 2021-07-12.
External links
- National Pollutant Inventory – Chlorine
- Reuters – Mystery solved: How bleach kills germs
- "From Ground to Tap": a summary of the municipal tapwater treatment process