Sodium hypochlorite

Sodium hypochlorite

Sodium, Na    Oxygen, O    Chlorine, Cl
Names
IUPAC name Sodium hypochlorite
Other names Antiformin Bleach Chloride of soda Sodium chloroxide In dilution: Carrel-Dakin solution Modified Dakin's solution Surgical chlorinated soda solution
Identifiers
CAS Number	7681-52-9 (anhydrous) Y 10022-70-5 (pentahydrate) Y
3D model (JSmol)	Interactive image
ChEBI	CHEBI:32146  Y
ChemSpider	22756  Y
DrugBank	DBSALT001517
ECHA InfoCard	100.028.790
EC Number	231-668-3
KEGG	D01711  Y
PubChem CID	23665760
RTECS number	NH3486300
UNII	DY38VHM5OD  Y
UN number	1791
CompTox Dashboard (EPA)	DTXSID8021276
InChI InChI=1S/ClO.Na/c1-2;/q-1;+1 Y Key: SUKJFIGYRHOWBL-UHFFFAOYSA-N Y InChI=1/ClO.Na/c1-2;/q-1;+1 Key: SUKJFIGYRHOWBL-UHFFFAOYAD
SMILES [Na+].[O-]Cl
Properties
Chemical formula	NaOCl
Molar mass	74.442 g/mol
Appearance	White crystalline solid (anhydrous); Colorless or slightly yellow [1] or greenish-yellow crystalline solid (pentahydrate)
Odor	Chlorine-like and sweetish (pentahydrate) [1]
Density	1.11 g/cm3
Melting point	18 °C (64 °F; 291 K) (pentahydrate)
Boiling point	101 °C (214 °F; 374 K) (decomposes) (pentahydrate)
Solubility in water	29.3 g/(100 mL) (0 °C) [2]
Acidity (pKa)	7.5185
Basicity (pKb)	6.4815
Thermochemistry
Std enthalpy of formation (ΔfH⦵298)	−347.1 kJ/mol
Pharmacology
ATC code	D08AX07 ( WHO )
Hazards
Occupational safety and health (OHS/OSH):
Main hazards	corrosive, oxidizing agent [3]
GHS labelling:
Pictograms
Signal word	Danger
Hazard statements	H302, H314, H410
Precautionary statements	P260, P264, P273, P280, P301+P330+P331, P303+P361+P353, P304+P340, P305+P351+P338, P310, P321, P363, P391, P405, P501
NFPA 704 (fire diamond)	2 0 1 OX
Safety data sheet (SDS)	ICSC 1119 (solution, > 10% active chlorine) ICSC 0482 (solution, < 10% active chlorine)
Related compounds
Other anions	Sodium chloride Sodium chlorite Sodium chlorate Sodium perchlorate
Other cations	Lithium hypochlorite Potassium hypochlorite Calcium hypochlorite Barium hypochlorite Silver hypochlorite
Related compounds	Hypochlorite Chlorine monoxide Hypochlorous acid Methyl hypochlorite
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

Sodium hypochlorite is an alkaline inorganic chemical compound with the formula Na O Cl (also written as NaClO). It is commonly known in a dilute aqueous solution as bleach or chlorine bleach. ^[4] It is the sodium salt of hypochlorous acid, consisting of sodium cations (Na⁺) and hypochlorite anions (⁻OCl, also written as OCl⁻ and ClO⁻).

The anhydrous compound is unstable and may decompose explosively. ^{[5] [6]} It can be crystallized as a pentahydrate NaOCl·5H₂O, a pale greenish-yellow solid which is not explosive and is stable if kept refrigerated. ^{[7] [8] [9]}

Sodium hypochlorite is most often encountered as a pale greenish-yellow dilute solution referred to as chlorine bleach, which is a household chemical widely used (since the 18th century) as a disinfectant and bleaching agent. In solution, the compound is unstable and easily decomposes, liberating chlorine, which is the active principle of such products. Sodium hypochlorite is still the most important chlorine-based bleach. ^{[10] [11]}

Its corrosive properties, common availability, and reaction products make it a significant safety risk. In particular, mixing liquid bleach with other cleaning products, such as acids found in limescale-removing products, will release chlorine gas. Chlorine gas was utilized as a chemical weapon in World War I. ^{[12] [13] [14]} A common misconception is that mixing bleach with ammonia also releases chlorine, but in reality they react to produce chloramines such as nitrogen trichloride. With excess ammonia and sodium hydroxide, hydrazine may be generated.

Chemistry

Stability of the solid

Anhydrous sodium hypochlorite can be prepared but, like many hypochlorites, it is highly unstable and decomposes explosively on heating or friction. ^[5] The decomposition is accelerated by carbon dioxide at Earth's atmospheric levels - around 4 parts per ten thousand. ^{[6] [15]} It is a white solid with the orthorhombic crystal structure. ^[16]

Sodium hypochlorite can also be obtained as a crystalline pentahydrate NaOCl·5H₂O, which is not explosive and is much more stable than the anhydrous compound. ^{[6] [7]} The formula is sometimes given in its hydrous crystalline form as 2NaOCl·10H₂O. ^[17] The Cl–O bond length in the pentahydrate is 1.686 Å. ^[9] The transparent, light greenish-yellow, orthorhombic ^{[18] [19]} crystals contain 44% NaOCl by weight and melt at 25–27 °C. The compound decomposes rapidly at room temperature, so it must be kept under refrigeration. At lower temperatures, however, it is quite stable: reportedly only 1% decomposition after 360 days at 7 °C. ^{[8] [20]}

A 1966 US patent claims that stable solid sodium hypochlorite dihydrate NaOCl·2H₂O can be obtained by carefully excluding chloride ions (Cl⁻), which are present in the output of common manufacturing processes and are said to catalyze the decomposition of hypochlorite into chlorate (ClO−3) and chloride. In one test, the dihydrate was claimed to show only 6% decomposition after 13.5 months of storage at −25 °C. The patent also claims that the dihydrate can be reduced to the anhydrous form by vacuum drying at about 50 °C, yielding a solid that showed no decomposition after 64 hours at −25 °C. ^[21]

Equilibria and stability of solutions

At typical ambient temperatures, sodium hypochlorite is more stable in dilute solutions that contain solvated Na⁺ and OCl⁻ ions. The density of the solution is 1.093 g/mL at 5% concentration, ^[22] and 1.21 g/mL at 14%, 20 °C. ^[23] Stoichiometric solutions are fairly alkaline, with pH 11 or higher ^[8] since hypochlorous acid is a weak acid:

OCl⁻ + H₂O ⇌ HOCl + OH⁻

The following species and equilibria are present in NaOCl/NaCl solutions: ^[24]

HOCl(aq) ⇌ H⁺ + OCl⁻

HOCl(aq) + Cl⁻ + H⁺ ⇌ Cl₂(aq) + H₂O

Cl₂(aq) + Cl⁻ ⇌ Cl−3

Cl₂(aq) ⇌ Cl₂(g)

The second equilibrium equation above will be shifted to the right if the chlorine Cl₂ is allowed to escape as gas. The ratios of Cl₂, HOCl, and OCl⁻ in solution are also pH dependent. At pH below 2, the majority of the chlorine in the solution is in the form of dissolved elemental Cl₂. At pH greater than 7.4, the majority is in the form of hypochlorite ClO⁻. ^[10] The equilibrium can be shifted by adding acids (such as hydrochloric acid) or bases (such as sodium hydroxide) to the solution:

ClO⁻(aq) + 2 HCl(aq) → Cl₂(g) + H₂O + Cl⁻(aq)

Cl₂(g) + 2 OH⁻ → ClO⁻(aq) + Cl⁻(aq) + H₂O(aq)

At a pH of about 4, such as obtained by the addition of strong acids like hydrochloric acid, the amount of undissociated (nonionized) HOCl is highest. The reaction can be written as:

⁻OCl + H⁺ ⇌ HOCl

Sodium hypochlorite solutions combined with acid evolve chlorine gas, particularly strongly at pH < 2, by the reactions:

HOCl(aq) + Cl⁻ + H⁺ ⇌ Cl₂(aq) + H₂O

Cl₂(aq) ⇌ Cl₂(g)

At pH > 8, the chlorine is practically all in the form of hypochlorite anions (OCl⁻). The solutions are fairly stable at pH 11–12. Even so, one report claims that a conventional 13.6% NaOCl reagent solution lost 17% of its strength after being stored for 360 days at 7 °C. ^[8] For this reason, in some applications one may use more stable chlorine-releasing compounds, such as calcium hypochlorite Ca(ClO)₂ or trichloroisocyanuric acid (CNClO)₃.^{[ citation needed ]}

Anhydrous sodium hypochlorite is soluble in methanol, and solutions are stable.^{[ citation needed ]}

Decomposition to chlorate or oxygen

In solution, under certain conditions, the hypochlorite anion may also disproportionate (autoxidize) to chloride and chlorate: ^[25]

3 ClO⁻ + H⁺ → HClO₃ + 2 Cl⁻

In particular, this reaction occurs in sodium hypochlorite solutions at high temperatures, forming sodium chlorate and sodium chloride: ^{[25] [26]}

3 NaOCl(aq) → 2 NaCl(aq) + NaClO₃(aq)

This reaction is exploited in the industrial production of sodium chlorate.

An alternative decomposition of hypochlorite produces oxygen instead:

2 OCl⁻ → 2 Cl⁻ + O₂

In hot sodium hypochlorite solutions, this reaction competes with chlorate formation, yielding sodium chloride and oxygen gas: ^[25]

2 NaOCl(aq) → 2 NaCl(aq) + O₂(g)

These two decomposition reactions of NaOCl solutions are maximized at pH around 6. For example, at 80 °C, with NaOCl and NaCl concentrations of 80 mM, over the pH range 5−10.5, both reactions have rate proportional to ${\displaystyle [{\ce {HOCl}}]^{2}[{\ce {OCl-}}]}$, decomposition is fastest at pH 6.5, and chlorate is produced with ~95% efficiency. ^[25] Above pH 11, both reactions have rate proportional to ${\displaystyle [{\ce {OCl-}}]^{2}}$, decomposition is much slower, and chlorate is produced with ~90% efficiency. ^[27] This decomposition is affected by light ^[26] and metal ion catalysts such as copper, nickel, cobalt, ^[25] and iridium. ^[28] Catalysts like sodium dichromate Na₂Cr₂O₇ and sodium molybdate Na₂MoO₄ may be added industrially to reduce the oxygen pathway, but a report claims that only the latter is effective. ^{[25] [ failed verification ]}

Titration

Titration of hypochlorite solutions is often done by adding a measured sample to an excess amount of acidified solution of potassium iodide (KI) and then titrating the liberated iodine (I₂) with a standard solution of sodium thiosulfate or phenylarsine oxide, using starch as indicator, until the blue color disappears. ^[19]

According to one US patent, the stability of sodium hypochlorite content of solids or solutions can be determined by monitoring the infrared absorption due to the O–Cl bond. The characteristic wavelength is given as 140.25 μm for water solutions, 140.05 μm for the solid dihydrate NaOCl·2H₂O, and 139.08 μm for the anhydrous mixed salt Na₂(OCl)(OH). ^[21]

Oxidation of organic compounds

Oxidation of starch by sodium hypochlorite, which adds carbonyl and carboxyl groups, is relevant to the production of modified starch products. ^[29]

In the presence of a phase-transfer catalyst, alcohols are oxidized to the corresponding carbonyl compound (aldehyde or ketone). ^{[30] [8]} Sodium hypochlorite can also oxidize organic sulfides to sulfoxides or sulfones; disulfides or thiols to sulfonyl halides; and imines to oxaziridines. ^[8] It can also de-aromatize phenols. ^[8]

Oxidation of metals and complexes

Heterogeneous reactions of sodium hypochlorite and metals such as zinc proceed slowly to give the metal oxide or hydroxide:^{[ citation needed ]}

NaOCl + Zn → ZnO + NaCl

Homogeneous reactions with metal coordination complexes proceed somewhat faster. This has been exploited in the Jacobsen epoxidation.^{[ citation needed ]}

Other reactions

If not properly stored in airtight containers, sodium hypochlorite reacts with carbon dioxide to form sodium carbonate:

2 NaOCl + CO₂ + H₂O → Na₂CO₃ + 2 HOCl

Sodium hypochlorite reacts with most nitrogen compounds to form volatile monochloramine, dichloramines, and nitrogen trichloride:

NH₃ + NaOCl → NH₂Cl + NaOH

NH₂Cl + NaOCl → NHCl₂ + NaOH

NHCl₂ + NaOCl → NCl₃ + NaOH

Neutralization

Sodium thiosulfate is an effective chlorine neutralizer. Rinsing with a 5 mg/L solution, followed by washing with soap and water, will remove chlorine odor from the hands. ^[31]

Production

Chlorination of soda

Potassium hypochlorite was first produced in 1789 by Claude Louis Berthollet in his laboratory on the Quai de Javel in Paris, France, by passing chlorine gas through a solution of potash lye. The resulting liquid, known as "Eau de Javel" ("Javel water"), was a weak solution of potassium hypochlorite. Antoine Labarraque replaced potash lye by the cheaper soda lye, thus obtaining sodium hypochlorite (Eau de Labarraque). ^{[32] [33]}

Cl₂(g) + 2 NaOH(aq) → NaCl(aq) + NaClO(aq) + H₂O

Hence, chlorine is simultaneously reduced and oxidized; this process is known as disproportionation.^{[ citation needed ]}

The process is also used to prepare the pentahydrate NaOCl·5H₂O for industrial and laboratory use. In a typical process, chlorine gas is added to a 45–48% NaOH solution. Some of the sodium chloride precipitates and is removed by filtration, and the pentahydrate is then obtained by cooling the filtrate to 12 °C. ^[8]

From calcium hypochlorite

Another method involved the reaction of sodium carbonate ("washing soda") with chlorinated lime ("bleaching powder"), a mixture of calcium hypochlorite Ca(OCl)₂, calcium chloride CaCl₂, and calcium hydroxide Ca(OH)₂:

Na₂CO₃(aq) + Ca(OCl)₂(aq) → CaCO₃(s) + 2 NaOCl(aq)

Na₂CO₃(aq) + CaCl₂(aq) → CaCO₃(s) + 2 NaCl(aq)

Na₂CO₃(aq) + Ca(OH)₂(s) → CaCO₃(s) + 2 NaOH(aq)

This method was commonly used to produce hypochlorite solutions for use as a hospital antiseptic that was sold after World War I under the names "Eusol", an abbreviation for Edinburgh University Solution Of (chlorinated) Lime – a reference to the university's pathology department, where it was developed. ^[34]

Electrolysis of brine

Near the end of the nineteenth century, E. S. Smith patented the chloralkali process: a method of producing sodium hypochlorite involving the electrolysis of brine to produce sodium hydroxide and chlorine gas, which then mixed to form sodium hypochlorite. ^{[35] [33] [36]} The key reactions are:

2 Cl⁻ → Cl₂ + 2 e⁻ (at the anode)

2 H₂O + 2 e⁻ → H₂ + 2 ⁻OH (at the cathode)

Both electric power and brine solutions were in cheap supply at the time, and various enterprising marketers took advantage of the situation to satisfy the market's demand for sodium hypochlorite. Bottled solutions of sodium hypochlorite were sold under numerous trade names.^{[ citation needed ]}

Today, an improved version of this method, known as the Hooker process (named after Hooker Chemicals, acquired by Occidental Petroleum), is the only large-scale industrial method of sodium hypochlorite production. In the process, sodium hypochlorite (NaClO) and sodium chloride (NaCl) are formed when chlorine is passed into a cold dilute sodium hydroxide solution. The chlorine is prepared industrially by electrolysis with minimal separation between the anode and the cathode. The solution must be kept below 40 °C (by cooling coils) to prevent the undesired formation of sodium chlorate.^{[ citation needed ]}

Commercial solutions always contain significant amounts of sodium chloride (common salt) as the main by-product, as seen in the equation above.

From hypochlorous acid and soda

A 1966 patent describes the production of solid stable dihydrate NaOCl·2H₂O by reacting a chloride-free solution of hypochlorous acid HClO (such as prepared from chlorine monoxide ClO and water), with a concentrated solution of sodium hydroxide. In a typical preparation, 255 mL of a solution with 118 g/L HClO is slowly added with stirring to a solution of 40 g of NaOH in water 0 °C. Some sodium chloride precipitates and is removed by filtration. The solution is vacuum evaporated at 40–50 °C and 1–2 mmHg until the dihydrate crystallizes out. The crystals are vacuum-dried to produce a free-flowing crystalline powder. ^[21]

The same principle was used in a 1993 patent to produce concentrated slurries of the pentahydrate NaClO·5H₂O. Typically, a 35% solution (by weight) of HClO is combined with sodium hydroxide at about or below 25 °C. The resulting slurry contains about 35% NaClO, and are relatively stable due to the low concentration of chloride. ^[37]

Packaging and sale

Main article: Bleach

Bleach packaged for household use, with 2.6%

Household bleach sold for use in laundering clothes is a 3–8% solution of sodium hypochlorite at the time of manufacture. Strength varies from one formulation to another and gradually decreases with long storage. Sodium hydroxide is usually added in small amounts to household bleach to slow down the decomposition of NaClO. ^[10]

Domestic use patio blackspot remover products are ~10% solutions of sodium hypochlorite.

A 10–25% solution of sodium hypochlorite is, according to Univar's safety sheet, supplied with synonyms or trade names bleach, Hypo, Everchlor, Chloros, Hispec, Bridos, Bleacol, or Vo-redox 9110. ^[38]

A 12% solution is widely used in waterworks for the chlorination of water, and a 15% solution is more commonly ^[39] used for disinfection of wastewater in treatment plants. Sodium hypochlorite can also be used for point-of-use disinfection of drinking water, ^[40] taking 0.2–2 mg of sodium hypochlorite per liter of water. ^[41]

Dilute solutions (50 ppm to 1.5%) are found in disinfecting sprays and wipes used on hard surfaces. ^{[42] [43]}

Uses

Bleaching

Household bleach is, in general, a solution containing 3–8% sodium hypochlorite, by weight, and 0.01–0.05% sodium hydroxide; the sodium hydroxide is used to slow the decomposition of sodium hypochlorite into sodium chloride and sodium chlorate. ^[44]

Cleaning

Sodium hypochlorite has destaining properties. ^[45] Among other applications, it can be used to remove mold stains, dental stains caused by fluorosis, ^[46] and stains on crockery, especially those caused by the tannins in tea. It has also been used in laundry detergents and as a surface cleaner. It is also used in sodium hypochlorite washes.

Its bleaching, cleaning, deodorizing, and caustic effects are due to oxidation and hydrolysis (saponification). Organic dirt exposed to hypochlorite becomes water-soluble and non-volatile, which reduces its odor and facilitates its removal.

Disinfection

See also: Hypochlorous acid

Sodium hypochlorite in solution exhibits broad-spectrum anti-microbial activity and is widely used in healthcare facilities in a variety of settings. ^[47] It is usually diluted in water depending on its intended use. "Strong chlorine solution" is a 0.5% solution of hypochlorite (containing approximately 5000 ppm free chlorine) used for disinfecting areas contaminated with body fluids, including large blood spills (the area is first cleaned with detergent before being disinfected). ^{[47] [48]} It may be made by diluting household bleach as appropriate (normally 1 part bleach to 9 parts water). ^[49] Such solutions have been demonstrated to inactivate both C. difficile ^[47] and HPV. ^[50] "Weak chlorine solution" is a 0.05% solution of hypochlorite used for washing hands, but is normally prepared with calcium hypochlorite granules. ^[48]

"Dakin's Solution" is a disinfectant solution containing a low concentration of sodium hypochlorite and some boric acid or sodium bicarbonate to stabilize the pH. It is effective with NaOCl concentrations as low as 0.025%. ^[51]

US government regulations allow food processing equipment and food contact surfaces to be sanitized with solutions containing bleach, provided that the solution is allowed to drain adequately before contact with food and that the solutions do not exceed 200 parts per million (ppm) available chlorine (for example, one tablespoon of typical household bleach containing 5.25% sodium hypochlorite, per gallon of water). ^[52] If higher concentrations are used, the surface must be rinsed with potable water after sanitizing.

A similar concentration of bleach in warm water is used to sanitize surfaces before brewing beer or wine. Surfaces must be rinsed with sterilized (boiled) water to avoid imparting flavors to the brew; the chlorinated byproducts of sanitizing surfaces are also harmful. The mode of disinfectant action of sodium hypochlorite is similar to that of hypochlorous acid.

Solutions containing more than 500 ppm available chlorine are corrosive to some metals, alloys, and many thermoplastics (such as acetal resin) and need to be thoroughly removed afterward, so the bleach disinfection is sometimes followed by an ethanol disinfection. Liquids containing sodium hypochlorite as the main active component are also used for household cleaning and disinfection, for example toilet cleaners. ^[53] Some cleaners are formulated to be viscous so as not to drain quickly from vertical surfaces, such as the inside of a toilet bowl.

The undissociated (nonionized) hypochlorous acid is believed to react with and inactivate bacterial and viral enzymes.

Neutrophils of the human immune system produce small amounts of hypochlorite inside phagosomes, which digest bacteria and viruses.

Deodorizing

Sodium hypochlorite has deodorizing properties, which go hand in hand with its cleaning properties. ^[45]

Waste water treatment

Sodium hypochlorite solutions have been used to treat dilute cyanide wastewater, such as electroplating wastes. In batch treatment operations, sodium hypochlorite has been used to treat more concentrated cyanide wastes, such as silver cyanide plating solutions. Toxic cyanide is oxidized to cyanate OCN⁻) that is not toxic, idealized as follows:

CN⁻ + ⁻OCl → OCN⁻ + Cl⁻

Sodium hypochlorite is commonly used as a biocide in industrial applications to control slime and bacteria formation in water systems used at power plants, pulp and paper mills, etc., in solutions typically of 10–15% by weight.

Endodontics

Sodium hypochlorite is the medicament of choice due to its efficacy against pathogenic organisms and pulp digestion in endodontic therapy. Its concentration for use varies from 0.5% to 5.25%. At low concentrations it dissolves mainly necrotic tissue; at higher concentrations, it also dissolves vital tissue and additional bacterial species. One study has shown that Enterococcus faecalis was still present in the dentin after 40 minutes of exposure of 1.3% and 2.5% sodium hypochlorite, whereas 40 minutes at a concentration of 5.25% was effective in E. faecalis removal. ^[54] In addition to higher concentrations of sodium hypochlorite, longer time exposure and warming the solution (60 °C) also increases its effectiveness in removing soft tissue and bacteria within the root canal chamber. ^[54] 2% is a common concentration as there is less risk of an iatrogenic hypochlorite incident. ^[55] A hypochlorite incident is an immediate reaction of severe pain, followed by edema, haematoma, and ecchymosis as a consequence of the solution escaping the confines of the tooth and entering the periapical space. This may be caused by binding or excessive pressure on the irrigant syringe, or it may occur if the tooth has an unusually large apical foramen. ^[56]

Nerve agent neutralization

At the various nerve agent (chemical warfare nerve gas) destruction facilities throughout the United States, 0.5-2.5% sodium hypochlorite is used to remove all traces of nerve agent or blister agent from Personal Protection Equipment after an entry is made by personnel into toxic areas. ^[57]

0.5-2.5% sodium hypochlorite is also used to neutralize any accidental releases of the nerve agent in the toxic areas. ^[58]

Lesser concentrations of sodium hypochlorite are used similarly in the Pollution Abatement System to ensure that no nerve agent is released into the furnace flue gas.

Reduction of skin damage

Dilute bleach baths have been used for decades to treat moderate to severe eczema in humans,. ^{[59] [60]} Still, it has not been clear why they work. One of the reasons why bleach helps is that eczema can frequently result in secondary infections, especially from bacteria like Staphylococcus aureus, which makes managing it difficult. Staphylococcus aureus infection is related to the pathogenesis of eczema and AD. Bleach baths are one method for lowering the risk of staph infections in people with eczema. The antibacterial and anti-inflammatory properties of sodium hypochlorite contribute to the reduction of harmful bacteria on the skin and the reduction of inflammation, respectively. ^[61] According to work published by researchers at the Stanford University School of Medicine in November 2013, a very dilute (0.005%) solution of sodium hypochlorite in water was successful in treating skin damage with an inflammatory component caused by radiation therapy, excess sun exposure or aging in laboratory mice. Mice with radiation dermatitis given daily 30-minute baths in bleach solution experienced less severe skin damage and better healing and hair regrowth than animals bathed in water. A molecule called nuclear factor kappa-light-chain-enhancer of activated B cells (NF-κB) is known to play a critical role in inflammation, aging, and response to radiation. The researchers found that if NF-κB activity was blocked in elderly mice by bathing them in bleach solution, the animals' skin began to look younger, going from old and fragile to thicker, with increased cell proliferation. The effect diminished after the baths were stopped, indicating that regular exposure was necessary to maintain skin thickness. ^{[59] [62]}

Safety

Dilute sodium hypochlorite solutions (as in household bleach) are irritating to mainly the skin and respiratory tract. Short-term skin contact with household bleach may cause dryness of the skin.

It is estimated that there are about 3,300 accidents needing hospital treatment caused by sodium hypochlorite solutions each year in British homes (RoSPA, 2002).

Oxidation and corrosion

Sodium hypochlorite is a strong oxidizer. Oxidation reactions are corrosive. Solutions burn the skin and cause eye damage, especially when used in concentrated forms. As recognized by the NFPA, however, only solutions containing more than 40% sodium hypochlorite by weight are considered hazardous oxidizers. Solutions less than 40% are classified as a moderate oxidizing hazard (NFPA 430, 2000).

Household bleach and pool chlorinator solutions are typically stabilized by a significant concentration of lye (caustic soda, NaOH) as part of the manufacturing reaction. This additive will by itself cause caustic irritation or burns due to defatting and saponification of skin oils and destruction of tissue. The slippery feel of bleach on the skin is due to this process.

Storage hazards

Contact of sodium hypochlorite solutions with metals may evolve flammable hydrogen gas. Containers may explode when heated due to the release of chlorine gas. ^[15]

Hypochlorite solutions are corrosive to common container materials such as stainless steel ^[8] and aluminium. The few compatible metals include titanium (which however is not compatible with dry chlorine) and tantalum. ^[10] Glass containers are safe. ^[8] Some plastics and rubbers are affected too; safe choices include polyethylene (PE), high density polyethylene (HDPE, PE-HD), polypropylene (PP), ^[8] some chlorinated and fluorinated polymers such as polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), and polyvinylidene fluoride (PVDF); as well as ethylene propylene rubber, and Viton. ^[10]

Containers must allow the venting of oxygen produced by decomposition over time, otherwise, they may burst. ^[5]

Reactions with other common products

Mixing bleach with some household cleaners can be hazardous.

Sodium hypochlorite solutions, such as liquid bleach, will release toxic chlorine gas when mixed with an acid, such as hydrochloric acid or vinegar.

A 2008 study indicated that sodium hypochlorite and organic chemicals (e.g., surfactants, fragrances) contained in several household cleaning products can react to generate chlorinated organic compounds. ^[63] The study showed that indoor air concentrations significantly increase (8–52 times for chloroform and 1–1170 times for carbon tetrachloride, respectively, above baseline quantities in the household) during the use of bleach containing products.

In particular, mixing hypochlorite bleaches with amines (for example, cleaning products that contain or release ammonia, ammonium salts, urea, or related compounds and biological materials such as urine) produces chloramines. ^{[64] [15]} These gaseous products can cause acute lung injury. Chronic exposure, for example, from the air at swimming pools where chlorine is used as the disinfectant, can lead to the development of atopic asthma. ^[65]

Bleach can react violently with hydrogen peroxide and produce oxygen gas:

H₂O₂(aq) + NaOCl(aq) → NaCl(aq) + H₂O + O₂(g)

Explosive reactions or byproducts can also occur in industrial and laboratory settings when sodium hypochlorite is mixed with diverse organic compounds. ^[15]

Limitations in health care

The UK's National Institute for Health and Care Excellence in October 2008 recommended that Dakin's solution should not be used in routine wound care. ^[66]

Environmental impact

In spite of its strong biocidal action, sodium hypochlorite per se has limited environmental impact, since the hypochlorite ion rapidly degrades before it can be absorbed by living beings. ^[67]

However, one major concern arising from sodium hypochlorite use is that it tends to form persistent chlorinated organic compounds, including known carcinogens, that can be absorbed by organisms and enter the food chain. These compounds may be formed during household storage and use as well as during industrial use. ^[44] For example, when household bleach and wastewater were mixed, 1–2% of the available chlorine was observed to form organic compounds. ^[44] As of 1994, not all the byproducts had been identified, but identified compounds include chloroform and carbon tetrachloride. ^{[44] [ needs update ]} The exposure to these chemicals from use is estimated to be within occupational exposure limits. ^[44]

See also

• Calcium hypochlorite Ca(OCl)₂ ("bleaching powder")
• Potassium hypochlorite KOCl (the original "Javel water")
• Lithium hypochlorite LiOCl
• Milton sterilizing fluid
• Sodium hypochlorite washes
• Mixed oxidant

References

1. "Sodium Hypochlorite".
2. Budavari S, O'Neil M, Smith A, Heckelman P, Obenchain J (1996). "Sodium hypochlorite". The Merck Index (12th ed.). p. 1478. ISBN   978-0-911910-12-4.
3. Sodium hypochlorite: chemical activity
4. "sodium hypochlorite | chemical compound | Britannica". britannica.com. Retrieved 21 March 2022.
5. Urben P (2006). Bretherick's Handbook of Reactive Chemical Hazards . Vol. 1 (7th ed.). Elsevier. p. 1433. ISBN   978-0-08-052340-8.
6. Hamano A (1997). "The formation and decomposition of sodium hypochlorite anhydrous salt and its pentahydrate". Science and Technology of Energetic Materials. 58 (4): 152–155.
7. Applebey MP (1919). "Sodium hypochlorite". Journal of the Chemical Society, Transactions. 115 (XCVI): 1106–1109. doi:10.1039/CT9191501106.
8. Kirihara M, Okada T, Sugiyama Y, Akiyoshi M, Matsunaga T, Kimura Y (December 2017). "Sodium Hypochlorite Pentahydrate Crystals (NaOCl· 5H2O): A Convenient and Environmentally Benign Oxidant for Organic Synthesis". Organic Process Research & Development. 21 (12): 1925–37. doi: 10.1021/acs.oprd.7b00288 .
9. Topić F, Marrett JM, Borchers TH, Titi HM, Barrett CJ, Friščić T (2021). "After 200 Years: The Structure of Bleach and Characterization of Hypohalite Ions by Single-Crystal X-Ray Diffraction". Angew. Chem. Int. Ed. 60 (46): 24400–24405. doi:10.1002/anie.202108843. PMID   34293249. S2CID   236199263.
10. "OxyChem Sodium Hypochlorite Handbook" (PDF). OxyChem. Archived from the original (PDF) on 18 April 2018. Retrieved 6 February 2015.
11. "Pamphlet 96, The Sodium Hypochorite Manual". The Chlorine Institute.
12. Faith T (2014). Behind the Gas Mask: The U.S. Chemical Warfare Service in War and Peace. Champaign, Illinois: University of Illinois Press. p. 9. ISBN   978-0252080265 . Retrieved 14 April 2017.
13. "April 22, 1915: Germans introduce poison gas". This Day In History. Retrieved 14 April 2017.
14. Gross DA (Spring 2015). "Chemical Warfare: From the European Battlefield to the American Laboratory". Distillations Magazine. 1 (1): 16–23. Retrieved 20 March 2018.
15. (2013): "Sodium Hypochlorite" Stanford Linear Accelerator Laboratory Safe Handling Guideline, chapter 53, product 202. Accessed on 2018-06-12
16. Yaws CL (2015). The Yaws Handbook of Physical Properties for Hydrocarbons and Chemicals (2nd ed.). Gulf Professional Publishing. p. 734. ISBN   978-0-12-801146-1.
17. Bell-Young L (29 September 2019). "What is sodium hypochlorite used for?". Chemicals.co.uk. Retrieved 29 August 2023.
18. " "Sodium Hypochlorite Pentahydrate, NaOCl·5H
    _²O". MatWeb Material Property Data website. Retrieved 12 July 2018.
19. "Sodium Hypochlorite". StudFiles. Retrieved 14 June 2018.
20. Okada T, Asawa T, Sugiyama Y, Iwai T, Kirihara M, Kimura Y (June 2016). "Sodium hypochlorite pentahydrate (NaOCl·5H2O) crystals; An effective re-oxidant for TEMPO oxidation". Tetrahedron. 72 (22): 2818–27. doi:10.1016/j.tet.2016.03.064.
21. US 3498924,Walsh RH, Dietz A,"Process for preparing stable sodium hypochlorites",issued 1966 
22. "Sodium hypochlorite". PubChem. U.S. National Library of Medicine.
23. Environment Canada (1985): "Tech Info for Problem Spills: Sodium Hypochlorite (Draft)".
24. Wang L, Bassiri M, Najafi R, Najafi K, Yang J, Khosrovi B, et al. (April 2007). "Hypochlorous acid as a potential wound care agent: part I. Stabilized hypochlorous acid: a component of the inorganic armamentarium of innate immunity". Journal of Burns and Wounds. 6: e5. PMC   1853323 . PMID   17492050.
25. Sandin S, Karlsson RK, Cornell A (April 2015). "Catalyzed and uncatalyzed decomposition of hypochlorite in dilute solutions". Industrial & Engineering Chemistry Research. 54 (15): 3767–74. doi:10.1021/ie504890a.
26. Hamano A, Ikeda A (1995). "The pH effect on the photodecomposition of sodium hypochlorite solution". Science and Technology of Energetic Materials. 56 (2): 59–63.
27. Adam LC, Gordon G (20 February 1999). "Hypochlorite Ion Decomposition: Effects of Temperature, Ionic Strength, and Chloride Ion". Inorganic Chemistry. 38 (6): 1299–1304. doi:10.1021/ic980020q. PMID   11670917.
28. Ayres GH, Booth MH (1955). "Catalytic Decomposition of Hypochlorite Solution by Iridium Compounds. I. The pH-Time Relationship". Journal of the American Chemical Society. 77 (4): 825–827. doi:10.1021/ja01609a001.
29. ASC – PT Asahimas Chemical (2009): "Sodium hypochlorite". Online product description. Accessed on 2018-06-14.
30. Mirafzal GA, Lozeva AM (1998). "Phase transfer catalyzed oxidation of alcohols with sodium hypochlorite". Tetrahedron Letters . 39 (40): 7263–7266. doi:10.1016/S0040-4039(98)01584-6.
31. Eaton AD, Greenberg AE, Rice EW, Clesceri LS, Franson MA, eds. (2005). Standard Methods For the Examination of Water and Wastewater (21 ed.). American Public Health Association. ISBN   978-0-87553-047-5. Method 9060a. Also available on CD-ROM and online by subscription.
32. Vogt H, Balej J, Bennett JE, Wintzer P, Sheikh SA, Gallone P (2007). "Chlorine Oxides and Chlorine Oxygen Acids". Ullmann's Encyclopedia of Industrial Chemistry (7th ed.). Wiley. p. 2.
33. "Sodium hypochlorite as a disinfectant". Lenntech.com. Retrieved 7 August 2011.
34. "eusol". Oxford English Dictionary. Archived from the original on 31 August 2013. Retrieved 3 July 2014.
35. May P. "Sodium Hypochlorite (Bleach)". University of Bristol. Archived from the original on 13 December 2016. Retrieved 13 December 2016.
36. "How Products Are Made Volume 2". May 2011.
37. US 5194238,Duncan BL, Ness RC,"Process for the production of highly pure concentrated slurries of sodium hypochlorite",issued 1991 
38. "SAFETY DATA SHEET Sodium Hypochlorite" (PDF). Univar. 9 August 2007.
39. Wastewater Engineering: Treatment, Disposal, & Reuse (3rd ed.). Metcalf & Eddy, Inc. 1991. p. 497.
40. Lantagne DS (2018). "Sodium hypochlorite dosage for household and emergency water treatment". IWA Publishing. 16 (1).
41. "What is Chlorination?". 27 November 2016.
42. Vieira ER (1999). Elementary Food Science. Springer. pp. 381–382. ISBN   978-0-8342-1657-0.
43. Wilhelm N, Kaufmann A, Blanton E, Lantagne D (February 2018). "Sodium hypochlorite dosage for household and emergency water treatment: updated recommendations". Journal of Water and Health. 16 (1): 112–125. doi: 10.2166/wh.2017.012 . PMID   29424725.
44. Smith WT. (1994). Human and Environmental Safety of Hypochlorite. In: Proceedings of the 3rd World Conference on Detergents: Global Perspectives, pp. 183–5.
45. "Benefits and Safety Aspects of Hypochlorite Formulated in Domestic Products" (PDF). AISE – International Association for Soaps, Detergents and Maintenance Products. March 1997. Archived (PDF) from the original on 30 March 2014. Retrieved 30 October 2024. This Support Dossier deals with information on the environmental and human safety evaluation of hypochlorite, and on its benefits as a disinfecting, deodorising, and stain removing agent.
46. Cárdenas Flores A, Flores Reyes H, Gordillo Moscoso A, Castanedo Cázares JP, Pozos Guillén A (2009). "Clinical efficacy of 5% sodium hypochlorite for removal of stains caused by dental fluorosis". The Journal of Clinical Pediatric Dentistry. 33 (3): 187–91. doi:10.17796/jcpd.33.3.c6282t1054584157 (inactive 3 December 2024). PMID   19476089.
47. Rutala WA, Weber DJ (15 February 2017) [2008]. "Guideline for Disinfection and Sterilization in Healthcare Facilities" (PDF). cdc.gov. Retrieved 30 October 2024.
48. "For General Healthcare Settings in West Africa: How to Prepare and Use Chlorine Solutions". Ebola Hemorrhagic Fever. Centers for Disease Control and Prevention. Retrieved 27 April 2016.
49. "How to Make Strong (0.5%) Chlorine Solution from Liquid Bleach" (PDF). Centers for Disease Control and Prevention.
50. Meyers J, Ryndock E, Conway MJ, Meyers C, Robison R (June 2014). "Susceptibility of high-risk human papillomavirus type 16 to clinical disinfectants". The Journal of Antimicrobial Chemotherapy. 69 (6): 1546–50. doi:10.1093/jac/dku006. PMC   4019329 . PMID   24500190.
51. Heggers JP, Sazy JA, Stenberg BD, Strock LL, McCauley RL, Herndon DN, Robson MC (1991). "Bactericidal and wound-healing properties of sodium hypochlorite solutions: the 1991 Lindberg Award". The Journal of Burn Care & Rehabilitation. 12 (5): 420–4. doi:10.1097/00004630-199109000-00005. PMID   1752875.
52. 21 CFR Part 178
53. "Toilet Cleaners: Learn About Chemicals Around Your House: Pesticides: US EPA". United States Environmental Protection Agency. 9 May 2012.
54. Root Canal Irrigants and Disinfectants. Endodontics: Colleagues for Excellence. Published for the Dental Professional Community by the American Association of Endodontists. Winter 2011.
55. Torabinejad M, Walton R (2008). Endodontics. VitalBook (4th ed.). W.B. Saunders Company. p. 265.
56. Hülsmann M, Hahn W (May 2000). "Complications during root canal irrigation--literature review and case reports" (PDF). International Endodontic Journal. 33 (3): 186–93. doi:10.1046/j.1365-2591.2000.00303.x. PMID   11307434.
57. "Sodium hypochlorite - Medical Countermeasure Database". chemm.hhs.gov. 16 November 2022. Retrieved 28 August 2023.
58. Gold M, Bongiovanni R (1994). "Hypochlorite solution as a decontaminant in sulfur mustard contaminated skin defects in the euthymic hairless guinea pig" (PDF). Vetarinary Medicine and Surgery Branch and Basic Assessment Branch, United States Army Medical Research. 17 (4): 499–527. doi:10.3109/01480549409014314. PMID   7821235.
59. Conger K (15 November 2013). "Inflammatory skin damage in mice blocked by bleach solution, study finds". Stanford School of Medicine. Archived from the original on 7 December 2013.
60. Pett K, Batta K, Vlachou C, Nicholls G. "Bleach baths using Milton Sterilising Fluid for recurrent infected atopic eczema". eczema.org. Archived from the original on 12 December 2013.
61. "Eczema Bleach Bath: A Step-by-Step Guide and Benefits". skinsuperclear.com. Retrieved 13 March 2023.
62. Leung TH, Zhang LF, Wang J, Ning S, Knox SJ, Kim SK (December 2013). "Topical hypochlorite ameliorates NF-κB-mediated skin diseases in mice". The Journal of Clinical Investigation. 123 (12): 5361–70. doi:10.1172/JCI70895. PMC   3859383 . PMID   24231355.
63. Odabasi M (March 2008). "Halogenated volatile organic compounds from the use of chlorine-bleach-containing household products" (PDF). Environmental Science & Technology. 42 (5): 1445–1451. Bibcode:2008EnST...42.1445O. doi:10.1021/es702355u. PMID   18441786.
64. Krieger GR, Sullivan JB Jr (2001). Clinical environmental health and toxic exposures (2nd ed.). Philadelphia, Pa.: Lippincott Williams & Wilkins. p. 968. ISBN   9780683080278 . Retrieved 30 August 2016.
65. Nickmilder M, Carbonnelle S, Bernard A (February 2007). "House cleaning with chlorine bleach and the risks of allergic and respiratory diseases in children". Pediatric Allergy and Immunology. 18 (1): 27–35. doi:10.1111/j.1399-3038.2006.00487.x. PMID   17295796. S2CID   24606118.
66. Do not use Eusol and gauze to manage surgical wounds that are healing by secondary intention, October 2008, NICE, London Archived 14 July 2014 at the Wayback Machine .Accessed 3 July 2014.
67. ASC – PT Asahimas Chemical (2009): "Sodium hypochlorite 10% Archived 12 July 2018 at the Wayback Machine ". Online Material Safety Data Sheet (MSDS). Accessed on 2018-06-14.

Bibliography

• Jones FL (December 1972). "Chloride poisoning from mixing household cleaners". JAMA. 222 (10): 1312. doi:10.1001/jama.222.10.1312. PMID   4678160.
• Bonnard M, Brondeau MT, Falcy M, Jargot D, Miraval S, Protois J, Schneider O. "Eaux et extraits de Javel Hypochlorite de sodium en solution". Fiche Toxicologique. 157.

External links

• International Chemical Safety Card 0482 (solutions < 10% active Cl)
• International Chemical Safety Card 1119 (solutions > 10% active Cl)
• Institut national de recherche et de sécurité (in French)
• Home and Leisure Accident Statistics 2002 (UK RoSPA)
• Emergency Disinfection of Drinking Water (United States Environmental Protection Agency)
• Chlorinated Drinking Water (IARC Monograph)
• NTP Study Report TR-392: Chlorinated & Chloraminated Water (US NIH)
• Guidelines for the Use of Chlorine Bleach as a Sanitizer in Food Processing Operations (Oklahoma State University)