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Production

Potassium hypochlorite was first produced in 1789 by Claude Louis Berthollet in his laboratory
on the quay 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).
[1]
However, this process was not very efficient, and
alternative production methods were sought. One such method involved the extraction of
chlorinated lime (known as bleaching powder) with sodium carbonate to yield low levels of
available chlorine. 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 - a reference to the university's pathology department, where it
was developed
[2]
- and "Dakin's Solution". The UK's National Institute for Health and Care
Excellence in October 2008 recommended the preparation should not be used in routine wound
care.
[3]

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.
[4][unreliable source?]
Both electric
power and brine solution 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.
Today, an improved version of this method, known as the Hooker process (named after Hooker
Chemicals, now 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 cold and dilute sodium hydroxide solution. It 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.
Cl
2
+ 2 NaOH → NaCl + NaClO + H
2
O
Hence, chlorine is simultaneously reduced and oxidized; this process is known as
disproportionation.
Commercial solutions always contain significant amounts of sodium chloride (common salt) as
the main by-product, as seen in the equation above.
Packaging and sale
Like many hypochlorites,
[citation needed]
anhydrous NaClO obtained by desiccation of the
pentahydrate will decompose violently on heating or friction,
[5]
however, it is more stable in cold
dilute solutions.
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.
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.
[6]

A 12% solution is widely used in waterworks for the chlorination of water, and a 15% solution is
more commonly
[7]
used for disinfection of waste water in treatment plants. Sodium hypochlorite
can also be used for point-of-use disinfection of drinking water.
[8]

Dilute solutions (50 ppm to 1.5%) are found in disinfecting sprays and wipes used on hard
surfaces.
[9][10]

Reactions
Sodium hypochlorite reacts with hydrochloric acid to release chlorine gas:
NaClO + 2 HCl → Cl
2
+ H
2
O + NaCl
It reacts with other acids, such as acetic acid, to release hypochlorous acid:
NaClO + CH
3
COOH → HClO + CH
3
COONa
It decomposes when heated to form sodium chlorate and sodium chloride:
3 NaClO → NaClO
3
+ 2 NaCl
In reaction with hydrogen peroxide it gives off molecular oxygen:
NaClO + H
2
O
2
→ H
2
O + NaCl + O
2

When dissolved in water it slowly decomposes, releasing sodium and chloride ions, and
hydroxyl radicals:
NaClO + H
2
O → Na
+
+ Cl
-
+ 2 HO•
Those hydroxyl radicals can oxidize organic compounds or self-react to form water and
oxygen
R-CH
2
-OH + 4 HO• → R-COOH + 3 H
2
O
4 HO• → 2 H
2
O + O
2
(dissolved or gas)
Sodium hypochlorite reacts with most nitrogen compounds to form volatile chloramines,
dichloramines, and nitrogen trichloride:
NH
3
+ NaOCl → NH
2
Cl + NaOH
NH
2
Cl+ NaOCl → NHCl
2
+ NaOH
NHCl
2
+ NaOCl → NCl
3
+ NaOH
In the presence of a phase-transfer catalyst, alcohols are oxidized to the corresponding carbonyl
compound.
[11]

Heterogeneous reactions of sodium hypochlorite and metals such as zinc proceed slowly to give
the metal oxide or hydroxide:
NaClO + Zn → ZnO + NaCl
Homogeneous reactions with metal coordination complexes proceed somewhat faster. This has
been exploited in the Jacobsen epoxidation.
Uses
Bleaching
Household bleach is, in general, a solution containing 3-8% sodium hypochlorite 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.
[12]

In household form, sodium hypochlorite is used for removal of stains from laundry. It is
particularly effective on cotton fiber, which stains easily but bleaches well. Usually 50 to 250
mL of bleach per load is recommended for a standard-size washer. The properties of household
bleach that make it effective for removing stains also result in cumulative damage to organic
fibers, such as cotton, and the useful lifespan of these materials will be shortened with regular
bleaching. The sodium hydroxide (NaOH) that is also found in household bleach (as noted later)
causes fiber degradation as well. It is not volatile, and residual amounts of NaOH not rinsed out
will continue slowly degrading organic fibers in the presence of humidity. For these reasons, if
stains are localized, spot treatments should be considered whenever possible. With safety
precautions, post-treatment with vinegar (or another weak acid) will neutralize the NaOH, and
volatilize the chlorine from residual hypochlorite. Old T-shirts and cotton sheets that rip easily
demonstrate the costs of laundering with household bleach. Hot water increases the effectiveness
of the bleach, owing to the increased reactivity of the molecules.
Stain removal
Sodium hypochlorite has destaining properties.
[13]
Amongst other applications, it can be used to
remove mold stains, dental stains caused by fluorosis,
[14]
and stains on crockery, especially those
caused by the tannins in tea.
Disinfection
See also: Hypochlorous acid
A weak solution of 2% household bleach in warm water is used to sanitize smooth surfaces prior
to brewing of beer or wine. Surfaces must be rinsed 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.
US Government regulations (21 CFR Part 178) 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). If higher concentrations are
used, the surface must be rinsed with potable water after sanitizing.
A 1-in-5 dilution of household bleach with water (1 part bleach to 4 parts water) is effective
against many bacteria and some viruses, and is often the disinfectant of choice in cleaning
surfaces in hospitals (primarily in the United States). The solution is corrosive and needs to be
thoroughly removed afterwards, 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.
[15]
Some cleaners are
formulated to be thick so as not to drain quickly from vertical surfaces, such as the inside of a
toilet bowl.
Deodorising

This section requires expansion. (June 2013)
Sodium hypochlorite has deodorising properties
[13]

Water treatment
In drinking water systems, swimming pools, etc., sodium hypochlorite is widely used for
chlorination. Hypochlorites are an alternative to chlorine gas, which is difficult to handle in
many contexts. Also, accidents involving chlorine gas are more serious than accidents involving
hypochlorites.
[citation needed]
Chlorination usually produces small quantities of harmful byproducts.
Hypochlorites are very similar to chlorine gas in this regard.
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 now used in endodontics during root canal treatments. It is the
medicament of choice due to its efficacy against pathogenic organisms and pulp digestion. In
previous times, Henry Drysdale Dakin's solution (0.5%) had been used. Its concentration for use
in endodontics today varies from 0.5% to 5.25%. At low concentrations it will dissolve mainly
necrotic tissue; whereas at higher concentrations tissue dissolution is better but it also dissolves
vital tissue, a generally undesirable effect. It has been shown that clinical effectiveness does not
increase conclusively for concentrations higher than 1%.
[16]

Nerve agent neutralization
At the various nerve agent (chemical warfare nerve gas) destruction facilities throughout the
United States, 50% sodium hypochlorite is used as a means of removing all traces of nerve agent
or blister agent from Personal Protection Equipment after an entry is made by personnel into
toxic areas. 50% sodium hypochlorite is also used to neutralize any accidental releases of nerve
agent in the toxic areas. Lesser concentrations of sodium hypochlorite are used in similar fashion
in the Pollution Abatement System to ensure that no nerve agent is released in furnace flue gas.
Reduction of skin damage
Dilute bleach baths have been used for decades to treat moderate to severe eczema in
humans,
[17][18]
but it has not been clear why they work. 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-kB)
is known to play a critical role in inflammation, ageing and response to radiation. The
researchers found that if NF-kB 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.
[17][19]

Safety
Sodium hypochlorite is a strong oxidizer. Oxidation reactions are corrosive, solutions burn skin
and cause eye damage, especially when used in concentrated forms. However, as recognized by
the NFPA, 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).
Mixing bleach with some household cleaners can be hazardous. For example, mixing an acid
cleaner with sodium hypochlorite bleach generates chlorine gas. Mixing with ammonia solutions
(including urine) produces chloramines. Mixtures of other cleaning agents and or organic matter
can result in a gaseous reaction that can cause acute lung injury.
[20]

NH
4
OH + NaClO → NaOH + NH
2
Cl + H
2
O
Both chlorine gas and chloramine gas are toxic. Bleach can react violently with hydrogen
peroxide and produce oxygen gas:
H
2
O
2
(aq) + NaClO(aq) → NaCl(aq) + H
2
O(l) + O
2
(g)
It is estimated that there are about 3300 accidents needing hospital treatment caused by sodium
hypochlorite solutions each year in British homes (RoSPA, 2002).
Household bleach and pool chlorinator solutions are typically stabilized by a significant
concentration of lye (caustic soda, NaOH) as part of the manufacturing reaction. Skin contact
will produce caustic irritation or burns due to defatting and saponification of skin oils and
destruction of tissue. The slippery feel of bleach on skin is due to this process. Trichloramine, the
gas that is in swimming pools can cause atopic asthma.
[20][verification needed]

A recent European study indicated that sodium hypochlorite and organic chemicals (e.g.,
surfactants, fragrances) contained in several household cleaning products can react to generate
chlorinated volatile organic compounds (VOCs).
[21]
These chlorinated compounds are emitted
during cleaning applications, some of which are toxic and probable human carcinogens. 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. The increase in chlorinated volatile organic
compound concentrations was the lowest for plain bleach and the highest for the products in the
form of “thick liquid and gel”. The significant increases observed in indoor air concentrations of
several chlorinated VOCs (especially carbon tetrachloride and chloroform) indicate that the
bleach use may be a source that could be important in terms of inhalation exposure to these
compounds. The authors suggested that using these cleaning products may significantly increase
the cancer risk.
[21]

Chlorination of drinking water can oxidize organic contaminants, producing chloroform and
other trihalomethanes, which are carcinogenic, and many hundreds of possible disinfection by-
products, the vast majority of which are not monitored.
One major concern arising from sodium hypochlorite use is that it tends to form chlorinated
organic compounds; this can occur during household storage and use as well during industrial
use.
[12]
For example, when household bleach and wastewater were mixed, 1-2% of the available
chlorine was observed to form organic compounds.
[12]
As of 1994, not all the byproducts had
been identified, but identified compounds include chloroform and carbon tetrachloride.
[12]
The
estimated exposure to these chemicals from use is estimated to be within occupational exposure
limits.
[12]

Neutralization
Sodium thiosulfate is an effective chlorine neutralizer. Rinsing with a 5 mg/L solution, followed
by washing with soap and water, quickly removes chlorine odor from the hands.
[citation needed]