Chlorine dioxide
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Names | |||
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IUPAC name
Chlorine dioxide
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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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100.030.135 | ||
EC Number |
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1265 | |||
MeSH | Chlorine+dioxide | ||
PubChem CID
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RTECS number
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UNII | |||
UN number | 9191 | ||
CompTox Dashboard (EPA)
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Properties | |||
ClO2 | |||
Molar mass | 67.45 g·mol−1 | ||
Appearance | Yellow to reddish gas | ||
Odor | Acrid | ||
Density | 2.757 g dm−3[1] | ||
Melting point | −59 °C (−74 °F; 214 K) | ||
Boiling point | 11 °C (52 °F; 284 K) | ||
8 g/L at 20 °C | |||
Solubility | Soluble in alkaline solutions and sulfuric acid | ||
Vapor pressure | >1 atm[2] | ||
Henry's law
constant (kH) |
4.01×10−2 atm m3 mol−1 | ||
Acidity (pKa) | 3.0(5) | ||
Thermochemistry | |||
Std molar
entropy (S⦵298) |
257.22 J K−1 mol−1 | ||
Std enthalpy of (ΔfH⦵298)formation |
104.60 kJ/mol | ||
Hazards | |||
Occupational safety and health (OHS/OSH): | |||
Main hazards
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Highly toxic, corrosive, unstable, powerful oxidizer | ||
GHS labelling: | |||
Danger | |||
H271, H300+H310+H330, H314, H372 | |||
P210, P220, P260, P264, P271, P280, P283, P284, P301+P310, P304+P340, P305+P351+P338, P306+P360, P371+P380+P375, P403+P233, P405, P501 | |||
NFPA 704 (fire diamond) | |||
Lethal dose or concentration (LD, LC): | |||
LD50 (median dose)
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94 mg/kg (oral, rat)[3] | ||
LCLo (lowest published)
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260 ppm (rat, 2 hr)[4] | ||
NIOSH (US health exposure limits): | |||
PEL (Permissible)
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TWA 0.1 ppm (0.3 mg/m3)[2] | ||
REL (Recommended)
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TWA 0.1 ppm (0.3 mg/m3) ST 0.3 ppm (0.9 mg/m3)[2] | ||
IDLH (Immediate danger) |
5 ppm[2] | ||
Safety data sheet (SDS) | Safety Data Sheet Archive. | ||
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Chlorine dioxide is a chemical compound with the formula ClO2 that exists as yellowish-green gas above 11 °C, a reddish-brown liquid between 11 °C and −59 °C, and as bright orange crystals below −59 °C. It is usually handled as an aqueous solution. It is commonly used as a bleach. More recent developments have extended its applications in food processing and as a disinfectant.
Structure and bonding
The molecule ClO2 has an odd number of valence electrons, and therefore, it is a paramagnetic radical. It is an unusual "example of an odd-electron molecule which is stable towards dimerization" (nitric oxide being another example).[5]
In 1933,
The crystal structure of ClO2 is orthorhombic, and displays the symmetry of the Pbca space group.[9]
Preparation
Chlorine dioxide was first prepared in 1811 by
The reaction of chlorine with oxygen under conditions of flash photolysis in the presence of ultraviolet light results in trace amounts of chlorine dioxide formation.[11]
- .
Chlorine dioxide can decompose violently when separated from diluting substances. As a result, preparation methods that involve producing solutions of it without going through a gas-phase stage are often preferred.
Oxidation of chlorite
In the laboratory, ClO2 can be prepared by oxidation of sodium chlorite with chlorine:[12]
Traditionally, chlorine dioxide for disinfection applications has been made from sodium chlorite or the sodium chlorite–hypochlorite method:
or the sodium chlorite–hydrochloric acid method:
or the chlorite–sulfuric acid method:
All three methods can produce chlorine dioxide with high chlorite conversion yield. Unlike the other processes, the chlorite–sulfuric acid method is completely chlorine-free, although it suffers from the requirement of 25% more chlorite to produce an equivalent amount of chlorine dioxide. Alternatively, hydrogen peroxide may be efficiently used in small-scale applications.[13]
Addition of sulfuric acid or any strong acid to chlorate salts produces chlorine dioxide.[7]
Reduction of chlorate
In the laboratory, chlorine dioxide can also be prepared by reaction of potassium chlorate with oxalic acid:
or with oxalic and sulfuric acid:
Over 95% of the chlorine dioxide produced in the world today is made by reduction of sodium chlorate, for use in pulp bleaching. It is produced with high efficiency in a strong acid solution with a suitable reducing agent such as methanol, hydrogen peroxide, hydrochloric acid or sulfur dioxide.[13] Modern technologies are based on methanol or hydrogen peroxide, as these chemistries allow the best economy and do not co-produce elemental chlorine. The overall reaction can be written as:[14]
As a typical example, the reaction of sodium chlorate with hydrochloric acid in a single reactor is believed to proceed through the following pathway:
which gives the overall reaction
The commercially more important production route uses methanol as the reducing agent and sulfuric acid for the acidity. Two advantages of not using the chloride-based processes are that there is no formation of elemental chlorine, and that sodium sulfate, a valuable chemical for the pulp mill, is a side-product. These methanol-based processes provide high efficiency and can be made very safe.[13]
The variant process using sodium chlorate, hydrogen peroxide and sulfuric acid has been increasingly used since 1999 for water treatment and other small-scale disinfection applications, since it produce a chlorine-free product at high efficiency, over 95%.[citation needed]
Other processes
Very pure chlorine dioxide can also be produced by electrolysis of a chlorite solution:[15]
High-purity chlorine dioxide gas (7.7% in air or nitrogen) can be produced by the gas–solid method, which reacts dilute chlorine gas with solid sodium chlorite:[15]
Handling properties
At partial pressures above 10 kPa (1.5 psi)
Uses
Chlorine dioxide is used for bleaching of wood pulp and for the disinfection (called chlorination) of municipal drinking water,[16][17]: 4–1 [18] treatment of water in oil and gas applications, disinfection in the food industry, microbiological control in cooling towers, and textile bleaching.[19] As a disinfectant, it is effective even at low concentrations because of its unique qualities.[13][17][19]
Bleaching
Chlorine dioxide is sometimes used for bleaching of wood pulp in combination with chlorine, but it is used alone in ECF (elemental chlorine-free) bleaching sequences. It is used at moderately acidic
Chlorine dioxide has been used to bleach flour.[22]
Water treatment
The water treatment plant at
Chlorine dioxide is also superior to chlorine when operating above
Chlorine dioxide is less corrosive than chlorine and superior for the control of Legionella bacteria.[18][30] Chlorine dioxide is superior to some other secondary water disinfection methods, in that chlorine dioxide is not negatively impacted by pH, does not lose efficacy over time, because the bacteria will not grow resistant to it), and is not negatively impacted by
It is more effective as a disinfectant than chlorine in most circumstances against waterborne pathogenic agents such as
The use of chlorine dioxide in water treatment leads to the formation of the by-product chlorite, which is currently limited to a maximum of 1 part per million in drinking water in the USA.[17]: 4–33 This EPA standard limits the use of chlorine dioxide in the US to relatively high-quality water, because this minimizes chlorite concentration, or water that is to be treated with iron-based coagulants, because iron can reduce chlorite to chloride.[32] The World Health Organization also advises a 1ppm dosification.[27]
Use in public crises
Chlorine dioxide has many applications as an oxidizer or disinfectant.
In addressing the COVID-19 pandemic, the
Other disinfection uses
Chlorine dioxide may be used as a fumigant treatment to "sanitize" fruits such as blueberries, raspberries, and strawberries that develop molds and yeast.[38]
Chlorine dioxide may be used to disinfect poultry by spraying or immersing it after slaughtering.[39]
Chlorine dioxide may be used for the disinfection of
Chlorine dioxide may be used for control of zebra and quagga mussels in water intakes.[17]: 4–34
Chlorine dioxide was shown to be effective in
For water purification during camping, disinfecting tablets containing chlorine dioxide are more effective against pathogens than those using household bleach, but typically cost more.[43][44]
Other uses
Chlorine dioxide is used as an oxidant for destroying phenols in wastewater streams and for odor control in the air scrubbers of animal byproduct (rendering) plants.[17]: 4–34 It is also available for use as a deodorant for cars and boats, in chlorine dioxide-generating packages that are activated by water and left in the boat or car overnight.
In dilute concentrations, chlorine dioxide is an ingredient that acts as an antiseptic agent in some mouthwashes.[45][46]
Safety issues in water and supplements
Potential hazards with chlorine dioxide include poisoning and the risk of spontaneous ignition or explosion on contact with flammable materials.[47][48]
Chlorine dioxide is toxic, and limits on human exposure are required to ensure its safe use. The
Chlorine dioxide has been fraudulently and illegally marketed as an ingestible cure for a wide range of diseases, including childhood autism[51] and coronavirus.[52][53][54] Children who have been given enemas of chlorine dioxide as a supposed cure for childhood autism have suffered life-threatening ailments.[51] The U.S. Food and Drug Administration (FDA) has stated that ingestion or other internal use of chlorine dioxide, outside of supervised oral rinsing using dilute concentrations, has no health benefits of any kind, and it should not be used internally for any reason.[55][56]
Pseudomedicine
On 30 July and 1 October 2010, the United States Food and Drug Administration warned against the use of the product "
References
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- ^ Aieta, E. Marco, and James D. Berg. "A Review of Chlorine Dioxide in Drinking Water Treatment." Journal (American Water Works Association) 78, no. 6 (1986): 62-72. Accessed April 24, 2021. http://www.jstor.org/stable/41273622
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- ^ ISBN 978-3527306732.
- ^ Ni, Y.; Wang, X. (1996). "Mechanism of the Methanol Based ClO2 Generation Process". International Pulp Bleaching Conference. TAPPI. pp. 454–462.[permanent dead link]
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External links
- Media related to chlorine dioxide at Wikimedia Commons