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Chlorine dioxide

physical science Maturity 5-7 Next article →

Chlorine dioxide is a highly reactive chemical compound with the formula ClO2. It is an essential tool in modern industry for bleaching and disinfection. This substance is unique because it exists in three distinct physical states depending on temperature. Above 55 degrees Celsius, it appears as a yellowish-green gas. Between -89 and 55 degrees Celsius, it is a reddish-brown liquid. Below -89 degrees Celsius, it forms bright orange crystals.

ClO2 orthorhombic Pbca cmp-23207 computed
ClO2 orthorhombic Pbca cmp-23207 computed

This compound is a paramagnetic radical. This means it has an odd number of valence electrons.

ClO2
ClO2

The molecular structure of chlorine dioxide is quite unusual. In 1933, Lawrence O. Brockway, a student of Linus Pauling, proposed a structure involving a three-electron bond and two single bonds. Pauling described the structure as a resonance hybrid in his book, General Chemistry. This hybrid includes a double bond to one oxygen and a single bond plus a three-electron bond to the other. The three-electron bond is weaker than the double bond. In molecular orbital theory, this happens because the third electron occupies an anti-bonding orbital.

ClO2
ClO2

Producing chlorine dioxide requires precise methods to ensure safety. It can be made through flash photolysis, where chlorine reacts with oxygen under ultraviolet light. However, this only produces trace amounts. It can also be prepared by the oxidation of sodium chlorite. Common laboratory methods include reacting sodium chlorite with chlorine, hydrochloric acid, or sulfuric acid. The chlorite-sulfuric acid method is unique because it is completely chlorine-free. It does, however, require 25% more chlorite to reach the same yield.

Chlorine-dioxide solution-vs-gas
Chlorine-dioxide solution-vs-gas

Industrial production often relies on the reduction of sodium chlorate. Today, over 95% of the world's chlorine dioxide is made this way for pulp bleaching. This process uses a strong acid and a reducing agent like methanol or hydrogen peroxide. Modern technologies prefer methanol or hydrogen peroxide because they are efficient and do not create elemental chlorine. Using methanol and sulfuric acid is a very important commercial route. This method produces sodium sulfate as a valuable side-product for pulp mills. Since 1999, a variant using hydrogen peroxide and sulfuric acid has been used for small-scale water treatment.

Handling chlorine dioxide requires extreme caution because it can be unstable. It is much more soluble in water than elemental chlorine, being about 10 times more soluble. However, if the gas concentration exceeds 10% in air at standard temperature and pressure, it may explode. This decomposition can be triggered by light, pressure shocks, or hot spots. To prevent this, it is almost never handled as a pure gas. Instead, it is kept in an aqueous solution between 0.1 and 10 grams per liter. In the United States, it is often produced on-site because it cannot be transported easily.

One of the most significant uses for this chemical is in the paper industry. About 95% of all bleached kraft pulp is produced using chlorine dioxide in ECF, or elemental chlorine-free, bleaching sequences. This process is vital because it minimizes the production of harmful organochlorine compounds. Beyond paper, it is a powerful disinfectant for drinking water. A plant in Niagara Falls, New York, first used it for water treatment in 1944. In 1956, Brussels, Belgium, began using it on a large scale. It is much more effective than chlorine against pathogens like the Giardia cysts and Cryptosporidium oocysts.

Chlorine dioxide also plays a role in public health and environmental safety. It was used to decontaminate buildings after the 2001 anthrax attacks in the United States. Following Hurricane Katrina, it helped remove dangerous mold from flooded houses. It is even used to sanitize fruits like blueberries and strawberries. In water treatment, it produces 70% fewer halomethanes than elemental chlorine does. This is important because halomethanes are suspected carcinogens. The EPA limits chlorine dioxide in drinking water to 0.8 mg/L to ensure safety and manage by-products like chlorite.

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File:ClO2.svg
ClO2.svg
File:Chlorine-dioxide solution-vs-gas.svg
Chlorine-dioxide solution-vs-gas.svg
File:ClO2 orthorhombic Pbca cmp-23207 computed.png
ClO2 orthorhombic Pbca cmp-23207 computed.png
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