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Concept
Chlorine dioxide
Summary
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.
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).
In 1933, Lawrence O. Brockway, a graduate student of Linus Pauling, proposed a structure that involved a three-electron bond and two single bonds. However, Pauling in his General Chemistry shows a double bond to one oxygen and a single bond plus a three-electron bond to the other. The valence bond structure would be represented as the resonance hybrid depicted by Pauling. The three-electron bond represents a bond that is weaker than the double bond. In molecular orbital theory this idea is commonplace if the third electron is placed in an anti-bonding orbital. Later work has confirmed that the highest occupied molecular orbital is indeed an incompletely-filled antibonding orbital.
The crystal structure of ClO2 is orthorhombic, and displays the symmetry of the Pbca space group.
Chlorine dioxide was first prepared in 1811 by Sir Humphry Davy.
Chlorine dioxide is a compound that 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.
In the laboratory, ClO2 can be prepared by oxidation of sodium chlorite with chlorine:
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.
Official source
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