Chlorine dioxide

Chlorine dioxide is a chemical compound with the formula ClO₂. This yellowish-green gas crystallizes as bright orange crystals at −59 °C. As one of several oxides of chlorine, it is a potent and useful oxidizing agent used in water treatment and in bleaching.

Structure and bonding

Chlorine dioxide is a neutral chlorine compound. It is very different from elementary chlorine, both in its chemical structure and in its behavior. One of the most important qualities of chlorine dioxide is its high water solubility, especially in cold water. Chlorine dioxide does not hydrolyze when it enters water; it remains a dissolved gas in solution. Chlorine dioxide is approximately 10 times more soluble in water than chlorine.

The molecule ClO₂ has an odd number of valence electrons, and therefore, it is a paramagnetic radical. Its electronic structure has long baffled chemists because none of the possible Lewis structures is very satisfactory. In 1933, L. O. Brockway proposed a structure that involved a three-electron bond. Chemist Linus Pauling further developed this idea and arrived at two resonance structures involving a double bond on one side and a single bond plus three-electron bond on the other. In Pauling's view the latter combination should represent a bond that is slightly 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 HOMO is indeed an incompletely-filled orbital.