Chlorine tetroxide

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Chlorine tetroxide is a chlorine oxide with the chemical formula ClO


Gomberg's mistaken 1923 production[edit]

In 1923, the famous radical chemist Moses Gomberg proposed a production method of chlorine tetroxide. He claimed that treating iodine and silver perchlorate in anhydrous diethyl ether produced it.[1]

I2 + 2 AgClO4 → 2 AgI + (ClO4)2

However, later researchers claimed that the product was iodine perchlorate.[2] So far, however, there is no certain evidence for the existence of iodine perchlorate, either.

Eachus' 1968 production[edit]

In 1968, Eachus synthesized it by exposing potassium chlorate to gamma rays at 77 K. It is a reaction intermediate of the decomposition of dichlorine heptoxide.


The electron affinity energy of chlorine tetroxide can be figured out using the Born-Haber cycle and the lattice energy data of perchlorates. It is about 561 kJ/mol.[3]

The structure of chlorine tetroxide is uncertain, and the symmetry point group may be Cs, C2v, or Td.[4]


  1. ^ Gomberg, M. (1 February 1923). "The Reaction Between Silver Perchlorate and Iodine. Chlorine Tetra-Oxide". Journal of the American Chemical Society. 45 (2): 398–421. doi:10.1021/ja01655a017. 
  2. ^ Alcock, N. W.; Waddington, T. C. (1 January 1962). "478. The reaction between iodine and silver perchlorate". Journal of the Chemical Society (Resumed): 2510. doi:10.1039/JR9620002510. 
  3. ^ (in simplified Chinese)张青莲. 《无机化学丛书》第六卷:卤素、铜分族、锌分族. 北京: 科学出版社. p. 272. ISBN 7-03-002238-6. 
  4. ^ Kopitzky, Rodion; Grothe, Hinrich; Willner, Helge (16 December 2002). "Chlorine Oxide Radicals ClOx (x=1-4) Studied by Matrix Isolation Spectroscopy". Chemistry: A European Journal. 8 (24): 5601–5621. doi:10.1002/1521-3765(20021216)8:24<5601::AID-CHEM5601>3.0.CO;2-Z.