Chlorine tetroxide
| Names | |
|---|---|
| IUPAC name
Tetraoxidochlorine
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| Identifiers | |
3D model (JSmol)
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| ChEBI | |
| ChemSpider | |
| 239881 | |
PubChem CID
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| Properties | |
| ClO4 | |
| Molar mass | 99.45 g mol−1 |
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 tetroxide is an unstable chlorine oxide with the chemical formula ClO4.
History
[edit]Gomberg's mistaken 1923 production
[edit]In 1923, chemist Moses Gomberg proposed a production method of chlorine tetroxide. He claimed that treating iodine and silver perchlorate in anhydrous diethyl ether produced it.[2]
- I2 + 2 AgClO4 → 2 AgI + (ClO4)2
However, later researchers claimed that the product was iodine perchlorate.[3] 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.[citation needed]
Properties
[edit]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.[4]
The structure of chlorine tetroxide is uncertain; the molecular point group may be Cs, C2v, or Td.[5]
In a solid oxygen matrix ClO4 reacts to form ClO6Cl, which has three double bonded oxygen atoms, and a chain of three oxygen atoms -O-O-O• attached to the chlorine.[5]
References
[edit]- ^ "Perchloryloxy". Active Thermochemical Tables.
- ^ 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.
- ^ 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.
- ^ (in Chinese)张青莲 (1991). 《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.
- ^ a b 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. PMID 12693042.
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