Chlorine tetroxide

Chlorine tetroxide  Names

IUPAC name

Tetraoxidochlorine

Identifiers

3D model (JSmol)

* Interactive image

ChEBI |

* CHEBI:29420

ChemSpider |

* 4574089

Gmelin Reference

| 239881

PubChem CID

* 5460591

InChI

* InChI=1S/ClO4/c2-1(3,4)5

Key: UXZQWBXGIHHEHG-UHFFFAOYSA-N

SMILES

* O=Cl(=O)(=O)[O]

Properties

Chemical formula

| 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).

Infobox references

Chemical compound

Chlorine tetroxide is an unstable chlorine oxide with the chemical formula ClO4.

## Contents

* 1 History
* 1.1 Gomberg's mistaken 1923 production
* 1.2 Eachus' 1968 production
* 2 Properties
* 3 References

## History[edit]

### 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.

## 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.[3]

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

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.[4]

## References[edit]

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 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. ^ 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.

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Chlorine compounds

Chlorides and acids|

* ClNO3
* HCl
* HClO
* HClO2
* HClO3
* HClO4
* SiCl4

Chlorine fluorides|

* ClF
* ClF3
* ClF5

Chlorine oxides|

* ClO
* ClO2
* Cl2O
* Cl2O2
* Cl2O3
* Cl2O4
* Cl2O5
* Cl2O6
* Cl2O7
* ClO4

Chlorine oxyfluorides|

* ClOF3
* ClO2F
* ClO3F

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