Chlorine perchlorate

Chlorine perchlorate

Names
IUPAC name Chloro perchlorate [1]
Systematic IUPAC name Chloro perchlorate [1]
Other names Chlorine(I,VII) oxide Dichlorine tetroxide (Chlorooxy)chlorane trioxide [2]
Identifiers
CAS Number	27218-16-2  Y
3D model (JSmol)	Interactive image
ChEBI	CHEBI:52353
ChemSpider	147540  N
PubChem CID	168667
CompTox Dashboard (EPA)	DTXSID00181686
InChI InChI=1S/Cl2O4/c1-6-2(3,4)5 N Key: JRONPIZRZBBOBR-UHFFFAOYSA-N N
SMILES ClO[Cl](=O)(=O)=O
Properties
Chemical formula	Cl2O4
Molar mass	134.90 g·mol−1
Appearance	Pale green liquid
Density	1.81 g·cm−3
Melting point	−117 °C (−179 °F; 156 K)
Boiling point	20 °C (68 °F; 293 K) (decomposes)
Solubility in water	Reacts
Hazards
Occupational safety and health (OHS/OSH):
Main hazards	oxidizer
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). N  verify  (what is  YN ?) Infobox references

Chlorine perchlorate is a chemical compound with the formula Cl₂O₄. This chlorine oxide is an asymmetric oxide, with one chlorine atom in +1 oxidation state and the other +7, with proper formula Cl−O−ClO₃. It is produced by the photodimerization of chlorine dioxide (ClO₂) at room temperature by 436 nm ultraviolet light: ^{[3] [4] [5]}

2 ClO₂ → ClOClO₃

Chlorine perchlorate can also be made by the following reaction at −45 °C.

CsClO₄ + ClOSO₂F → CsSO₃F + ClOClO₃

Properties

Chlorine perchlorate is a pale greenish liquid. It is less stable than ClO₂ (chlorine dioxide)^{[ citation needed ]} and decomposes at room temperature to give O₂ (oxygen), Cl₂ (chlorine) and Cl₂O₆ (dichlorine hexoxide):

2 ClOClO₃ → O₂ + Cl₂ + Cl₂O₆

Chlorine perchlorate reacts with metal chlorides to form chlorine and the corresponding anhydrous perchlorate:

CrO₂Cl₂ + 2 ClOClO₃ → 2 Cl₂ + CrO₂(ClO₄)₂

TiCl₄ + 4 ClOClO₃ → 4 Cl₂ + Ti(ClO₄)₄

2 AgCl + 2 ClOClO₃ → 2 AgClO₄ + Cl₂

Reactions

Reactant	Conditions	Products
—	Heat	dichlorine hexoxide (80%), chlorine dioxide, chlorine, oxygen
—	Ultraviolet light	dichlorine heptoxide, chlorine, oxygen [5]
caesium iodide	−45 °C	caesium tetraperchloratoiodate(III) Cs+[I(OClO3)4]− [note 1]
ClOSO2F or ClF	—	M+ClO−4 (M = Cs or [NO2]) [note 2]
bromine	−45 °C	bromine perchlorate (BrOClO3) [note 2]
iodine(0.33  mol)	−50 °C	iodine(III) perchlorate I(OClO3)3 [note 3]

Notes

1. Cs⁺[I(OClO₃)₄]⁻ is a pale yellow salt which is stable at room temperature. It has a square IO₄ unit.
2. M⁺ClO−4 (M = Cs or [NO₂]) reacts with BrOSO₂F at −20 °C and produces bromine perchlorate (BrOClO₃). Bromine perchlorate then reacts with hydrogen bromide (HBr) at −70 °C and produces elemental bromine (Br₂) and perchloric acid (HClO₄).
3. The last ^[6] attempt to form iodine monoperchlorate (IOClO₃) occurred in 1972, ^[7] and even at low temperatures yielded instead the triperchlorate. On warming, the latter then decomposes to iodate.

References

1. "Chloro Perchlorate - PubChem Public Chemical Database". The PubChem Project. USA: National Center for Biotechnology Information.
2. nih.gov
3. A. J. Schell-Sorokin; D. S. Bethune; J. R. Lankard; M. M. T. Loy; P. P. Sorokin (1982). "Chlorine perchlorate a major photolysis product of chlorine dioxide". J. Phys. Chem. 86 (24): 4653–4655. doi:10.1021/j100221a001.
4. M. I. Lopez; J. E. Sicre (1988). "Ultraviolet spectrum of chlorine perchlorate". J. Phys. Chem. 92 (2): 563–564. doi:10.1021/j100313a062.
5. Rao, Balaji; Anderson, Todd A.; Redder, Aaron; Jackson, W. Andrew (2010-04-15). "Perchlorate Formation by Ozone Oxidation of Aqueous Chlorine/Oxy-Chlorine Species: Role of ClxOy Radicals". Environmental Science & Technology. 44 (8): 2961–2967. Bibcode:2010EnST...44.2961R. doi:10.1021/es903065f. ISSN   0013-936X. PMID   20345093.
6. Zefirov, N. S.; Zedankin, V. V.; Koz'min, A. S. (1988). "The synthesis and properties of covalent organic perchlorates". Russian Chemical Reviews. 57 (11). Turpion: 1047. doi:10.1070/RC1988v057n11ABEH003410. Translated from Uspekhi Khimii volume 57 (1988), pp. 1815-1839.
7. Christe, Karl O.; Schack, Carl J. (1972) [20 September 1971]. "Iodine tris­(perch1orate) and cesium tetrakis­(perchlorato)­iodate(III)". Inorganic Chemistry. 11 (7): 1684. doi:10.1021/ic50113a047.