Chlorine perchlorate
{{Chembox
| Verifiedfields = changed
| Watchedfields = changed
| ImageFileL1 = Dichlorine tetraoxide.svg
| ImageSizeL1 = 120
| ImageFileR1 = Chlorine perchlorate molecule spacefill.png
| ImageSizeR1 = 120
| ImageAlt1 = Space-filling model of the chlorine perchlorate molecule
| verifiedrevid = 409937153
| IUPACName = Chloro perchlorate{{Cite web|title = Chloro Perchlorate - PubChem Public Chemical Database|url = https://pubchem.ncbi.nlm.nih.gov/summary/summary.cgi?cid=168667|work = The PubChem Project|location = USA|publisher = National Center for Biotechnology Information}}
| SystematicName = Chloro perchlorate
| OtherNames = {{ubl|Chlorine(I,VII) oxide|Dichlorine tetroxide|(Chlorooxy)chlorane trioxidehttps://pubchem.ncbi.nlm.nih.gov/compound/chlorine_perchlorate}}
| Section1 = {{Chembox Identifiers
| CASNo_Ref = {{cascite|correct|??}}
| CASNo = 27218-16-2
| PubChem = 168667
| ChemSpiderID = 147540
| ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}}
| SMILES = ClO[Cl](=O)(=O)=O
| StdInChI = 1S/Cl2O4/c1-6-2(3,4)5
| StdInChI_Ref = {{stdinchicite|changed|chemspider}}
| StdInChIKey = JRONPIZRZBBOBR-UHFFFAOYSA-N
| StdInChIKey_Ref = {{stdinchicite|changed|chemspider}}
| ChEBI = 52353
}}
| Section2 = {{Chembox Properties
| Cl=2 | O=4
| Appearance = Pale green liquid
| Density = 1.81 g·cm−3
| MeltingPtC = -117
| BoilingPtC = 20
| BoilingPt_notes = (decomposes)
| Solubility = Reacts
}}
| Section3 = {{Chembox Hazards
| MainHazards = oxidizer
}}
}}
Chlorine perchlorate is a chemical compound with the formula {{chem2|Cl2O4}}. This chlorine oxide is an asymmetric oxide, with one chlorine atom in +1 oxidation state and the other +7, with proper formula {{chem2|Cl\sO\sClO3}}. It is produced by the photodimerization of chlorine dioxide ({{chem2|ClO2}}) at room temperature by 436 nm ultraviolet light:{{cite journal|title=Chlorine perchlorate a major photolysis product of chlorine dioxide|journal=J. Phys. Chem.|year=1982|volume=86|issue=24|pages=4653–4655|doi=10.1021/j100221a001|author1=A. J. Schell-Sorokin |author2=D. S. Bethune |author3=J. R. Lankard |author4=M. M. T. Loy |author5=P. P. Sorokin}}{{cite journal|title=Ultraviolet spectrum of chlorine perchlorate|journal=J. Phys. Chem.|year=1988|volume=92|issue=2|pages=563–564|doi=10.1021/j100313a062|author1=M. I. Lopez |author2=J. E. Sicre}}{{Cite journal|last1=Rao|first1=Balaji|last2=Anderson|first2=Todd A.|last3=Redder|first3=Aaron|last4=Jackson|first4=W. Andrew|date=2010-04-15|title=Perchlorate Formation by Ozone Oxidation of Aqueous Chlorine/Oxy-Chlorine Species: Role of ClxOy Radicals|journal=Environmental Science & Technology|volume=44|issue=8|pages=2961–2967|doi=10.1021/es903065f|pmid=20345093|bibcode=2010EnST...44.2961R |issn=0013-936X}}
:{{chem2|2 ClO2 → ClOClO3}}
Chlorine perchlorate can also be made by the following reaction at −45 °C.
:{{chem2|CsClO4 + ClOSO2F → CsSO3F + ClOClO3}}
Properties
Chlorine perchlorate is a pale greenish liquid. It is less stable than {{chem2|ClO2}} (chlorine dioxide){{cn|date=July 2020}} and decomposes at room temperature to give {{chem2|O2}} (oxygen), {{chem2|Cl2}} (chlorine) and {{chem2|Cl2O6}} (dichlorine hexoxide):
:{{chem2|2 ClOClO3 → O2 + Cl2 + Cl2O6}}
Chlorine perchlorate reacts with metal chlorides to form chlorine and the corresponding anhydrous perchlorate:
:{{chem2|CrO2Cl2 + 2 ClOClO3 → 2 Cl2 + CrO2(ClO4)2}}
:{{chem2|TiCl4 + 4 ClOClO3 → 4 Cl2 + Ti(ClO4)4}}
Reactions
| class="wikitable" | ||
| Reactant | Conditions | Products |
|---|---|---|
| — | Heat | dichlorine hexoxide (80%), chlorine dioxide, chlorine, oxygen |
| — | Ultraviolet light | dichlorine heptoxide, chlorine, oxygen |
| caesium iodide | −45 °C | caesium tetraperchloratoiodate(III) {{chem2|Cs+[I(OClO3)4]-}}{{NoteTag|name=note1|{{chem2|Cs+[I(OClO3)4]-}} is a pale yellow salt which is stable at room temperature. It has a square {{chem2|IO4}} unit.}} |
| {{chem2|ClOSO2F}} or ClF | — | {{chem2|M+ClO4-}} (M = Cs or nitronium){{NoteTag|name=note2|{{chem2|M+ClO4-}} (M {{=}} Cs or {{chem2|[NO2]}}) reacts with {{chem2|BrOSO2F}} at −20 °C and produces bromine perchlorate ({{chem2|BrOClO3}}). Bromine perchlorate then reacts with hydrogen bromide (HBr) at −70 °C and produces elemental bromine ({{chem2|Br2}}) and perchloric acid ({{chem2|HClO4}}).}} |
| bromine | −45 °C | bromine perchlorate ({{chem2|BrOClO3}}){{NoteTag|name=note2}} |
| iodine(0.33 mol) | −50 °C | iodine(III) perchlorate {{chem2|I(OClO3)3}}{{NoteTag|name=note3|The last{{cite journal|doi=10.1070/RC1988v057n11ABEH003410|journal=Russian Chemical Reviews|publisher=Turpion|title=The synthesis and properties of covalent organic perchlorates|volume=57|issue=11|year=1988|page=1047|first1=N. S.|last1=Zefirov|first2=V. V.|last2=Zedankin|first3=A. S.|last3=Koz'min}} Translated from Uspekhi Khimii volume 57 (1988), pp. 1815-1839. attempt to form iodine monoperchlorate ({{chem2|IOClO3}}) occurred in 1972,{{cite journal|doi=10.1021/ic50113a047|page=1684|journal=Inorganic Chemistry|volume=11|issue=7|year=1972|first1=Karl O.|last1=Christe|first2=Carl J.|last2=Schack|orig-date=20 September 1971|title=Iodine tris(perch1orate) and cesium tetrakis(perchlorato)iodate(III)}} and even at low temperatures yielded instead the triperchlorate. On warming, the latter then decomposes to iodate.}} |
Notes
{{NoteFoot}}
References
{{Reflist}}
{{Perchlorates}}
{{Chlorine compounds}}
{{oxygen compounds}}