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Chlorine perchlorate
Chemical compound

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:

2 ClO2 → ClOClO3

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

CsClO4 + ClOSO2F → CsSO3F + ClOClO3
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Properties

Chlorine perchlorate is a pale greenish liquid. It is less stable than ClO2 (chlorine dioxide) 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

ReactantConditionsProducts
—Heatdichlorine hexoxide (80%), chlorine dioxide, chlorine, oxygen
—Ultraviolet lightdichlorine heptoxide, chlorine, oxygen4
caesium iodide−45 °Ccaesium tetraperchloratoiodate(III) Cs+[I(OClO3)4]−5
ClOSO2F or ClF—M+ClO−4 (M = Cs or [NO2])6
bromine−45 °Cbromine perchlorate (BrOClO3)7
iodine(0.33 mol)−50 °Ciodine(III) perchlorate I(OClO3)38

Notes

References

  1. 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. /wiki/Doi_(identifier) ↩

  2. M. I. Lopez; J. E. Sicre (1988). "Ultraviolet spectrum of chlorine perchlorate". J. Phys. Chem. 92 (2): 563–564. doi:10.1021/j100313a062. /wiki/Doi_(identifier) ↩

  3. 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. /wiki/Bibcode_(identifier) ↩

  4. 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. /wiki/Bibcode_(identifier) ↩

  5. Cs+[I(OClO3)4]− is a pale yellow salt which is stable at room temperature. It has a square IO4 unit. /wiki/Salt_(chemistry) ↩

  6. 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). /wiki/Hydrogen_bromide ↩

  7. 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). /wiki/Hydrogen_bromide ↩

  8. 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. ↩