Chlorine perchlorate

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Chlorine perchlorate
Names
IUPAC name
Chloro perchlorate[1]
Systematic IUPAC name
Chloro perchlorate[1]
Other names
Chlorine(I,VII) oxide
Dichlorine tetroxide
Identifiers
3D model (
JSmol
)
ChemSpider
  • InChI=1S/Cl2O4/c1-6-2(3,4)5 ☒N
    Key: JRONPIZRZBBOBR-UHFFFAOYSA-N ☒N
  • ClO[Cl](=O)(=O)=O
Properties
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)
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).
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Chlorine perchlorate is a

photodimerization of chlorine dioxide (ClO2) at room temperature by 436 nm ultraviolet light:[2][3][4]

2ClO2 → ClOClO3

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

CsClO4 + ClOSO2F → Cs(SO3)F + 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):

2ClOClO3 → O2 + Cl2 + Cl2O6

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

CrO2Cl2 + 2ClOClO3 → 2Cl2 + CrO2(ClO4)2
TiCl4 + 4ClOClO3 → 4Cl2 + Ti(ClO4)4
2AgCl + 2 ClOClO3 → 2AgClO4 + Cl2

Reactions

Reactant Conditions Products
Heat dichlorine hexoxide (80%), chlorine dioxide, chlorine, oxygen
Ultraviolet light
dichlorine heptoxide, chlorine, oxygen[4]
caesium iodide −45 °C Cs[I(OClO3)4][note 1]
ClOSO2F or ClF MClO4(M =
bromine −45 °C bromine perchlorate (BrOClO3)[note 2]
iodine(0.33 mol) −50 °C 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. ^ a b MClO4 (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[5] attempt to form iodine monoperchlorate (IOClO3) occurred in 1972,[6] and even at low temperatures yielded instead the triperchlorate. On warming, the latter then decomposes to iodate.

References

  1. ^ a b "Chloro Perchlorate - PubChem Public Chemical Database". The PubChem Project. USA: National Center for Biotechnology Information.
  2. .
  3. .
  4. ^ .
  5. volume 57 (1988), pp. 1815-1839.
  6. .