Chlorine perchlorate

Chlorine perchlorate is a chemical compound with the formula Cl2O4. This chlorine oxide is an asymmetric oxide, with one chlorine atom in oxidation state +1 and the other +7, with proper formula ClOClO3. It is produced by the photolysis of chlorine dioxide at room temperature with 436 nm ultraviolet light:[2][3]

2 ClO2 → ClOClO3
Chlorine perchlorate
Names
IUPAC name
Chlorine perchlorate
Systematic IUPAC name
Chloro perchlorate[1]
Other names
Chlorine (I,VII) oxide
Dichlorine tetroxide
Identifiers
3D model (JSmol)
ChemSpider
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
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 can also be made the following reactions at −45 °C.

CsClO4 + ClOSO2F → Cs(SO3)F + ClOClO3

Chlorine perchlorate is a pale greenish liquid which decomposes at room temperature. IUPAC Name of this compound is chlorane trioxide (chloroxyoxy)

Properties

It is less stable than ClO2 and decomposes to O2, Cl2 and Cl2O6 at room temperature.

2 ClOClO3 → O2 + Cl2 + Cl2O6

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

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

Reactions[4]
chemicals react with chlorine perchlorateconditionsproducts
—heatdichlorine hexoxide(80%),chlorine dioxide,chlorine,oxygen
—ultraviolet raydichlorine heptoxide,chlorine,oxygen
caesium iodide-45℃Cs[I(OClO3)4][note 1]
ClOSO2F or ClFMClO4(M=Cs or NO2)[note 2]
bromine-45℃bromine perchlorate(BrOClO3)[note 2]
iodine(0.33mol)-50℃I(OClO3)3[note 3]

Notes：

  • 1.Cs[I(OClO3)4] is a pale yellow salt that is stable at room temperature. It has a square IO4 unit.
  • 2.MClO4(M=Cs or NO2) can react with BrOSO2F at -20℃ to produce bromine perchlorate(BrOClO3). Bromine perchlorate can react with hydrogen bromide in -70℃,and produce elemental bromine and perchloric acid.
  • 3.As of now, attempts to form iodine(I) perchlorate(IOClO3) have all failed. The iodine atom oxidizes to +3 oxidation state immediately.

References
  1. "Chloro Perchlorate - PubChem Public Chemical Database". The PubChem Project. USA: National Center for Biotechnology Information.
  2. 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.
  3. M. I. Lopez; J. E. Sicre (1988). "Ultraviolet spectrum of chlorine perchlorate". J. Phys. Chem. 92 (2): 563–564. doi:10.1021/j100313a062.
  4. 《无机化学》丛书.第六卷.P343.(c)卤素高氯酸盐.张青莲 主编
Compounds containing perchlorate group
HClO4 He
LiClO4 Be(ClO4)2 B(ClO
4)−
4
B(ClO4)3		 ROClO3 N(ClO4)3
NH4ClO4
NOClO4		 O FClO4 Ne
NaClO4 Mg(ClO4)2 Al(ClO4)3 Si P S ClO−
4
ClOClO3
Cl2O7		 Ar
KClO4 Ca(ClO4)2 Sc(ClO4)3 Ti(ClO4)4 VO(ClO4)3
VO2(ClO4)		 Cr(ClO4)3 Mn(ClO4)2 Fe(ClO4)3 Co(ClO4)2,
Co(ClO4)3		 Ni(ClO4)2 Cu(ClO4)2 Zn(ClO4)2 Ga(ClO4)3 Ge As Se Br Kr
RbClO4 Sr(ClO4)2 Y(ClO4)3 Zr(ClO4)4 Nb(ClO4)5 Mo Tc Ru Rh(ClO4)3 Pd(ClO4)2 AgClO4 Cd(ClO4)2 In(ClO4)3 Sn(ClO4)4 Sb TeO(ClO4)2 I Xe
CsClO4 Ba(ClO4)2   Hf(ClO4)4 Ta(ClO4)5 W Re Os Ir Pt Au Hg2(ClO4)2,
Hg(ClO4)2		 Tl(ClO4),
Tl(ClO4)3		 Pb(ClO4)2 Bi(ClO4)3 Po At Rn
FrClO4 Ra   Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
↓
La Ce(ClO4)x Pr Nd Pm Sm(ClO4)3 Eu(ClO4)3 Gd(ClO4)3 Tb(ClO4)3 Dy(ClO4)3 Ho(ClO4)3 Er(ClO4)3 Tm(ClO4)3 Yb(ClO4)3 Lu(ClO4)3
Ac Th(ClO4)4 Pa UO2(ClO4)2 Np Pu Am Cm Bk Cf Es Fm Md No Lr
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