Chlorine perchlorate

Chlorine perchlorate

Names
IUPAC name Chlorine perchlorate
Systematic IUPAC name Chloro perchlorate[1]
Other names Chlorine (I,VII) oxide Dichlorine tetroxide
Identifiers
CAS Number	27218-16-2
3D model (Jmol)	Interactive image
ChemSpider	147540
PubChem	168667
InChI InChI=1S/Cl2O4/c1-6-2(3,4)5 Key: JRONPIZRZBBOBR-UHFFFAOYSA-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
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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Infobox references

Chlorine perchlorate is the 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 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.

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 forming anhydrous perchlorates:

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

TiCl₄ + 4 ClOClO₃ → 4 Cl₂ + Ti(ClO₄)₄

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.

Salts and the ester of the perchlorate ion
HClO4																	He
LiClO4	Be(ClO4)2											B(ClO4)4^−	ROClO3	N(ClO4)3 NH4ClO4	O	FClO4	Ne
NaClO4	Mg(ClO4)2											Al(ClO4)3	Si	P	S	ClO4^− ClOClO3 Cl2O7	Ar
KClO4	Ca(ClO4)2	Sc(ClO4)3	Ti(ClO4)4	VO(ClO4)3	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	Zr	Nb	Mo	Tc	Ru	Rh	Pd(ClO4)2	AgClO4	Cd(ClO4)2	In	Sn	Sb	Te	I	Xe
CsClO4	Ba(ClO4)2		Hf	Ta	W	Re	Os	Ir	Pt	Au	Hg2(ClO4)2, Hg(ClO4)2	Tl(ClO4)3	Pb(ClO4)2	Bi(ClO4)3	Po	At	Rn
Fr	Ra		Rf	Db	Sg	Bh	Hs	Mt	Ds	Rg	Cn	Nh	Fl	Mc	Lv	Ts	Og
		↓
		La	Ce(ClO4)x	Pr	Nd	Pm	Sm	Eu	Gd	Tb	Dy	Ho	Er	Tm	Yb	Lu
		Ac	Th	Pa	UO2(ClO4)2	Np	Pu	Am	Cm	Bk	Cf	Es	Fm	Md	No	Lr