Diiodine tetroxide

Diiodine tetroxide
IUPAC name	iodosyl iodate
Identifiers
CAS number	1024652-24-1
PubChem	54579881
SMILES	O=IOI(=O)=O
Properties
Molecular formula	2O4
Molar mass	317.78 g mol-1
Density	2.57
	Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)

Diiodine tetraoxide, I₂O₄, is a chemical compound of oxygen and iodine. It belongs to the class of iodine oxides, and is a mixed oxide, consisting of iodine(III) and iodine(V) oxidation states.

Synthesis

The oxide is formed by the reaction of hot concentrated sulfuric acid on iodic acid for several days.^[1]

3HIO
3 → I
2O
4 + HIO
4 + H
2O

It is formed from diiodine pentoxide and iodine in concentrated sulfuric acid or iodosyl sulfate (IO)₂SO₄ added to water:^[2]

4(IO)
2SO
4 + 4H
2O → I
2O
4 + I
2 + 4H
2SO
4

Physical properties

Diiodine tetraoxide is a yellow, granular powder. At temperatures above 85 °C it decomposes to diiodine pentoxide and iodine:^[1]

5I
2O
4 → 4I
2O
5 + I
2

This process is even faster at 135 °C. It dissolves in hot water to form iodate and iodide.^[1] Structurally, the compound is an iodyl iodite O₂I-OIO (iodine(V,III) oxide)^[1] with bent I^VO₂ units (I–O distances 1.80 and 1.85 Å; ∠OIO angle 97°) and bent I^IIIO₂ units (IO distances 1.93 Å, OIO angle 95.8°). Both units are linked via I—O—I bridges to form polymeric zigzag chains (I₂O₄)_x.^[1]

Diiodine tetraoxide has a monoclinic crystal structure with the space group P2₁/c (space group number 14). Unit cell dimensions are a = 8.483 b = 6.696 c = 8.333 Å and β = 124.69°. Unit cell volume = 389.15 Å³. Z = 4. Density is 2.57 Mg/m³^[2]^[3]

Reactions

Diiodine tetroxide oxidises hydrochloric acid:^[4]

I
2O
4 + 8H+
+ 8Cl−
→ 2ICl + 4H
2O + 3Cl
2

References

↑ ^1.0 ^1.1 ^1.2 ^1.3 ^1.4 Holleman-Wiberg inorganic chemistry. San Diego, Calif. London: Academic. 2001. pp. 465–466. ISBN 0123526515.
↑ ^2.0 ^2.1 Fjellvåg, Helmer; Kjekshus, Arne; Persson, Ingmar; Figgis, Brian N.; Liaaen-Jensen, Synnøve; Balzarini, Jan; Fransson, Bengt; Ragnarsson, Ulf; Francis, George W. (1994). "The Crystal Structure of I2O4 and its Relations to Other Iodine--Oxygen-Containing Compounds". Acta Chemica Scandinavica. 48: 815–822. doi:10.3891/acta.chem.scand.48-0815.
↑ Wu, Zhongqing; Kalia, Rajiv K.; Nakano, Aiichiro; Vashishta, Priya (28 May 2011). "First-principles calculations of the structural and dynamic properties, and the equation of state of crystalline iodine oxides I2O4, I2O5, and I2O6". The Journal of Chemical Physics. 134 (20). doi:10.1063/1.3590278. PMID 21639450.
↑ Advances in Inorganic Chemistry and Radiochemistry. Academic Press. 1 January 1963. p. 77-78. ISBN 978-0-08-057854-5.

^[1]

↑ William M. Haynes, ed. (2014). CRC Handbook of Chemistry and Physics. CRC Press. p. S.4-67. ISBN 978-1482208689.

[hwic-1] 1.0 ^1.1 ^1.2 ^1.3 ^1.4 Holleman-Wiberg inorganic chemistry. San Diego, Calif. London: Academic. 2001. pp. 465–466. ISBN 0123526515.

[fjell-2] 2.0 ^2.1 Fjellvåg, Helmer; Kjekshus, Arne; Persson, Ingmar; Figgis, Brian N.; Liaaen-Jensen, Synnøve; Balzarini, Jan; Fransson, Bengt; Ragnarsson, Ulf; Francis, George W. (1994). "The Crystal Structure of I2O4 and its Relations to Other Iodine--Oxygen-Containing Compounds". Acta Chemica Scandinavica. 48: 815–822. doi:10.3891/acta.chem.scand.48-0815.

[3] Wu, Zhongqing; Kalia, Rajiv K.; Nakano, Aiichiro; Vashishta, Priya (28 May 2011). "First-principles calculations of the structural and dynamic properties, and the equation of state of crystalline iodine oxides I2O4, I2O5, and I2O6". The Journal of Chemical Physics. 134 (20). doi:10.1063/1.3590278. PMID 21639450.

[4] Advances in Inorganic Chemistry and Radiochemistry. Academic Press. 1 January 1963. p. 77-78. ISBN 978-0-08-057854-5.

[5] William M. Haynes, ed. (2014). CRC Handbook of Chemistry and Physics. CRC Press. p. S.4-67. ISBN 978-1482208689.

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