Tetrachloroiodic acid
| Identifiers | |
|---|---|
3D model (JSmol)
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| Properties | |
| HICl4 | |
| Appearance | Orange crystals (hydrate) |
| Melting point | 19 °C (66 °F; 292 K) (hydrate) |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references
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Tetrachloroiodic acid is an inorganic compound with the formula HICl4, which acts the only example of a stable acid derived from a polyhalide. An orange crystalline tetrahydrate is known. No anhydrous tetrachloroiodic acid is known to exist; rather, it is isolated as hydronium salts of the tetrachloroiodate anion. It is unstable in air.[1]
Synthesis
Tetrachloroiodic acid may be formed by dissolution of iodine trichloride in concentrated hydrochloric acid:[2][3]
- ICl3 + HCl → HICl4
Tetrachloroiodic acid may also be made by adding hydrochloric acid to iodates or periodates, or by passing chlorine through a solution of iodine in concentrated hydrochloric acid,
- I2 + 3 Cl2 + 2 HCl + 4 H2O → 2 HICl4
although it quickly decomposes into iodine and iodate when introduced into less acidic conditions.
Physical properties
Tetrachloroiodic acid forms a crystal hydrate which has orange crystals that are unstable in air and melt by dissolving in their own water of crystallization at 19 °C. Crystals of HICl4·4H2O contain square planar tetrachloroiodate anions associated with various hydronium cations, such as H5O+2,[3] showing structural similarities to the hydrates of other chloride-based inorganic acids, most notably HAuCl4·4H2O.
Related compounds
Hydrates of the sodium and potassium salts of the tetrachloroiodate anion (ICl−4) have been isolated, along with tetrachloroiodates of various alkaloids.[3][4] The lighter alkali tetrachloroiodates tend to lose iodine over time, in the form of iodine trichloride:
- KICl4 ⇌ KCl + ICl3
Caesium tetrachloroiodate rapidly crashes out of solution when caesium chloride and aqueous potassium tetrachloroiodate are mixed. It is stable at room temperature and relatively insoluble in water.
The potassium salt of the corresponding iodine(I) anion, dichloroiodate (ICl−2), has been isolated.[5] Caesium dichloroiodate is formed from the thermal decomposition of CsICl4.[6] ICl−2 solutions are described as being dark orange, while ICl−4 solutions are yellow. The ICl−2 anion is linear.[7]
See also
References
- ^ Guber, F.; Shmajser, M. (1985). "Tetrachloroiodic (3) acid HICl4x4H2O". Handbook on inorganic synthesis. V. 2. p. 346. Archived from the original on 11 August 2024.
- ^ Brauer, Georg, ed. (2012) [1st pub. 1963]. "Tetrachloroiodic acid HICl4·4H2O". Handbook of Preparative Inorganic Chemistry. Vol. 1. Elsevier. p. 299. ISBN 978-0-323-16127-5.
- ^ a b c Bateman, Richard J.; Bateman, Linda R. (1972). "Solid-state structure, nuclear quadrupole resonance spectrum, and the resultant symmetry implications for tetrachloroiodic acid tetrahydrate". Journal of the American Chemical Society. 94 (4): 1130–1134. Bibcode:1972JAChS..94.1130B. doi:10.1021/ja00759a017.
- ^ Chattaway, Frederick Daniel; Parkes, George David (1930). "CXXIV.—Tetrachloroiodides of the alkaloids". Journal of the Chemical Society (Resumed): 1003–1005. doi:10.1039/jr9300001003.
- ^ Lima, Edson L. S.; Garden, Simon J. (15 April 2003). "Potassium Dichloroiodate". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289x.rn00249.
- ^ Huvenne, J.P.; Boniface, B.; Wallart, F.; Legrand, P. (December 1975). "Etude structurale et vibrationnelle de CsICl4 solide par diffraction X et diffusion Raman. Interpretation des spectres d'absorption en i.r. lointain" [Structural and vibrational study of solid CsICl4 by X-ray diffraction and Raman scattering. Interpretation of far-infrared absorption spectra.]. Spectrochimica Acta Part A (in French). 31 (12): 1937–1943. doi:10.1016/0584-8539(75)80250-9.
- ^ Soled, S.; Carpenter, G. B. (1 October 1973). "The crystal structures of KICl2 and KICl2.H2O". Acta Crystallographica Section B. 29 (10): 2104–2109. doi:10.1107/s0567740873006187.