Iodine
Hydrogen iodide

The simplest compound of iodine is hydrogen iodide, HI. It is a colourless gas that reacts with oxygen to give water and iodine. Although it is useful in iodination reactions in the laboratory, it does not have large-scale industrial uses, unlike the other hydrogen halides. Commercially, it is usually made by reacting iodine with hydrogen sulfide or hydrazine:

At room temperature, it is a colourless gas, like all of the hydrogen halides except hydrogen fluoride, since hydrogen cannot form strong hydrogen bonds to the large and only mildly electronegative iodine atom. It melts at −51.0 °C (−59.8 °F) and boils at −35.1 °C (−31.2 °F). It is an endothermic compound that can exothermically dissociate at room temperature, although the process is very slow unless a catalyst is present: the reaction between hydrogen and iodine at room temperature to give hydrogen iodide does not proceed to completion. The H–I bond dissociation energy is likewise the smallest of the hydrogen halides, at 295 kJ/mol.

Aqueous hydrogen iodide is known as hydroiodic acid, which is a strong acid. Hydrogen iodide is exceptionally soluble in water: one litre of water will dissolve 425 litres of hydrogen iodide, and the saturated solution has only four water molecules per molecule of hydrogen iodide. Commercial so-called "concentrated" hydroiodic acid usually contains 48–57% HI by mass; the solution forms an azeotrope with boiling point 126.7 °C (260.1 °F) at 56.7 g HI per 100 g solution. Hence hydroiodic acid cannot be concentrated past this point by evaporation of water. Unlike gaseous hydrogen iodide, hydroiodic acid has major industrial use in the manufacture of acetic acid by the Cativa process.

Unlike hydrogen fluoride, anhydrous liquid hydrogen iodide is difficult to work with as a solvent, because its boiling point is low, it has a small liquid range, its permittivity is low and it does not dissociate appreciably into H I and HI ions – the latter, in any case, are much less stable than the bifluoride ions (HF) due to the very weak hydrogen bonding between hydrogen and iodine, though its salts with very large and weakly polarising cations such as Cs and NR (R = Me, Et, Bu) may still be isolated. Anhydrous hydrogen iodide is a poor solvent, able to dissolve only small molecular compounds such as nitrosyl chloride and phenol, or salts with very low lattice energies such as tetraalkylammonium halides.
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