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Iodine compounds
Iodine compounds are compounds containing the element iodine. Iodine can form compounds using multiple oxidation states. Iodine is quite reactive, but it is much less reactive than the other halogens. For example, while chlorine gas will halogenate carbon monoxide, nitric oxide, and sulfur dioxide (to phosgene, nitrosyl chloride, and sulfuryl chloride respectively), iodine will not do so. Furthermore, iodination of metals tends to result in lower oxidation states than chlorination or bromination; for example, rhenium metal reacts with chlorine to form rhenium hexachloride, but with bromine it forms only rhenium pentabromide and iodine can achieve only rhenium tetraiodide. By the same token, however, since iodine has the lowest ionisation energy among the halogens and is the most easily oxidised of them, it has a more significant cationic chemistry and its higher oxidation states are rather more stable than those of bromine and chlorine, for example in iodine heptafluoride.
The iodine molecule, I2, dissolves in CCl4 and aliphatic hydrocarbons to give bright violet solutions. In these solvents the absorption band maximum occurs in the 520 – 540 nm region and is assigned to a π* to σ* transition. When I2 reacts with Lewis bases in these solvents a blue shift in I2 peak is seen and the new peak (230 – 330 nm) arises that is due to the formation of adducts, which are referred to as charge-transfer complexes.
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 and boils at −35.1 °C. 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 at 56.7 g HI per 100 g solution. Hence hydroiodic acid cannot be concentrated past this point by evaporation of water.
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 dielectric constant is low and it does not dissociate appreciably into H2I+ and HI−
2 ions – the latter, in any case, are much less stable than the bifluoride ions (HF−
2) 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+
4 (R = Me, Et, Bun) 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.
Nearly all elements in the periodic table form binary iodides. The exceptions are decidedly in the minority and stem in each case from one of three causes: extreme inertness and reluctance to participate in chemical reactions (the noble gases); extreme nuclear instability hampering chemical investigation before decay and transmutation (many of the heaviest elements beyond bismuth); and having an electronegativity higher than iodine's (oxygen, nitrogen, and the first three halogens), so that the resultant binary compounds are formally not iodides but rather oxides, nitrides, or halides of iodine. (Nonetheless, nitrogen triiodide is named as an iodide as it is analogous to the other nitrogen trihalides.)
Given the large size of the iodide anion and iodine's weak oxidising power, high oxidation states are difficult to achieve in binary iodides, the maximum known being in the pentaiodides of niobium, tantalum, and protactinium. Iodides can be made by reaction of an element or its oxide, hydroxide, or carbonate with hydroiodic acid, and then dehydrated by mildly high temperatures combined with either low pressure or anhydrous hydrogen iodide gas. These methods work best when the iodide product is stable to hydrolysis; otherwise, the possibilities include high-temperature oxidative iodination of the element with iodine or hydrogen iodide, high-temperature iodination of a metal oxide or other halide by iodine, a volatile metal halide, carbon tetraiodide, or an organic iodide. For example, molybdenum(IV) oxide reacts with aluminium(III) iodide at 230 °C to give molybdenum(II) iodide. An example involving halogen exchange is given below, involving the reaction of tantalum(V) chloride with excess aluminium(III) iodide at 400 °C to give tantalum(V) iodide:
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Iodine compounds
Iodine compounds are compounds containing the element iodine. Iodine can form compounds using multiple oxidation states. Iodine is quite reactive, but it is much less reactive than the other halogens. For example, while chlorine gas will halogenate carbon monoxide, nitric oxide, and sulfur dioxide (to phosgene, nitrosyl chloride, and sulfuryl chloride respectively), iodine will not do so. Furthermore, iodination of metals tends to result in lower oxidation states than chlorination or bromination; for example, rhenium metal reacts with chlorine to form rhenium hexachloride, but with bromine it forms only rhenium pentabromide and iodine can achieve only rhenium tetraiodide. By the same token, however, since iodine has the lowest ionisation energy among the halogens and is the most easily oxidised of them, it has a more significant cationic chemistry and its higher oxidation states are rather more stable than those of bromine and chlorine, for example in iodine heptafluoride.
The iodine molecule, I2, dissolves in CCl4 and aliphatic hydrocarbons to give bright violet solutions. In these solvents the absorption band maximum occurs in the 520 – 540 nm region and is assigned to a π* to σ* transition. When I2 reacts with Lewis bases in these solvents a blue shift in I2 peak is seen and the new peak (230 – 330 nm) arises that is due to the formation of adducts, which are referred to as charge-transfer complexes.
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 and boils at −35.1 °C. 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 at 56.7 g HI per 100 g solution. Hence hydroiodic acid cannot be concentrated past this point by evaporation of water.
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 dielectric constant is low and it does not dissociate appreciably into H2I+ and HI−
2 ions – the latter, in any case, are much less stable than the bifluoride ions (HF−
2) 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+
4 (R = Me, Et, Bun) 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.
Nearly all elements in the periodic table form binary iodides. The exceptions are decidedly in the minority and stem in each case from one of three causes: extreme inertness and reluctance to participate in chemical reactions (the noble gases); extreme nuclear instability hampering chemical investigation before decay and transmutation (many of the heaviest elements beyond bismuth); and having an electronegativity higher than iodine's (oxygen, nitrogen, and the first three halogens), so that the resultant binary compounds are formally not iodides but rather oxides, nitrides, or halides of iodine. (Nonetheless, nitrogen triiodide is named as an iodide as it is analogous to the other nitrogen trihalides.)
Given the large size of the iodide anion and iodine's weak oxidising power, high oxidation states are difficult to achieve in binary iodides, the maximum known being in the pentaiodides of niobium, tantalum, and protactinium. Iodides can be made by reaction of an element or its oxide, hydroxide, or carbonate with hydroiodic acid, and then dehydrated by mildly high temperatures combined with either low pressure or anhydrous hydrogen iodide gas. These methods work best when the iodide product is stable to hydrolysis; otherwise, the possibilities include high-temperature oxidative iodination of the element with iodine or hydrogen iodide, high-temperature iodination of a metal oxide or other halide by iodine, a volatile metal halide, carbon tetraiodide, or an organic iodide. For example, molybdenum(IV) oxide reacts with aluminium(III) iodide at 230 °C to give molybdenum(II) iodide. An example involving halogen exchange is given below, involving the reaction of tantalum(V) chloride with excess aluminium(III) iodide at 400 °C to give tantalum(V) iodide: