Properties
Iodine is the fourth halogen, being a member of group 17 in the periodic table, below fluorine, chlorine, and bromine; since astatine and tennessine are radioactive, iodine is the heaviest stable halogen. Iodine has an electron configuration of [Kr]5s24d105p5, with the seven electrons in the fifth and outermost shell being its valence electrons. Like the other halogens, it is one electron short of a full octet and is hence an oxidising agent, reacting with many elements in order to complete its outer shell, although in keeping with periodic trends, it is the weakest oxidising agent among the stable halogens: it has the lowest electronegativity among them, just 2.66 on the Pauling scale (compare fluorine, chlorine, and bromine at 3.98, 3.16, and 2.96 respectively; astatine continues the trend with an electronegativity of 2.2, while that of tennessine is unknown). Elemental iodine hence forms diatomic molecules with chemical formula I2, where two iodine atoms share a pair of electrons in order to each achieve a stable octet for themselves; at high temperatures, these diatomic molecules reversibly dissociate a pair of iodine atoms. Similarly, the iodide anion, I−, is the strongest reducing agent among the stable halogens, being the most easily oxidised back to diatomic I2. (Astatine goes further, being indeed unstable as At− and readily oxidised to At0 or At+.)
The halogens darken in colour as the group is descended: fluorine is a very pale yellow, chlorine is greenish-yellow, bromine is reddish-brown, and iodine is violet.
Elemental iodine is slightly soluble in water, with one gram dissolving in 3450 mL at 20 °C and 1280 mL at 50 °C; potassium iodide may be added to increase solubility via formation of triiodide ions, among other polyiodides. Nonpolar solvents such as hexane and carbon tetrachloride provide a higher solubility. Polar solutions, such as aqueous solutions, are brown, reflecting the role of these solvents as Lewis bases; on the other hand, nonpolar solutions are violet, the colour of iodine vapour. Charge-transfer complexes form when iodine is dissolved in polar solvents, hence changing the colour. Iodine is violet when dissolved in carbon tetrachloride and saturated hydrocarbons but deep brown in alcohols and amines, solvents that form charge-transfer adducts.
The density, and the melting and boiling points of iodine follow the trend across all of the halogens of increasing with atomic number. Among the stable halogens, iodine has the largest electron cloud among them that is the most easily polarised, resulting in its molecules having the strongest Van der Waals interactions among the stable halogens. Similarly, iodine is the least volatile of the stable halogens, though the solid still can be observed to give off purple vapour. Due to this property iodine is commonly used to demonstrate sublimation directly from solid to gas, which gives rise to a misconception that it does not melt in atmospheric pressure. Because it has the largest atomic radius among the stable halogens, iodine has the lowest first ionisation energy, lowest electron affinity, lowest electronegativity and lowest reactivity of the stable halogens.
The interhalogen bond in diiodine is the weakest of all the stable halogens. As such, 1% of a sample of gaseous iodine at atmospheric pressure is dissociated into iodine atoms at 575 °C. Temperatures greater than 750 °C are required for fluorine, chlorine, and bromine to dissociate to a similar extent. Most bonds to iodine are weaker than the analogous bonds to the lighter halogens. Gaseous iodine is composed of I2 molecules with an I–I bond length of 266.6 pm. The I–I bond is one of the longest single bonds known. It is even longer (271.5 pm) in solid orthorhombic crystalline iodine, which has the same crystal structure as chlorine and bromine. (The record is held by iodine's neighbour xenon: the Xe–Xe bond length is 308.71 pm.) As such, within the iodine molecule, significant electronic interactions occur with the two next-nearest neighbours of each atom, and these interactions give rise, in bulk iodine, to a shiny appearance and semiconducting properties. Iodine is a two-dimensional semiconductor with a band gap of 1.3 eV (125 kJ/mol): it is a semiconductor in the plane of its crystalline layers and an insulator in the perpendicular direction.