Iodine is a chemical element with the symbol I and atomic number 53. The heaviest of the stable halogens, it exists as a semi-lustrous, non-metallic solid at standard conditions that melts to form a deep violet liquid at 114 °C (237 °F), and boils to a violet gas at 184 °C (363 °F). The element was discovered by the French chemist Bernard Courtois in 1811 and was named two years later by Joseph Louis Gay-Lussac, after the Ancient Greek Ιώδης ‘violet-coloured’.
Iodine occurs in many oxidation states, including iodide (I−), iodate (IO−
3), and the various periodate anions. It is the least abundant of the stable halogens, being the sixty-first most abundant element. It is the heaviest essential mineral nutrient. Iodine is essential in the synthesis of thyroid hormones. Iodine deficiency affects about two billion people and is the leading preventable cause of intellectual disabilities.
The dominant producers of iodine today are Chile and Japan. Iodine and its compounds are primarily used in nutrition. Due to its high atomic number and ease of attachment to organic compounds, it has also found favour as a non-toxic radiocontrast material. Because of the specificity of its uptake by the human body, radioactive isotopes of iodine can also be used to treat thyroid cancer. Iodine is also used as a catalyst in the industrial production of acetic acid and some polymers.
It is on the World Health Organization’s List of Essential Medicines.
Iodine is the fourth halogen, being a member of group 17 in the periodic table, below fluorine, chlorine, and bromine; it is the heaviest stable member of its group. (The fifth and sixth halogens, the radioactive astatine and tennessine, are not well-studied due to their expense and inaccessibility in large quantities, but appear to show various unusual properties for the group due to relativistic effects.) Iodine has an electron configuration of [Kr]4d105s25p5, 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). 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 color 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 melting and boiling points of iodine are the highest among the halogens, conforming to the increasing trend down the group, since 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 halogens. Similarly, iodine is the least volatile of the halogens, though the solid still can be observed to give off purple vapor. 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 halogens, iodine has the lowest first ionisation energy, lowest electron affinity, lowest electronegativity and lowest reactivity of the halogens.
The interhalogen bond in diiodine is the weakest of all the 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.
About half of all produced iodine goes into various organoiodine compounds, another 15% remains as the pure element, another 15% is used to form potassium iodide, and another 15% for other inorganic iodine compounds. Among the major uses of iodine compounds are catalysts, animal feed supplements, stabilisers, dyes, colourants and pigments, pharmaceutical, sanitation (from tincture of iodine), and photography; minor uses include smog inhibition, cloud seeding, and various uses in analytical chemistry.
The iodide and iodate anions are often used for quantitative volumetric analysis, for example in iodometry. Iodine and starch form a blue complex, and this reaction is often used to test for either starch or iodine and as an indicator in iodometry. The iodine test for starch is still used to detect counterfeit banknotes printed on starch-containing paper.
The iodine value is the mass of iodine in grams that is consumed by 100 grams of a chemical substance typically fats or oils. Iodine numbers are often used to determine the amount of unsaturation in fatty acids. This unsaturation is in the form of double bonds, which react with iodine compounds. In biology, linoleic acid (C18:2 n-6), omega-6 and alpha-linolenic (C18:3 n-3) omega-3, arachidonic acid (AA) – omega-6 (C20: 4n-6), and docosahexaenoic acid (DHA) – omega-3 (C22:6n-3) synthesised with iodine iodolipids developed among cell membranes during the evolution of life, important in the mechanism of apoptosis, carcinogenesis and degenerative diseases.
Potassium tetraiodomercurate(II), K2HgI4, is also known as Nessler’s reagent. It is often used as a sensitive spot test for ammonia. Similarly, Cu2HgI4 is used as a precipitating reagent to test for alkaloids. Aqueous alkaline iodine solution is used in the iodoform test for methyl ketones.
The spectrum of the iodine molecule, I2, consists of (not exclusively) tens of thousands of sharp spectral lines in the wavelength range 500–700 nm. It is therefore a commonly used wavelength reference (secondary standard). By measuring with a spectroscopic Doppler-free technique while focusing on one of these lines, the hyperfine structure of the iodine molecule reveals itself. A line is now resolved such that either 15 components (from even rotational quantum numbers, Jeven), or 21 components (from odd rotational quantum numbers, Jodd) are measurable.
Cesium iodide and thallium-doped sodium iodide are used in crystal scintillators for the detection of gamma rays. The efficiency is high and energy dispersive spectroscopy is possible, but the resolution is rather poor.
In early 2021, the French group ThrustMe performed an in-orbit demonstration of an electric-powered ion thruster for spacecraft, where iodine was used in lieu of xenon as the source of plasma, in order to generate thrust by accelerating ions with an electrostatic field.
Propulsion systems employing iodine as the propellant can be built more compactly, with less mass (and cost), and operate more efficiently than the gridded ion thrusters that were utilised to propel previous spacecraft, such as Japan’s Hayabusa probes, ESA’s GOCE satellite, or NASA’s DART mission, all of which used xenon as the reaction mass. Yet iodine’s atomic weight is only 3.3% less than that of xenon, while its first two ionisation energies average 12% less; together, these make iodine ions a promising substitute.
Use of iodine should allow more widespread application of ion-thrust technology, particularly with smaller-scale space vehicles. According to the European Space Agency, “This small but potentially disruptive innovation could help to clear the skies of space junk, by enabling tiny satellites to self-destruct cheaply and easily at the end of their missions, by steering themselves into the atmosphere where they would burn up.”
Elemental iodine is used as an antiseptic either as the element, or as the water-soluble triiodide anion I3− generated in situ by adding iodide to poorly water-soluble elemental iodine (the reverse chemical reaction makes some free elemental iodine available for antisepsis). Elemental iodine may also be used to treat iodine deficiency.
In the alternative, iodine may be produced from iodophors, which contain iodine complexed with a solubilizing agent (the iodide ion may be thought of loosely as the iodophor in triiodide water solutions). Examples of such preparations include:
- Tincture of iodine: iodine in ethanol, or iodine and sodium iodide in a mixture of ethanol and water.
- Lugol’s iodine: iodine and iodide in water alone, forming mostly triiodide. Unlike tincture of iodine, Lugol’s iodine has a minimised amount of the free iodine (I2) component.
- Povidone iodine (an iodophor).
- Iodine-V: iodine (I2) and fulvic acid form a clathrate compound (iodine molecules are “caged” by fulvic acid in this host-guest complex). A water-soluble, solid, stable, crystalline complex. Unlike other iodophors, Iodine-V only contains iodine in molecular (I2) form.
The antimicrobial action of iodine is quick and works at low concentrations, and thus it is used in operating theatres. Its specific mode of action is unknown. It penetrates into microorganisms and attacks particular amino acids (such as cysteine and methionine), nucleotides, and fatty acids, ultimately resulting in cell death. It also has an antiviral action, but nonlipid viruses and parvoviruses are less sensitive than lipid enveloped viruses. Iodine probably attacks surface proteins of enveloped viruses, and it may also destabilise membrane fatty acids by reacting with unsaturated carbon bonds.
In medicine, a saturated solution of potassium iodide is used to treat acute thyrotoxicosis. It is also used to block uptake of iodine-131 in the thyroid gland (see isotopes section above), when this isotope is used as part of radiopharmaceuticals (such as iobenguane) that are not targeted to the thyroid or thyroid-type tissues.
Iodine-131 (usually as iodide) is a component of nuclear fallout, and is particularly dangerous owing to the thyroid gland’s propensity to concentrate ingested iodine and retain it for periods longer than this isotope’s radiological half-life of eight days. For this reason, people at risk of exposure to environmental radioactive iodine (iodine-131) in fallout may be instructed to take non-radioactive potassium iodide tablets. The typical adult dose is one 130 mg tablet per 24 hours, supplying 100 mg (100,000 micrograms) of ionic iodine. (The typical daily dose of iodine for normal health is of order 100 micrograms; see “Dietary Intake” below.) Ingestion of this large dose of non-radioactive iodine minimises the uptake of radioactive iodine by the thyroid gland.
As an element with high electron density and atomic number, iodine absorbs X-rays weaker than 33.3 keV due to the photoelectric effect of the innermost electrons. Organoiodine compounds are used with intravenous injection as X-ray radiocontrast agents. This application is often in conjunction with advanced X-ray techniques such as angiography and CT scanning. At present, all water-soluble radiocontrast agents rely on iodine.
The production of ethylenediamine dihydroiodide, provided as a nutritional supplement for livestock, consumes a large portion of available iodine. Another significant use is a catalyst for the production of acetic acid by the Monsanto and Cativa processes. In these technologies, which support the world’s demand for acetic acid, hydroiodic acid converts the methanol feedstock into methyl iodide, which undergoes carbonylation. Hydrolysis of the resulting acetyl iodide regenerates hydroiodic acid and gives acetic acid.
Inorganic iodides find specialised uses. Titanium, zirconium, hafnium, and thorium are purified by the van Arkel–de Boer process, which involves the reversible formation of the tetraiodides of these elements. Silver iodide is a major ingredient to traditional photographic film. Thousands of kilograms of silver iodide are used annually for cloud seeding to induce rain.
The iodine clock reaction (in which iodine also serves as a test for starch, forming a dark blue complex), is a popular educational demonstration experiment and example of a seemingly oscillating reaction (it is only the concentration of an intermediate product that oscillates).
Although iodine has widespread roles in many species, agents containing it can exert a differential effect upon different species in an agricultural system. The growth of all strains of Fusarium verticillioides is significantly inhibited by an iodine-containing fungistatic (AJ1629-34EC) at concentrations that do not harm the crop. This might be a less toxic anti-fungal agricultural treatment due to its relatively natural chemistry.